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October 2017

Backing
Infrared
Claims

Avobenzone
Exposed

Color Cosmetics
Level Up
Penetrating
Skin

WANT MORE?
Check out our digital edition exclusives!

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Untitled-1 1 2/12/16 2:21 PM
Cover Story Contents
October 2017 | Volume 132, number 9

Digital Edition Exclusives


8 [podcast] Lauder Eyes
Infrared Skin Damage
with Tom Mammone, Ph.D., Estée Lauder

18 From the Vault:


Photostability Enlightenment

36 [podcast] Age of Inflammation


with Larry Weiss, M.D., AOBiome

60 [podcast] Cosmetic
Influencer Insight

60
with Franziska Wandrey, Ph.D., Mibelle AG and
2017 Maison G. DeNavarre Young Scientist Winner

DE1 More Than Makeup


Multifunctionality Speaks Volumes by L. Doyle

DE5 Expanded Formulary: Face Care

In Every Issue
6 Editor’s Note: Discontinuity and
Your Inner Innovator by R. Grabenhofer

8 Industry Insight: Lauder Eyes Infrared


Skin Damage with Tom Mammone, Ph.D.

72 Ad Index

Market Intelligence

44 10 Technology Launches

18
Regulatory
12 Navigating a Brave New Nature
Cosmetics vs. Drugs
by R.H.R. Fichtner, A. Mazza, M.D., and
A. Schwanke

Research
18 In Light of Exposure
Understanding Avobenzone, Part I: Characterization
by P. Dutta and B. Wang

2 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

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23 2017

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Editor’s note | C&T ®
Contents EDITORIAL
Director Jo-El M. Grossman
Managing Editor Rachel L. Grabenhofer | 1-630-344-6072/rgrabenhofer@allured.com
Assistant Editors Jennifer Novoseletsky | 1-630-344-6045/jnovoseletsky@allured.com
Brooke Schleehauf | 630-344-6032/bschleehauf@allured.com
Lisa Schryver | 630-344-6068/lschryver@allured.com

36
Digital/Social Media Editor Audrey Latimer | 1-630-344-6067/alatimer@allured.com
Research Analyst Nicole Urbanowicz | 1-630-344-6053/nurbanowicz@allured.com

ADVERTISING SALES
Business Development Manager/
C&T Summit Exhibits
& Sponsorships Tom Harris | 1-201-445-4702/tharris@allured.com
Business Development Manager
Fragrance Paige Crist | 1-630-344-6060/pcrist@allured.com
Coordinator Kasia Smialkowski | 1-630-344-6025/ksmialkowski@allured.com

AUDIENCE DEVELOPMENT
Marketing Lead Marie Galvan
Marketing Specialist Alyssa Derby
Customer Service 1-888-355-5962/customerservice@cosmeticsandtoiletries.com

DESIGN
Graphic Design Manager Lisa Hede
Graphic Designer James Fergus
Production Manager Bryan Crowe

EVENTS
36 Breaking Through, Part II Group Show Director Maria Prior | 1-630-344-6065/mprior@allured.com
Chemical Ingredient Delivery Show Manager Brittany Peck | 1-630-344-6073/bpeck@allured.com

by M. Rule and H.I. Maibach, M.D. CORPORATE


Partner & President Janet Ludwig
Partner & CEO George Fox

Testing Controller
Digital Products Director
Linda Getner
Rose Southard
Executive Assistant Maria Romero
44 Are Your Sunscreens Infra-ready?
New In vitro Method Puts Data Behind the Claims OTHER ALLURED PRODUCTS
by E. Delamour, S. Miksa and D. Lutz Alluredbooks
Allured Business Media Cosmetics & Toiletries Bench Reference
1-630-653-2155 • fax 1-630-653-2192 Cosmetics & Toiletries magazine: Portuguese edition
336 Gundersen Drive, Suite A Cosmetics & Toiletries Summit

Formulating Carol Stream, IL 60188-2403 USA


www.Allured.com
GCI (Global Cosmetic Industry) magazine
Skin Inc. magazine
Face & Body Midwest Spa Expo and Conference
Face & Body Northern California Spa Expo and Conference
60 Leveling Up Face & Body Southeast Spa Expo and Conference
Perfumer & Flavorist magazine
Passion Fruit Drives Color Cosmetics Into World Perfumery Congress
New Dimensions Flavorcon
by N. Lourith et al.

Subscriptions: Subscribe online: www.CosmeticsandToiletries.com/subscribe


70 Face Care Formulary In the US, telephone: 1-888-355-5962; outside the US, telephone: 1-847-559-7558
(8 AM–5 PM Central, Monday–Friday) Fax: 1-847-291-4816
E-mail: customerservice@cosmeticsandtoiletries.com
Print subscriptions: Available free to qualified individuals located in the United States. All other countries may subscribe to
the digital edition. Periodicals Postage paid at Carol Stream, Illinois, and additional mailing offices.
Change of address: Give both the new and old addresses. Allow two months for a change to become effective.
Missing issues: Claims for missing issues must be made within three months of the date of issue.

Cosmetics & Toiletries® (ISSN 0361-4387CTOIDG) is published ten times per year as Jan., Feb., March, April, May, June,
July/Aug., Sept., Oct. and Nov./Dec. by Allured Business Media.
Connect with us Address: Cosmetics & Toiletries, 336 Gundersen Drive, Suite A, Carol Stream, IL 60188-2403 |
www.CosmeticsandToiletries.com

POSTMASTER: Send address changes to Cosmetics & Toiletries, PO Box 3009, Northbrook, IL 60065-3009
LinkedIn Allured Business Media makes all attempts to publish accurate information; however, this publication may contain technical
Cosmetics & Toiletries inaccuracies or typographical errors. The reader assumes all risks concerning the suitability and accuracy of the informa-
tion within this publication. Allured Business Media assumes no responsibility for and disclaims all liability for any such
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US$6 per copy per item is paid directly to the Copyright Clearance Center Transactional Reporting Service, 21 Congress St.,
Salem Ma 01970--Publication No. 0361-4387CTOIDG/01/$6.

4 | www.CosmeticsandToiletries.com
Cosmetics & Toiletries and C&T are registered trademarks of Allured Publishing Corporation.
Vol. 132, No. 9 | October 2017

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Editor’s Note | C&T ®

Discontinuity and Your Inner Innovator


Discontinued can be a scary word for marketers but it doesn’t have to be; in fact, according
to Pantini,1 discontinuity can be a real impetus for innovation. He recently illustrated this in his
description of innovation and innovators—i.e., those driven by discontinuity and change.
“The expertise of the innovator consists in the knowledge of as many industries and applications
as possible ... and to manifestations of any kind,” he writes. “The innovator has no motivation to
improve existing products but instead to create different products by the transfer and combination
of already existing technologies...”
Perhaps one of the most eye-catching industry fusions we’ve seen recently is between food/
beverages and beauty. Fun examples include truffle-inspired bath bombs, bubbling face masks
and ice cream-textured skin care, among others.2 However, while products like these capture the
imagination, another innovative mash-up has been capturing consumer dollars: multifunctional
color cosmetics. Whether fortified with SPF, anti-pollution, antioxidant, etc., properties, cosmetics
with added benefits are a major driver in the color category.3
But multifunctionality doesn’t stop there. It’s also seeping into sun care. Companies are
reinforcing sunscreens with anti-aging, intense repair4 and even infrared activities.
Regardless of the product category, from a technical standpoint, many of these added
benefits must eventually cross paths with the effects of UV radiation. And for this
reason, we’ve combined color with sun protection in our very own
manifestation of innovation: the Cosmetics & Toiletries before you.
We hope it inspires your inner innovator.

1. CosmeticsandToiletries.com/research/methodsprocesses/Innovation-vs-Research-
Revolutionizing-Product-Development--439287953.html
2. Popsugar.com/beauty/Food-Inspired-Beauty-Products-43536548?
stream_view=1#photo-43536615
3. GCImagazine.com/marketstrends/segments/cosmetics/Global-Cosmetics-Market-
Report-417457843.html
4. GCImagazine.com/marketstrends/segments/suncare/Three-Trends-Driving-the-Global-Sun- Rachel L. Grabenhofer
Care-Products-Market-Through-2020-408530935.html C&T Managing Editor

6 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

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Scientific Industry Insight | C&T ®
Advisory Board

Lauder Eyes
Infrared Skin Damage
Eric Abrutyn
TPC2 Advisors Ltd.

Zoe Diana Draelos, M.D.


Dermatology
Consulting Services Returning to the pages of Cosmetics & Toiletries this
month, Tom Mammone, Ph.D., of The Estée Lauder
Angela R. Eppler, Ph.D.
Pfizer Consumer Healthcare Companies and Clinique Labs, describes his research
on the effects of infrared radiation in skin. The follow-
Trefor Evans, Ph.D.
TA Evans LLC ing excerpt was adapted from a podcast—hear more at
CosmeticsandToiletries.com/multimedia.
S. Peter Foltis

C&T: What’s driving Lauder’s interest in infrared?


L’Oréal

Mindy Goldstein, Ph.D.


Atlantic Coast Media Group
Mammone: The biggest driver is more from a
Shuzo Ishidate, Ph.D.
scientific interest. Over the years, we’ve worked with
Shiseido Research Center many experts who have educated us on UVA and
UVB, and infrared (IR) was just the further end of
John Jiménez the spectrum. Of the high energy wavelengths that
Belcorp Colombia
come from the sun and reach the earth’s surface, IR is
Karl Laden, Ph.D. about 54-56%, so it’s a big component.
Alpa Cosmetics
As far as our skin, IR penetrates deeply. So, we
Prithwiraj Maitra, Ph.D. started to work with dermatologists and other
Johnson & Johnson scientists, and other studies were coming out, all
of which indicated IR could be damaging to skin;
Jennifer Marsh, Ph.D.
Procter & Gamble
so we added this to the repertoire of how we could
protect consumers.

C&T: How did you test these effects?


Marc Pissavini, Ph.D.
Coty-Lancaster

Luigi Rigano, Ph.D.


Industrial Consulting Research Mammone: We grew artificial skin in the lab
and irradiated it with different doses of IR that were
Sylvianne Schnebert, M.D. similar to what someone would be exposed to on a
LVMH Recherche
beach or during a really sunny day. We found pretty
Ron Sharpe significant changes in the skin barrier and activities
Amway along the inflammatory pathway.

Leslie C. Smith, Ph.D.


Consultant
C&T: Were the findings what you expected?
David C. Steinberg Mammone: Yes, in terms of similar data
Steinberg & Associates to what the dermatology field was finding.
What was exciting was when we went back
Peter Tsolis to look for ways to remediate the damage Tom Mammone, Ph.D.
The Estée Lauder Companies Vice President of Skin
and protect against IR.
Antioxidants are a great initial line of Physiology and Pharmacology
Russel Walters, Ph.D.
Johnson & Johnson protection but we identified two new ways The Estée Lauder Companies
to mitigate damage. First, energy enhanc- and Clinique Labs
Claudie Willemin
L’Oréal ers offset the energy depleted from cell
mitochondria by IR. Second, antagonists
Shuliang Zhang, Ph.D. of the TRPV1 receptor, which translate
Unilever IR radiation to thermal heat in the body,
show efficacy. Want More?
For more insight from Mammone or others,
log onto www.CosmeticsandToiletries.com

8 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

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Technology Launches
Mitochondrion Protection Double Skin Action

Photo Credit: Silab DSM has launched Beauactive (INCI: Hydroxystearic


With skin relying on mitochondria for cell energy, Silab Acid), a new active manufactured using green
introduced an active, Algophagyl (INCI: Chlorella Sorokiniana technology. The ingredient corrects noticeable age
Extract), to help preserve the equilibrium and correct the spots resulting from UVB stress. It also reduces the
functioning of mitochondria. Chlorella sorokiniana is a appearance of facial pores by helping skin generate
microalgae that protects the mitochondrion by enabling it to more collagen. In vitro, Beauactive was shown to
adapt to its environment and boost metabolism. activate the master cell regulator PPARα, which
www.silab.fr benefits skin in a variety of ways.
www.dsm.com

Chemical Defense Reduce Inflammaging

Oléos has launched Organic Diam Oléoactif (INCI:


Cocos Nucifera Oil (and) Oak Root Extract), an active
Botaneco presents Karmyn (proposed INCI: Carmin lipid complex that helps reduce inflammaging. This
(Carthamus Tinctorius) Protein), an ingredient produced ingredient was shown in vitro to reduce the secretion
from the protein encapsulating the triglycerides, vitamins rate of the inflammatory cytokine TNF-α, and to
and phospholipid bilayers in the plant’s seeds. This scavenge free radicals. In vivo, it helped to prevent
thermally stable, naturally high molecular weight protein the appearance of skin redness. Derived from cork
has applications in hair and skin care, particularly for hair oak and coconut, Organic Diam Oléoactif is 100%
color retention and defense against chemical damage. natural and 70% organic.
www.botaneco.com www.oleoactif.com

10 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

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Advertorial

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Performance without compromise
Today’s consumers want innovative, high-performance products created with natural, sustainable and ethically
sourced ingredients. When choosing AAK’s technologically advanced shea-based emollients for your formulations, you
do more than just excel at meeting these challenges. You also make a positive difference to the social, environmental
and economic development of the communities that depend on shea for their livelihood.

Shea is renowned for its anti-inflammatory, anti-ageing and skin barrier strengthening properties and has come a long way
from a simple butter. AAK leads the way in developing shea-based ingredients for the beauty industry and opening up new
opportunities for both the cosmetic formulator and the estimated 16 million women in West Africa who rely on shea for an
income. Increasing demand from cosmetic manufacturers is helping to build a bigger, better shea industry and halt rural-urban
migration. Generating more earnings to empower the shea-collecting women, improving local livelihoods and securing
supplies for the future. A win-win situation all round.

Creating value and sustainability through direct sourcing. Streamlined supply chains give local women more negotiating
power, a higher income and greater independence. The AAK direct sourcing programme was introduced in Burkina Faso in
2009 and has recently been extended to Ghana. Based on fair trade principles, including access to pre-financing, education
and logistical support, the programme involves over 115,000 women and continues to grow.

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community.” Kamboule Kibekoun

Sustainability is about empowering people, enabling prosperity and protecting the planet.
Our commitment to conserving energy and natural resources extends across the supply chain. Our Swedish manufacturing site
has been awarded an EcoVadis Gold ranking and initiatives include establishing Life Cycle Assessments to ensure that total
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CT1710_AAK_Advertorial.indd 1 9/18/17 5:28 PM


Regulatory | C&T ®

KEY POINTS
• While many can distinguish a drug from a
cosmetic, per regulations in North America, the
written text of how a product benefits the skin
can determine how it is categorized.

• In Canada, a product is a cosmetic, a drug


or a natural health product. In the United
States, a product can be either, or comply with
regulations for both cosmetics and drugs.

North American Regulatory Review

Navigating a Brave
New Nature

A
Cosmetics vs. Drugs

Robert H.R. Fichtner,


Angela Mazza, M.D., and
Anna Schwanke
Focal Point Research Inc.,
Mississauga, Ontario
“ ctive” ingredients are everywhere in
the cosmetics industry. They present
formulators with incredible new tools
to make products more effective than
we ever could have imagined. How-
ever, to those of us who have been
around a while, we remember when our legal departments prohib-
ited the use of the term active anywhere around a cosmetic. If the
marketing department loved an ingredient, it went into the product
at 0.00001% with a carefully worded claim and a creative demo for
broadcast advertising. Cosmetics were cosmetics, and drugs were

Reproduction in English or any other language of


12 | www.CosmeticsandToiletries.com all or part of this article is strictly prohibited. Vol. 132, No. 9 | October 2017
© 2017 Allured Business Media.

CT1710_Regulatory_Fichtner_fcx.indd 12 9/19/17 11:48 AM


InfraGuard
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Infrared A rays (IRA) and high energy visible (HEV) light, also known as blue
Infrared
light are Aknown
rays (IRA) and higheven
energy visible (HEV)
the light, also UV
known
rays.asThey
blue
/ Switzerland,

to penetrate deeper into skin than


/ Switzerland,

light are known to penetrate even deeper into the skin than UV
generate oxidative stress and contribute to the reduction of mitochondrialrays. They
generate oxidative stress
energy production, to skinand
cellcontribute
damage and to the reduction
to skin aging.of mitochondrial
Based on organic
energy production,
sunflower to skin cell
shoots InfraGuard damage and
significantly to skinskin
protects aging.
fromBased on organic
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sunflower shoots InfraGuard significantly protects skin from photo-aging.


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Inhibits light-induced skin aging
Biochemistry,

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Active Ingredients in Cosmetics

Both ingredient suppliers and brand owners


must ensure they have the evidence to prove
product claims and safety, especially for long
term use and in vulnerable populations.

drugs, and we treated them very differently. we advise they be removed before sale.
With the exponential developments in science Today we are hearing forecasts that the
today, this is no longer the case. active ingredient market for cosmetics will be
It was not until several groups of doctors worth more than $4 billion by 2026.1 Entire
and scientists approached us that this reality suppliers’ portfolios are based on active ingre-
struck home. We were presented with molecules dients. No anti-aging product would dare go
or analogues of molecules that were developed to market today without careful consideration
over years in chemotherapy and fundamental and selection of active ingredients. The skin
genetic research. When we asked about safety whitening category has exploded with all
testing, we expected to review data similar manners of active ingredients utilizing diverse
to what we see for new drugs. However, this biochemical modifiers.
was—and typically has not been—the case. It This exposes two fundamental questions.
seems many entrepreneurs entering cosmetics One, where do cosmetics end and drugs begin?
research believe the historic tools of human And two, do these various active ingredients
repeat insult patch testing and six-week home really work? The literature reveals a wide
trials are sufficient. variety of mechanisms for cosmetic actives,
We typically see before and after photos including the regulation of many biochemi-
of faces, legs and arms showing substantial cal pathways. Raw material catalogs feature
improvements in wrinkles, aging and other benefits such as “inhibits 5α-reductase,”
parameters. We dig down deep, looking for “stimulates epithelial cell oxygen consumption,”
regulatory barriers for these projects. Most and “rapidly regenerates UV-related cell and
often, the actives are not on any North Ameri- DNA damage.” Yet these claims are absent on
can list of restricted or prohibited ingredients. finished cosmetic products. Instead, phrases
In some cases, the entrepreneurs produce like “younger-looking skin,” “softens skin,” or
finished-packaged products, ready to be sold. “helps prevent the look of aging” are used. If the
If there are outrageous claims on the packages, active ingredients really do what they advertise,
these claims cannot be used on product labels
and marketing material because that would
make them drugs.

North America conquers premium beauty and Cosmetic or Drug?


personal care in per capita expenditure. The region’s
premium beauty forecast predicts absolute gains Regulating Claims
from 2016–2021 to amount to $5.8 billion, double In the U.S. and Canada, there are firm
the prospects in mass beauty. restrictions on claims cosmetic products can
make. First, they must not make therapeutic
Source: Global Cosmetic Industry claims such as references to treating or prevent-
(www.GCImagazine.com) ing a disease. Second, they cannot claim to alter
the structure or function of the body. Lastly,
they cannot be misleading to the consumer.2, 3

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CT1710_Regulatory_Fichtner_fcx.indd 14 9/19/17 11:48 AM


The term cosmeceutical is not recognized
or defined by regulators in either country. In
Canada, a product is a cosmetic, a drug or a
natural health product.2 In the United States,
a product can be either, or comply with the
regulations for both cosmetics and drugs.4 But
with the advance of science such as epigenetics,
cosmetic products may stumble into the
grey zone of these two categories. Sadly, the
regulatory architecture for cosmetics in North
America was built in the 1930s and 1940s, for
products like lipsticks and shampoos, and is
woefully out of date. In fairness, federal health
regulators are swamped with countless urgent
priorities, all of which can take precedence.

Epigenetics—Going One
Step Further?
In the past, cosmetic science was largely
driven by chemistry and the innovations With the advance of science such as epigenetics, cosmetic products may stumble into the grey
zone between cosmetics and drugs.
involved, delivering enhanced benefits in cleans-
ing, conditioning, moisturizing, etc. However,
recent work expanding our understanding of or other similar components of the body.6, 7
genetics is pushing the industry toward biology- These are the exact actions promised by many
based cosmetic formulation. For example, in active ingredients.
the last few years, we have seen an increase in Beyond the regulatory aspects, these actives
the mention of epigenetics for skin care. also pose safety questions. What is the potential
Epigenetics cause specific tissue changes impact on ecosystems when products contain-
by reprogramming cells without altering their ing these actives are disposed of, or washed
DNA sequences.5 Chemical compounds act on down the drain? What happens when plant and
the genome to alter what it does, as well as animal organisms take up epigenetic-altering
when and where. An important epigenetic reac- substances into their tissues? Epigenetic
tion is the regulation of methylation. Altering changes are durable, are inclined to spread to
methylation patterns allows enzymes to attach non-target tissues and can be transmitted from
to DNA and turn genes on.5 Understanding one generation to the next.8 Are there safety
epigenetic regulation has allowed us to improve concerns for pregnant or lactating users of
the accuracy and efficiency of active ingredi- products containing these technologies? And
ent delivery by targeting fundamental cellular has the potential impact on reproduction and
and genetic processes. While this fast-moving fertility been studied?
corner of biology is an exciting development in Many proteins and enzymes that are the
skin care, it raises some questions. epigenetic targets of anti-aging products are
First, we know that cosmetic products can- also essential to other body functions. Elastin,
not claim to alter the structure or function of for example, plays a role in wrinkle prevention
the body. Yet this is what these active ingredi- as well as being key to lung compliance for
ents are meant to do, not only macroscopically, normal breathing.9 In our development of these
but also on cellular and genetic levels. Health new ingredients, are we adequately studying
Canada and the U.S. Food and Drug Adminis- their percutaneous absorption and potential
tration guidelines clearly state that acceptable systemic effects?
cosmetic claims cannot make any reference to These are all questions we carefully address
action at the cellular or even tissue level, work- when presented with new drugs and even some
ing from the inner layers of the skin outward oral nutritional supplements. What makes
or influencing collagen, elastin, enzymes cosmetics more challenging is we cannot assess

Vol. 132, No. 9 | October 2017 Cosmetics & Toiletries® | 15

CT1710_Regulatory_Fichtner_fcx.indd 15 9/19/17 11:48 AM


Active Ingredients in Cosmetics

If cosmetics cannot make drug claims,


yet they demonstrate drug activity, is this
misleading the consumer by omission?

their safety using animal models like we do for nocompromised. Innovators working on the
drugs, and we typically do not see the phased frontier of these cosmetic sciences would be
approach to testing human exposure, starting well-advised to study some of the models used
with Class I clinical trials on small numbers in drug development and determine if any could
of subjects. be applicable to their technology. Developing a
cosmetovigilance plan should become routine.
Misleading by Omission? With increasing consumer concerns for
The other regulatory consideration is the product safety and the ever-present watchful
constraint that cosmetic product claims must eye of NGOs, we must continue to innovate for
not be misleading to the consumer. Tradition- all the exciting possibilities but do so with cau-
ally, this has been thought of in the context as tion. As an industry, we must be careful in the
promising unrealistic benefits. But if consumers excitement of innovation and new science so
are unaware of the effects of cosmetic active we are not blind to safety and ethical consider-
ingredients at a cellular level, is this misleading ations as we navigate this brave new world.
by omission?
As a hypothetical example, two products References
could have the exact same formula, intended All websites accessed on Aug. 28, 2017.
use and level of active ingredient. One of them 1. marketsandmarkets.com/PressReleases/active-ingredient-
claiming to “give the skin radiance” would be cosmetic.asp
regulated as a cosmetic, while the other claim- 2. canada.ca/en/health-canada.html
ing to “maximize skin cell turnover” would be 3. www.fda.gov/cosmetics/labeling/claims/ucm2005200.htm
a drug. If marketed as a cosmetic, the question 4. www.fda.gov/Cosmetics/GuidanceRegulation/LawsRegula-
is, do consumers have the right to know that tions/ucm074201.htm
5. H Epstein, RJ Gadberry and MR Rosen, Understanding the
what they're putting onto their skin is turning
value of molecular cell biology and gene analysis for the
genes on/off, inhibiting/stimulating enzymes, next generation of cosmetic products, Harry's Cosmeticol-
accelerating cell turnover, or influencing free ogy 9(1) (2015)
radical scavenging? 6. MA Rothstein, Y Cai and GE Marchant, The ghost in our
genes: Legal and ethical implications of epigenetics, Health

Protecting the Industry and Matrix: J of Law-Medicine 19(1) 1-63 (2009)


7. BC Starcher, Elastin and the lung, Thorax 41 577-585
the Consumer (1986)

With the aforementioned promising forecast 8. www.fda.gov/Cosmetics/GuidanceRegulation/LawsRegula-


tions/ucm074201.htm
for the actives market, it is likely the use of
9. www.fda.gov/cosmetics/labeling/claims/ucm2005200.htm
sciences such as epigenetics in cosmetics will
continue to thrive. Does our industry have
sufficient safeguards in place to assess risks
to human health and the environment? Both
ingredient suppliers and brand owners must C&T Daily Newsletter
ensure they have the evidence to prove product
Get the latest from Cosmetics & Toiletries
claims and safety, especially for long-term use delivered straight to your inbox every day!
and in vulnerable populations such as children,
pregnant and lactating women and the immu- http://www.CosmeticsandToiletries.com/newsletter

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Research | C&T ®

KEY POINTS
• Avobenzone is a widely used UV-absorbing
organic filter. Its dynamic nature and
photophysical and photochemical properties
are responsible for its widespread use.

• This first in a two-part series reviews its


inherent characteristics and behavior in
solvents; part two will consider its behavior
with other sunscreens and in formulas.

In Light of
Exposure Reproduction in English or any other language of
18 | www.CosmeticsandToiletries.com all or part of this article is strictly prohibited. Vol. 132, No. 9 | October 2017
© 2017 Allured Business Media.

CT1710_Research_Dutta_fcx2.indd 18 9/20/17 4:19 PM


Understanding
Avobenzone
Part I: Characterization

Prabir K. Dutta
Ohio State University, Columbus, Ohio, USA
Bo Wang
ZeoVation, Columbus, Ohio, USA

1
Avobenzone has the empirical formula
C20H22O3 and a molecular weight of 310.39 g/
mol. It is a yellow powder with a weak char-
acteristic odor. While it is soluble in a variety
of polar and non-polar solvents, it exhibits low
-4-(tert-butylphenyl)- solubility in water; i.e., 0.01 mg/L at 20°C.
3-(4-methoxyphenyl) Within the UV region of the electromag-
propane-1,3 dione is netic spectrum, the portion of radiation that
a member of the class reaches the earth’s surface is divided into UVB
of dibenzonyl meth- (290–320 nm) and UVA (320–400 nm)—and
ane molecules and is avobenzone is one of the most effective
widely used as an active UV filter in sun- absorbers in the UVA range, which explains
screen and cosmetic products. Indeed, in its popularity.
a 2014 review of cosmetic products in the Considering the extensive use of sunscreens
United Kingdom, UV filters were present and cosmetic products, the implication is that
in a wide variety of cosmetics; this one in a significant fraction of consumers around
particular appeared in 48.7% of the 4,447 the world is applying avobenzone to their
products examined.6 bodies. Many studies have focused on the
This molecule is also referred to in the photochemistry, photodegradation, photosta-
literature as butylmethoxy dibenzoylmeth- bilization and interaction of this material both
ane (BMDM), avobenzone and the trade with biological and nonbiological systems;
names Escalol 517, Eusolex 9020, Parsol recent reviews are available.1–5 In this paper,
1789 and NeoHeliopan 357. The present we review the literature on the photochemistry
paper will refer to it as avobenzone. of avobenzone, with particular emphasis on

Vol. 132, inNo.


Reproduction 9 | or
English October 2017 of all or part of this article is strictly prohibited. © 2017 Allured Business Media.
any other language Cosmetics & Toiletries® | 19

CT1710_Research_Dutta_fcx2.indd 19 9/20/17 4:19 PM


In Light of Exposure

Considering the extensive use of sunscreens


and cosmetic products, a significant fraction
of consumers uses avobenzone.

how its unique molecular structure and related and cyclohexane are 10 and 46, respectively,
photochemistry determine its end use. favoring the enol form.8 The enol is converted
to the keto form upon photolysis in certain
Avobenzone Structure solvents and will revert slowly to the enol form
Solutions of avobenzone consist of an equi- in the dark. The rate constant varies between
librium mixture of a chelated enol form and the solvents: for conversion of keto to enol in the
corresponding keto form, as shown in Figure 1. dark, it is 1.8 × 10-3s-1, 8.6 × 10-4s-1 and 7.0 ×
Two isomeric forms of the enolic form coexist 10-5s-1 in ethyl acetate, DMSO and cyclohexane,
in solution. Calculations suggest the O-H group respectively.8
on the benzene with the t-butyl group is slightly
energetically favored (see structure A in Fig- Absorption Spectra
ure  1; DE (intramolecular hydrogen bond) = Figure 2 shows the absorption spectrum
69.8 kJ/mol) versus the other enol (see structure of 2 × 10-5 M of avobenzone in cyclohexane.
B in Figure 1; DE (intramolecular hydrogen The band at 355 nm (ε = 32400 M-1cm-1) is
bond) = 71.7 kJ/mol).7 due to the enol, and the band at 265 nm (ε =
The enol structure is planar while the keto 28400 M-1cm 1) is due to the keto form. The
form has a butterfly-like structure. The methoxy enol band shifts to higher wavelengths in
group promotes extended delocalization of the more polar solvents: ethyl acetate = 356 nm;
enolic form. The H-bonding in the chelated enol DMSO = 363 nm; and methanol = 358 nm.9 The
form is a resonance-assisted, strong H-bond singlet excited state of the enol (1S) is reached
arising from a synergistic effect of p-delocaliza- via pp* transition and that of the keto form
tion and H-bond formation. via a np* transition. In the nonpolar solvent
The equilibrium favors the enol over the cyclohexane, the 1S lifetime (420 ± 40 fs) of the
keto form, with the exact ratio of enol to keto enol is one-third of that observed in methanol
being solvent-dependent. The enolic form is (1.4 ± 0.2 ps), indicating a charge localized
favored in non-polar solvents, e.g., the equilib- excited state.10
rium constant in dimethyl sulfoxide (DMSO)
Fluorescence Spectra
The enol form exhibits fluorescence
with significant vibronic structure between
400–450 nm (the energy of the 0-0 singlet
excited state is 390 nm) and weak phospho-
In developing countries, where the highest rescence with peaks at 490 nm and 530 nm;
growth in sun protection is expected, 30% all measurements were in ethanol at 77K.11
to 40% of consumers opt to buy sunscreen The lack of fluorescence at room temperature
products with multifunctional ingredients. indicates efficient nonradiative relaxation and/
or a fast photochemical reaction. The lifetime
of the phosphorescent state of the enol is 30 ms.
Source: Euromonitor International The electron paramagnetic resonance (EPR)
spectrum of the triplet state at 77K suggests the
two unpaired electrons are not localized on the
phenyl or carbonyl fragment.11 In another study,

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CT1710_Research_Dutta_fcx.indd 20 9/19/17 5:39 PM


Figure 1. Solution equilibrium forms of avobenzone

Figure 2. UV-vis spectrum of avobenzone (2.0 × 10-5 M solution in cyclohexane)

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CT1710_Research_Dutta_fcx.indd 21 9/19/17 5:39 PM


In Light of Exposure

room temperature fluorescence was observed state is ~190 ms. The triplet state does not
for avobenzone dissolved in ethyl acetate, with exhibit an EPR signal.11 For the triplet state, in
the fluorescence maxima at 405 nm, a quan- both keto and enol forms, there is more 3pp*
tum yield of 0.01 and fluorescence lifetime of character. The methoxy and tert-butyl groups
13 ps.12 influence the mixing of the 3np* and 3pp* state,
The keto form is only weakly fluorescent increasing the lifetime of the triplet state.11
but does exhibit strong phosphorescence at This long-lived triplet state of the keto form is
410–450 nm, and the lifetime of the triplet relevant for the photo instability of avobenzone.

Figure 3. Possible structures formed upon photoexcitation of the enolic form


of avobenzone

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CT1710_Research_Dutta_fcx.indd 22 9/19/17 5:39 PM


Various theoretical
methods have examined
the structural and
photochemical aspects
of avobenzone.

In acetonitrile, excitation with ns 355 nm


Transient Spectroscopy pulses resulted in a photoexcited species with
Several transient spectroscopy studies λmax at 300 nm, with a quantum yield of 0.25.13
have unraveled the fate of photoexcited avo- This species, originating from the enol form,
benzone9, 10, 13, 14 and related compounds.15 In was assigned to a mixture of the isomers
relation, a review of the ultrafast photochem- formed by rotation around the C2-C3 single
istry of molecules used as sunscreens was bond (NCE2) and the isomeric species formed
recently publishes.16 Figure 3 summarizes the by isomerization around the C1-C2 double
results from the transient spectroscopy studies, bond (NCE1), as shown in Figure 3.13 It was
and is discussed below. proposed that the isomer formed via rotation
Transient absorption spectra of avobenzone around the single bond () quickly reverts to
in different solvents showed that photoexcited the chelated enol, with the primary species
enol (absorbing at 300 nm) decays with varying responsible for the ns transient spectra being
lifetimes in different solvents: 0.08 ms in CCl4, the non-chelated isomer NCE1 formed via
1.21 ms in cyclohexane and to 24.4 ms in ace- double bond isomerization. The kinetics of
tonitrile.14 To explain this solvent-dependence, decay of this NCE1 isomer exhibited both first
different degrees of exciplex formation with the and second-order decay, with first order decay
various solvents was proposed. more evident in polar solvents. The lifetime

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In Light of Exposure

of the NCE1 state was solvent-dependent, With 266 nm excitation of avobenzone


being faster in protic solvents, and varied from in acetonitrile, a broad transient spectrum
159 ms in acetonitrile to 12 ms in cyclohexane (300–500 nm) with a lifetime of 500 ns was
and 0.7 ms in butanol. NCE1 can follow two observed.13 These features are characteristic
solvent-dependent pathways: reformation of the of alkylated avobenzone, which can only exist
chelated enol, or shifting to the keto form via in the keto form.17 Also, this species formed in
hydrogen transfer. avobenzone was quenched rapidly with oxygen

Figure 4. Transformation of the photoexcited enolic corm to the keto isomer

Figure 5. Excited state dynamics of avobenzone

24 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Research_Dutta_fcx.indd 24 9/19/17 5:39 PM


(5 x109 M-1s-1), and is most likely the triplet state gesting the excited singlet state of the enol was
of the keto form. Permanent loss of avobenzone responsible for the formation of the keto form.9
occurred upon 266 nm excitation, indicating Transient photolysis at 266 nm of the keto form
photodegradation via the excited keto form resulted in a triplet excited state (390 nm) but
is occurring.13 showed no evidence for tautomerization to the
Another ns laser photolysis in acetonitrile enol form—requiring a 1,3-H atom shift in the
and ethanol gave similar observations but for excited state—though this reaction takes place
the transient excited state; besides the NCE1 in the dark; demonstrating a lifetime of 5.1 hr
isomer, a non-chelated enol formed by the at 295K in acetonitrile.
rotation around the C-OH bond (breaking A recent picosecond transient photolysis
of H-bond, NCE3, Figure 3) was proposed.9 study with 350 nm excitation of avobenzone
The decay pathways for the isomer involves in acetonitrile, methanol and cyclohexane has
relaxation to the chelated enol via isomeriza- been reported.10 The transient absorption sig-
tion around the C1-C2 double bond, promoted nals monitored at 266 nm were believed to arise
in polar solvents via H-bonding; or shifting to from the relaxation of three isomers includ-
the keto form through a 1,3-H atom shift, as ing: NCE1 or the keto form (this could not be
observed in acetonitrile, which through rotation distinguished but was most likely NCE1), NCE2
around C2-C3) can relax back to the regular keto and the non-chelated isomer NCE3 formed via
form, as shown in Figure 4. rotation around the C-OH bond.10 The NCE3
This study estimated a quantum yield for the form was solvent-insensitive and returned to
keto formation of 0.014 ± 0.002 in acetonitrile the chelated enol with a lifetime of 1.3 ps. The
and was independent of dissolved oxygen, sug- NCE2 form reverted back to the chelated enol

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CT1710_Research_Dutta_fcx.indd 25 9/19/17 5:39 PM


In Light of Exposure

chelated enol with a lifetime of 30 ± 10 ps in note that the quantum yield of the NCE1 form
methanol, 59 ± 8 ps in cyclohexane and 80 ± 20 was similar for methanol and acetonitrile, though
ps in acetonitrile. NCE1 dynamics were slow the steady-state photochemistry of avobenzone is
on the picosecond time scale. It is interesting to quite different in these solvents, as detailed below.

Figure 6. UV-vis spectrum of avobenzone in acetonitrile (2 x 10-5M), which involved photolysis


with λ > 280 nm, 80 mW/cm2 for 1 hr followed by 1 hr storage in dark

Figure 7. Primary step in the photodegradation of avobenzone

26 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Research_Dutta_fcx2.indd 26 9/20/17 4:31 PM


The photolysis of
avobenzone is both solvent-
and wavelength-dependent.

Figure 5 summarizes the following observa- avobenzone than in polar solvents. The struc-
tions from the transient spectroscopy studies: tural change that takes place in avobenzone is
the phototautomerization of the enol to the keto
• There are at least three intermediate
form. The keto form will revert back to enol in
structures in the excited state, accessible
the dark. There can also be further photodegra-
by excitation of the enolic form.
dation and it appears this happens primarily in
• These structures result from rotation
the keto form.
around single bonds, disruptions of the
Water: Solar simulated photolysis (250 W/m2
H-bond or isomerization around the
for 4 min, repeated 5×) of avobenzone in water
double bond.
shows considerable degradation.18 Consider-
• Of particular interest is the longer-lived
ing the low solubility of avobenzone in water,
isomer formed by isomerization since it
these were dilute solutions. Water appears to
can convert to the keto form.
be different from other protic solvents, which
• Upon excitation of the keto isomer, a
stabilize the enolic form.
long-lived triplet state is formed and
Methanol: In methanol, 2.6 × 10-5 M avo-
is relevant since it can take part in
benzone is relatively photostable, with λexcitation
further photochemistry.
> 300 nm (high-pressure Hg lamp, 150 min
illumination; flux not reported). In methanol,
Steady State Photolysis the H-exchange of the photoexcited transient
The photolysis of avobenzone is both nonchelated enol and the solvent was proposed
solvent- and wavelength-dependent. There is to promote the reformation of ground state
considerable variation in the literature in this enol. Presence or absence of dissolved oxygen
area, primarily due to different irradiation does not influence the photolysis.8
conditions, both flux and wavelength, and Ethyl acetate: There is a marked decrease
the concentrations used. In general, there is in the enolic form by about 60%, with λexcitation
agreement that in nonpolar solvents there are > 300 nm, in air-equilibrated 2.4 × 10-5 M avo-
more changes in the absorption spectra of benzone in ethyl acetate, along with an increase

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In Light of Exposure

in the keto form, with a clear isosbestic point (high-pressure Hg lamp, 30


min illumination; flux not reported). Photodegradation was also noted by
HPLC analysis. Removing oxygen did not significantly impact the photosta-
bility.8 In another report, with the solar simulated photolysis (250 W/m2 for
4 min, repeated 5×) of a dilute solution of avobenzone in ethyl acetate, no
change in the absorption spectra of avobenzone was observed.18
Cyclohexane and other hydrocarbon solvents: In air-equilibrated
cyclohexane, considerable loss of the enolic form occurs within an hour
upon photoexcitation at λexcitation > 300 nm of 1.0 × 10-5 M avobenzone, with
formation of the keto form (high-pressure Hg lamp; flux not reported). The
keto form undergoes photodegradation within 30 min of photoirradiation.
The presence of oxygen accelerated the photoconversion.8 Another study
also noted the enol to keto phototautomerization with solar-simulated
photolysis (250 W/m2 for 4 min, repeated 5×) for a dilute solution of
avobenzone and in the dark, the enolic form of avobenzone was fully recov-
ered. Similar behavior was noted in hexane and heptane.18
Acetonitrile: In neat acetonitrile, the spectrum changed significantly
with disappearance of the enol band (355 nm) and appearance of the keto
form (265 nm).9, 14 Removal of dissolved oxygen did not influence this
process. With avobenzone in acetonitrile, upon 80 mW of 355 nm illumina-
tion for 3 hr, the formation of photoproducts was noted, being different for
oxygen and argon saturated samples.19 One report observed little change
in absorbance upon solar simulated light irradiation (250 W/m2 for 4 min,
repeated 5×) of diluted avobenzone in acetonitrile.18 In support of the
above observations, Figure 6 demonstrates the partial disappearance of
avobenzone in acetonitrile upon photolysis with > 280 nm (~80 mW/cm2)
for an hour and reappearance with an hour in the dark.
Dimethyl sulfoxide: In air-equilibrated DMSO, almost a complete
conversion of the enol to the keto form occurs within 40 min, with λexcitation
> 300 nm, with a clear isosbestic point (1.5 × 10-5 M solution). With deaer-
ated DMSO, the enol form is stable, indicating that oxygen plays a role in
the photochemical conversion of enol to the keto form.
It has been proposed that the key structural feature responsible for the
photoisomerization of the enol to keto is the ability of DMSO to H-bond
with the OH group of the enol, disrupting the chelated enol in the ground
state. The photoexcited keto form, with its tail of absorption extend-
ing beyond 300 nm, can react with oxygen to form singlet oxygen. The
singlet oxygen was proposed to promote the photoisomerization to the
keto form.8 It is unclear why minimal photodegradation via the keto form
was observed in DMSO, compared with ethyl acetate, cyclohexane and
acetonitrile.
The important aspects gleaned from photolysis studies are as follows:

• The excited state of the enol formed due to the isomerization around
the C=C bond (NCE1) is the most relevant to photolysis;
• This isomer can revert to the ground-state enolic form or can convert
to the keto form;
• The chemistry of the isomer is solvent-dependent; in particular, the
H-bonding property of the solvent;
• Nonpolar solvents promote conversion to the keto form; and
• The keto form does not photochemically transform to the enol form
but will do so in the dark, slowly.

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Photodecomposition p-tertbutylbenzoic acid (see C in Figure 8)
Several studies have examined the photo- and t-butylbenzene (see I in Figure 8)—were
degradation of avobenzone.8, 18–24 The possible observed by GC and MS. These severe photo-
pathways of photodecomposition and resulting chemical conditions decomposed some of the
products that have been reported are shown in primary photoproducts that were formed. A
Figures 7 and 8, and discussed below. mechanism involving the fission of either one
The total photodecomposition of avobenzone of the two C-C bonds adjacent to the C=O of the
in cyclohexane was observed upon irradiation keto form, as shown in Figure 7, could explain
by a mercury lamp (185–4000 nm) for 100 the formation of benzoic acids. With this type
hr.22 Three degradation products—including of symmetric bond breakage, it was surprising
p-methoxybenzoic acid (see E in Figure 8), that methoxybenzene was not observed.22

Figure 8. Possible products formed from the photodegradation of avobenzone

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In Light of Exposure

In another study,23 a solar simulator with hydroperoxide product was also identified (see
two cutoff filters showed the photolysis of a N).18 In ethyl acetate, two photodegradation
3.5 mM solution of avobenzone in cyclohexane: products, 4-t-butyl-4'-methoxybenzyl (J, K or L
filter A, with λ > 260 nm 12.4 mW/cm2 of UVA in Figure 4) and 4-t-butyl phenylglyoxal (D or G
and 0.54 mW/cm2 of UVB; and filter B, with λ > in Figure 4) were identified.8
320 nm, 11.1 mW/cm2 of UVA and 0 mW/cm2 of In non-volatile industrial solvents, mineral
UVB; incident on the samples for up to 8 hr. oil, alkyl tartrate, capric/caprylic triglyceride,
As expected, photodegradation with the light isostearyl isostearate, alkyl lactate and glycerol,
source including UVB was more pronounced, 495 kJ/m2 of illumination using a solar simulator
although even with UVA only, photodegradation showed a significant loss of avobenzone; up to
was still observed.23 Twelve products, includ- 80%.18 LC/MS analysis showed a complex mix-
ing benzaldehydes (see B and E in Figure 8), ture of photodegraded products, some of which
benzoic acids (see C and F), phenylglyoxals are shown in Figure 8, but there were other
(see D and G), acetophenones (see A), benzils peaks whose structures were not analyzed.18
(see J, K and L) dibenzoylmethane (see N) The photodegradation is proposed to occur
and dibenzoylethane (see M and O), were in the keto form, which can undergo α-cleavage
identified by HPLC and GC/MS. These photo- reactions from the singlet state to form benzoyl
products primarily absorb around 250 nm, in and phenacyl free radicals, as shown in Figure 7.
the UVC range. Support of the formation of carbon-centered
In water (250 W/m2 for 4 min, repeated 5× radicals upon photodecomposition is provided
with a solar simulator) several photoproducts by EPR studies of mixtures of avobenzone
were identified by HPLC-MS, including E, F, K, and piperidine nitroxide or indolinic nitroxide
O, P and Q shown in Figure 8. In addition, a radical. The EPR signal of the nitroxide radicals

30 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Research_Dutta_fcx2.indd 30 9/20/17 4:36 PM


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In Light of Exposure

decreases with photolysis time, and suggests These photodecomposition experiments


the carbon-centered radicals from avobenzone indicate that:
couple with the nitroxide radical to form a spin-
• The photoexcited keto form is responsible
paired adduct.25
for photodegradation;
The photochemistry of the methylated form
• In the triplet state of the keto form, there
of avobenzone that restricts the molecule to
is C-C bond fission, and the Norrish Type I
only the keto form (CH3 group at position 2 in
process is initiated;
Figure 1) also demonstrates the importance of
• Photodecomposition is complex and gen-
the triplet state.17 Upon photoexcitation of this
erates many species that absorb primarily
blocked diketo form at 308 nm, a broad absorp-
at wavelengths below 260 nm;
tion band centered at 380 nm was observed. This
• The triplet keto form can also generate
band has been previously assigned to the triplet
singlet oxygen, which can react with
state of the keto form of avobenzone.13 In keep-
ground-state enol to form oxygenated
ing with the triplet assignment, the excited state
products; and
was quenched by oxygen and β-carotene. Direct
• The enol form can be completely
photoexcitation of the keto form of avobenzone
destroyed in photolysis.
also leads to a long-lived (~ 500 ns) triplet state
that is quenched by oxygen to form singlet
The following scheme summarizes the sec-
oxygen with rate constant of 2.2 x 109 M-1s-1 (in
tions above:
acetonitrile). A quantum yield of 0.3 was esti-
mated for singlet oxygen formation;17 and singlet AB ↔ NCE1 + NCE2 + NCE3
oxygen can cause further photodegradation. NCE1 ↔ AB (K)
Modifications to the functional groups of avo-
AB (K) ↔ 3AB(K)
benzone have an influence on its photostability.
Replacement of tert-butyl group with isopropyl
3
AB(K) → Photoproducts
makes the molecule more susceptible to UVA 3
AB(K) + O2 → AB(K) + 1O2
photodegradation. The presence of an –OH
AB + 1O2 → Products
group adjacent to the C=O (4-t-butyl 21 hydroxyl
41 methoxy dibenzoyl methane) shows a 5% loss AB(K) + 1O2 → Products
upon photolysis, as compared with a 36% loss
with avobenzone.21 Here, AB is the enolic form of avobenzone
and K is the keto form.

Behavioral Theories
Various theoretical methods have examined
the structural and photochemical aspects of
avobenzone. Coupled cluster theory suggests
the solvent-dependent photolability of avo-
benzone arises due to the change in relative
ordering of the lowest triplet states of the pp*
and np* states of the keto isomer.26 Density
Functional Theory (DFT) calculations sug-
gest the enol form is more stable due to the
resonance-assisted hydrogen bond and
that photodegradation occurs
from the triplet state of the
keto form; where breakage of
the C2-C3 bond (see Figure
7) is slightly more favor-
able.7 Another DFT study
explained the difference

32 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Research_Dutta_fcx.indd 32 9/19/17 5:39 PM


otanical
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In Light of Exposure

6. W Uter, M Gonçalo, K Yazar, E-M Kratz, G Mildau and


Want More? C Lidén, Coupled exposure to ingredients of cosmetic prod-
ucts: III. Ultraviolet filters, Contact Dermatitis 71(3) 162–169
Check out page 18 of the October digital edition (2014) doi: 10.1111/cod.12245
for an exclusive "From the Vault" on Photostability.
7. L Pinto da Silva, PJ Ferreira, DJR Duarte, MS Miranda
and JCG Esteves da Silva, Structural, energetic and
UV–vis spectral analysis of UVA filter 4-tert-butyl-
4′-methoxydibenzoylmethane, J Phys Chem 118(8)
1511–1518 (A 2014) doi: 10.1021/jp4123375
8. GJ Mturi and BS Martincigh, Photostability of the sun-
screening agent 4-tert-butyl-4′-methoxydibenzoylmethane
in keto and enol electronic spectra based on (avobenzone) in solvents of different polarity and proticity,
J Photochem Photobiol Chem 200 (2) 410–420 (2008) doi:
their nonplanar and planar conformations, 10.1016/j.jphotochem.2008.09.007
respectively; the latter facilitating electronic 9. M Yamaji and M Kida, Photothermal tautomerization of a
resonance across the molecule.27 UV sunscreen (4-tert-butyl-4′-methoxydibenzoylmethane) in
How will this behavior translate to formula- acetonitrile studied by steady-state and laser flash photoly-
sis, J Phys Chem 117(9) 1946–1951 (A 2013) doi: 10.1021/
tions, in the presence of other chemistries? jp312774e
Part II in this series will explore this facet 10. AD Dunkelberger, RD Kieda, BM Marsh and FF Crim,
of avobenzone. Picosecond dynamics of avobenzone in solution, J Phys
Chem 119(24) 6155–6161 (A 2015) doi: 10.1021/acs.
jpca.5b01641
References 11. A Kikuchi, N Oguchi and M Yagi, Optical and electron
1. U Osterwalder and B Herzog, Chemistry and proper- paramagnetic resonance studies of the excited states of
ties of organic and inorganic UV filters, in Clinical Guide 4-tert-butyl-4′-methoxydibenzoylmethane and 4-tert-
to Sunscreens and Photoprotection; Basic and Clinical butyl-4′-methoxydibenzoylpropane, J Phys Chem 113(48)
Dermatology, CRC Press (2008) pp 11–38 13492–13497 (A 2009) doi: 10.1021/jp905236m
2. U Osterwalder, M Sohn and B Herzog, Global state of sun- 12. C Bonda and A Pavlovic, Singlet quenching proves faster is
screens, Photodermatol Photoimmunol Photomed 30(2–3) better for photostability, Cosm & Toil 125(2) 40–48 (2010)
62–80 (2014) 13. A Cantrell and DJ McGarvey, Photochemical studies of
3. C Stiefel and W Schwack, Photoprotection in changing 4-tert-butyl-4’-methoxydibenzoylmethane (BM-DBM),
times–UV filter efficacy and safety, sensitization processes J Photochem Photobiol 64(2–3) 117–122 (B 2001)
and regulatory aspects, Intl J Cosm Sci 37 (1) 2–30 (2015) 14. I Andrae et al, A UVA filter (4-tert-butyl-4′-
doi: 10.1111/ics.12165 methoxydibenzoylmethane): Photoprotection reflects
4. SQ Wang, Principles and Practice of Photoprotection, photophysical properties, J Photochem Photobiol 37(1)
Springer (2016) 147–150 (B 1997) doi: 10.1016/S1011-1344(96)07330-7
5. J Kockler, M Oelgemöller, S Robertson and BD Glass, 15. PK Verma, F Koch, A Steinbacher, P Nuernberger and T
Photostability of sunscreens, J Photochem Photobiol Brixner, Ultrafast UV-induced photoisomerization of intramo-
C Photochem Rev 13 (1) 91–110 (2012) doi: 10.1016/j. lecularly H-bonded symmetric β-diketones, J Am Chem Soc
jphotochemrev.2011.12.001 136 (42) 14981–14989 (2014) doi: 10.1021/ja508059p

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CT1710_Research_Dutta_fcx2.indd 34 9/20/17 4:49 PM


16. LA Baker, SE Greenough and VG Stavros, A Perspective on the
ultrafast photochemistry of solution-phase sunscreen molecules,
J Phys Chem Lett 7(22) 4655–4665 (2016) doi: 10.1021/acs.
jpclett.6b02104
17. C Paris, V Lhiaubet-Vallet, O Jiménez, C Trullas and MA Miranda,
A blocked diketo form of avobenzone: Photostability, photo-
sensitizing properties and triplet quenching by a triazine-derived
UVB-filter, Photochem Photobiol 85(1) 178–184 (2009) doi:
10.1111/j.1751-1097.2008.00414.x
18. SP Huong, E Rocher, J-D Fourneron, L Charles, V Monnier, H Bun
and V Andrieu, Photoreactivity of the sunscreen Butylmethoxydiben-
zoylmethane (DBM) under various experimental conditions, J
Photochem Photobiol Chem 196(1) 106–112 (2008) doi: 10.1016/j.
jphotochem.2007.11.023
19. AR Abid, B Marciniak, T Pȩdziński and M Shahid, Photo-stability
and photo-sensitizing characterization of selected sunscreens’
ingredients J Photochem Photobiol Chem 332 241–250 (2017) doi:
10.1016/j.jphotochem.2016.08.036
20. N Tarras-Wahlberg, A Rosén, G Stenhagen, O Larkö, A-M Wennberg
and O Wennerström, Changes in ultraviolet absorption of sunscreens
after ultraviolet irradiation, J Invest Dermatol 113 (4) 547–553 (1999)
doi: 10.1046/j.1523-1747.1999.00721.x
21. A Deflandre and G Lang, Photostability assessment of sunscreens.
Benzylidene camphor and dibenzoylmethane derivatives, Int J
Cosmet Sci 10(2) 53–62 (1988) doi: 10.1111/j.1467-2494.1988.
tb00002.x
22. NM Roscher, MKO Lindemann, S Bin Kong, CG Cho and P Jiang,
Photodecomposition of several compounds commonly used as
sunscreen agents, J Photochem Photobiol Chem 80 (1) 417–421
(1994) doi: 10.1016/1010-6030(94)01043-9
23. W Schwack and T Rudolph, Photochemistry of dibenzoyl methane
UVA filters part 1, J Photochem Photobiol 28(3) 229–234 (B 1995)
doi: 10.1016/1011-1344(95)07118-L
24. JJ Vallejo, M Mesa and C Gallardo, Evaluation of the avobenzone
photostability in solvents used in cosmetic formulations, Vitae 18(1)
63–71 (2011)
25. E Damiani, L Greci, R Parsons and J Knowland, Nitroxide radicals
protect DNA from damage when illuminated in vitro in the presence
of dibenzoylmethane and a common sunscreen ingredient, Free
Radic Biol Med 26 (7–8) 809–816 (1999)
26. M Kojić, M Petković, and M Etinski, A new insight into the photo-
chemistry of avobenzone in gas phase and acetonitrile from ab initio
calculations, Phys Chem Chem Phys 18(32) 22168–22178 (2016)
doi: 10.1039/C6CP03533G
27. GHG Trossini, VG Maltarollo, RD Garcia, CASO Pinto, MVR Velasco,
KM Honorio and AR Baby, Theoretical study of tautomers and
photoisomers of avobenzone by DFT methods, J Mol Model 21(12)
319 (2015) doi: 10.1007/s00894-015-2863-2

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CT1710_Research_Dutta_fcx.indd 35 9/19/17 5:39 PM


Research | C&T ®

KEY POINTS
• Chemical delivery systems use additional
chemicals to introduce ingredients into
the skin.

• This installment concludes our skin delivery


series with a discussion on chemical
penetration; part one covered physical delivery.

A Dermatological View

Breaking
Part II:
Through Chemical Ingredient Delivery*

B
Mike Rule and
Howard I. Maibach, M.D.
University of California
San Francisco iochemical means of penetration enhance-
ment include the use of pro-drug molecules,1
chemical modification,2 enzyme inhibition,3
and vesicular systems or colloidal particles.4
While the previous column discussed physi-
*Adapted with permission from M Rule,
cal means for the active and passive delivery
K Saliesh, T Haw-Yueh, H Zhai and HI Maibach,
Percutaneous penetration enhancers: An Over- of chemicals through skin, this installment focuses on examples of
view, in Handbook of Cosmetic Science and chemical approaches, which are gaining acceptance for the delivery of
Technology, 4th edn, CRC Press, Boca Raton, chemicals into skin.
FL (2014) pp 141–156

Reproduction in English or any other language of


36 | www.CosmeticsandToiletries.com all or part of this article is strictly prohibited. Vol. 132, No. 9 | October 2017
© 2017 Allured Business Media.

CT1710_Research_Maibach_irv.indd 36 9/19/17 2:40 PM


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CT16_ad_template.indd 1 8/9/17 11:49 AM


A Dermatological View

Once a surfactant contacts skin, it binds


to deeper proteins by denaturing surface
proteins, causing the SC to swell.

Colloidal Particles Transferosomes: Transferosomes consist of


phospholipids, cholesterol and additional “edge
Among the various chemical strategies
activators”—i.e., surfactant molecules such as
used, special formulation approaches—based
sodium cholate. Transferosome inventors state
mainly on the usage of colloidal carriers—are
that 200–300 nm transferosomes are ultra-
perhaps the most promising. Liposomes, i.e.,
deformable and squeeze through pores less
phospholipid-based artificial vesicles, and nio-
than one-tenth of their diameter, and are thus
somes, which are nonionic surfactant vesicles,
able to penetrate intact into skin. The penetra-
are widely used to enhance drug delivery
tion of these colloidal particles works best
across skin. In addition, proliposomes and
under in vivo conditions and requires a hydra-
proniosomes, which are converted to liposomes
tion gradient from the skin surface toward the
and niosomes upon hydration, are also used in
viable tissues to encourage skin penetration
transdermal drug delivery.5
under non-occluded conditions.
Generally, these colloidal carriers are not
Ethosomes: In addition, ethosomes, which
expected to penetrate into viable skin. Most
are liposomes high in ethanol content (up to
reports cite a localizing effect, whereby the
45%), penetrate skin and enhance compound
carriers accumulate in the stratum corneum
delivery into deep skin strata or even system-
(SC) or other upper skin layers. However, a new
atically. Their suggested mechanism is that
type of liposome, called a transferosome, has
ethanol fluidizes both ethosomal lipids and lipid
been introduced, which is believed to penetrate
bilayers in the SC, allowing the soft, malleable
deeper and intact.6, 7
vesicles to penetrate through the disorganized
lipid bilayers.8
Surfactant interactions: In recent years,
Read Part 1 (“Physical Ingredient Delivery”) new information on the interactions between
of this series in the September 2017 issue surfactants and the skin has been reported,
of Cosmetics & Toiletries. Find them in your which explains their utility in these delivery
digital edition (click on Back Issues) or online systems. Once a surfactant contacts the
at www.cosmeticsandtoiletries.com/ skin, it binds to the skin’s deeper proteins by
magazine/pastissues/2017/. denaturing the surface proteins, causing the
stratum corneum to swell. This disorganizes
the intercellular lipids of the skin—i.e., the
fluid lipids and removal of the calcium ions
The skin care segment is expected to earn or surrounding ions, causing a reduction of
$130 billion in sales by 2017, accounting corneocyte adhesion—leading to accessibility of
deeper proteins.9
for 41% of the global volume of ingredients,
Mechanisms of action: Six potential mecha-
according to Kline Group.
nisms of action for colloidal carriers have been
proposed:10
Source: Global Cosmetic Industry
1. Penetration by a free drug process—i.e.,
(www.GCImagazine.com) the drug releases from the vesicle then
penetrates skin independently;

38 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Research_Maibach_fcx.indd 38 9/20/17 4:59 PM


2. Penetration of the SC by intact liposomes; In particular, the efficacy of PEs toward
3. Enhancement due to the release of lipids the delivery of high-molecular weight drugs
from carriers and interaction with the remains limited. Attempts to improve enhance-
SC lipids; ment by increasing the potency of enhancers
4. Improved drug uptake by skin; inevitably lead to compromised safety; indeed,
5. Different enhancement efficiencies to achieving sufficient potency without irritancy
control drug input; and has proven challenging.
6. The role of protein, which requires Nano-structured lipid carriers, nanoemul-
elaboration. sions and oil solutions are receiving increased
attention for advantages such as ease of manu-
Chemical facturing, thermodynamic stability, enhanced
Penetration Enhancers drug solubilization and increased drug perme-
Substances that help promote drug diffusion ation rate.12
through the SC and epidermis are referred to For example, Tsai and colleagues created a
as penetration enhancers (PEs), accelerants, hesperetin-carrying microemulsion that showed
adjuvants or sorption promoters.11 PEs have improved permeation in comparison to non-
been extensively studied given their advantages, microemulsion aqueous solutions.12 A similar
such as design flexibility with formulation oil-based nano-carrier system of ropinirole,
chemistry and patch application over large used to treat Parkinson’s Disease, was found
areas. PEs improve drug transport by reducing to have good pharmacokinetic features, with
the resistance of the SC to drug permeation. To potential to replace oral dosage forms; it also
date, no existing chemical penetration enhancer showed sufficient manipulation of the stratum
has proven to be perfect. corneum barrier.13

Vol. 132, No. 9 | October 2017 Cosmetics & Toiletries® | 39

CT1710_Research_Maibach_fcx.indd 39 9/20/17 11:01 AM


A Dermatological View

The increasing understanding of mechanisms


of penetration should accelerate the
development of passive and active enhancers
for use with active cosmetic ingredients.

The solubility of microemulsions and as carriers for topical drugs. For instance, a
nanoemulsions is the reason for their increased chemical complex of arginine and chitosan
permeation for improved drug delivery. This was formed to see what value it may hold as a
is due to the partitioning of the drug between penetration enhancer for the drug adefovir—an
the internal oil phase and external aqueous acyclic nucleoside phosphonate used as a
phase.14 An increase in drug solubility within broad-spectrum antiviral that is highly effec-
the external phase will progress the partitioning tive against herpes-, retro- and hepadviruses.18
effect from the internal to the external phase; Here, N-arginine chitosan (N-Arg-CS) proved
thus, the drug will be able to diffuse easier to its potential as a novel transdermal enhancer,18
be discharged.14 offering an alternative method to disrupt the
In relation, emulsifiers can explain increased molecular protein side-chains within the stra-
skin permeation due to enhanced partitioning tum corneum, in turn creating specific methods
of the actives into skin.15 Micelles and liquid for enhancement.
crystalline phases affect the solubility proper-
ties of active ingredients, in turn changing their Conclusion
thermodynamic movement.15 Otto confirmed All in all, the increasing understanding of
that emulsifiers arranged in liquid crystalline mechanisms of penetration, along with wide-
structures in the water phase enhanced the skin spread use of penetration enhancers, should
penetration of active ingredients.15 accelerate the development of both passive and
Interestingly, a recent study by Degim active—physical and chemical—enhancers for
found that multi- and double-walled carbon use with active cosmetic ingredients.
nanotubules also have permeation effects, For more on this subject, the Dragicevic
similar to drug carriers.16 While their penetra- textbooks referenced provide detailed summa-
tion enhancement is through absorption and ries of this rapidly expanding literature.19–23
subsequent desorption, i.e., a depot effect, the
carbon nanotubules did not penetrate the skin. References
However, Degim gave the nanotubules a high
1. S Wang, M Kara and TR Krishnan, Transdermal delivery of
loading to enhance the transdermal penetration cyclosporin-A using electroporation, J Control Release 50
of especially hydrophobic drugs.16 (1–3) 61–70 (1998)
Additional information has been published 2. A Boucaud et al, Effect of sonication parameters on trans-
dermal delivery of insulin to hairless rats, J Control Release
on the advantages of nanostructured lipid
81 (1–2) 113–119 (2002)
carriers. Using idbenone (IDB), a compara-
3. E Vranic, Sonophoresis-mechanisms and application, Bosn
tive study was made between nanostructured J Basic Med Sci 4 (2) 25–32 (2004)
lipid carriers (NLCs), nano-emulsions and oil 4. KB Sloanand and N Bodor, Hydroxymethyl and acyloxy-
solutions in order to determine which improved methyl prodrugs of theophylline: Enhanced delivery of polar
drugs through skin, Int J Pharm 12 299 (1982)
chemical stability and enhanced skin delivery.
5. HK Choi, GL Flynn and GL Amidon, Transdermal delivery of
NLCs significantly improved the chemical
bioactive peptides: The effect of N-decylmethyl sulfoxide,
stability of IDB, as well as skin permeation and pH and inhibitor on enkephalin metabolism and transport,
formulation stability, compared with NE and Pharm Res 7 1099 (1990)
oil solution.17 6. K Morimoto et al, Effects of proteolytic enzyme inhibitors on
enhancement of transdermal iontophoretic delivery of vaso-
NLCs will continue to progress in the pressin and analogue in rats, Int J Pharm 81 119 (1992)
transdermal field and can effectively be used

40 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Research_Maibach_irv.indd 40 9/19/17 2:40 PM


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CT16_ad_template.indd 1 9/14/17 10:31 AM


A Dermatological View

Ingredients can be introduced to the skin through penetrating chemical delivery systems in formulas.

7. M Mezei and V Gulasekharam, Liposomes-a selective drug 16. Azeem et al, Oil based nanocarrier system for transdermal
delivery system for the topical route of administration. I. delivery of ropinirole: A mechanistic, pharmacokinetic and
Lotion dosage form Life Sci 26 1473 (1980) biochemical investigation, Int J Pharm 422 1–2 436–44
8. MJ Choi and HI Maibach, Liposomes and niosomes as (2012)
topical drug delivery systems, Skin Pharmacol Physiol 18 17. Abdullah et al, In vitro permeation and in vivo anti-inflam-
209–219 (2005) matory and analgesic properties of nanoscaled emulsions
9. MD Planas et al, Noninvasive percutaneous induction of containing ibuprofen for topical delivery, Int J Nanomedicine
topical analgesia by a new type of drug carrier and prolon- 6 387–96 (2011)
gation of local pain insensitivity by anesthetic liposomes, 18. Otto et al, Effect of emulsifiers and their liquid crystalline
Anesth Analg 75 615–621 (1992) structures in emulsions on dermal and transdermal delivery
10. BW Barry, Novel mechanisms and devices to enable of hydroquinone, salicylic acid and octadecenedioic acid,
successful transdermal drug delivery, Eur JPharm Sci 14 Skin Pharmacol Physiol 23 5 273–82 (2010)
101–104 (2001) 19. N Dragicevic and HI Maibach, Percutaneous penetration
11. G Cevc, Transfersomes, liposomes and other lipid suspen- enhancers, chemical methods, in Penetration Enhancement:
sions on the skin: Permeation enhancement, vesicle Modification of the Stratum Corneum, vol 1, Springer, Berlin
penetration and transdermal drug delivery, Crit Rev Ther (2016)
Drug Career Syst 13 257–388 (1996) 20. N Dragicevic and HI Maibach, Percutaneous penetration
12. E Touiton et al, Ethosomes-novel vesicular carriers for enhancers, chemical methods in Penetration Enhancement:
enhanced delivery: characterization and skin penetration Drug Manipulation Strategies and Vehicle Effects, vol 2,
properties, J Control Rel 65 403–418 (2000) Berlin, Springer (2016)

13. Som et al, Status of surfactants as penetration enhancers 21. N Dragicevic and HI Maibach, Percutaneous penetration
in transdermal drug delivery, J Pharm Bioallied Sci 4(1) 2–9 enhancers, chemical methods, in Penetration Enhancement:
(2012) Nanocarriers, vol 3, Springer, Berlin (2016)

14. WR Pfister, S Dean and ST Hsieh, Permeation enhancers 22. N Dragicevic and HI Maibach, Percutaneous penetration
compatible with transdermal drug delivery systems. I, Selec- enhancers, chemical methods, in Penetration Enhancement,
tion and formulation considerations, Pharm Tech 8 132 vol 4, Springer, Berlin (2016)
(1990) 23. N Dragicevic and HI Maibach, Percutaneous penetration
15. Tsai et al, In vitro permeation and in vivo whitening effect enhancers, chemical methods, in Penetration Enhancement,
of topical hesperetin microemulsion delivery system, Int J vol 5, Springer, Berlin (2016)
Pharm 388 1–2 257–62 (2010)

42 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Research_Maibach_irv.indd 42 9/19/17 2:40 PM


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CT16_ad_template.indd 1 9/20/17 9:47 AM


Testing | C&T ®

KEY POINTS
• Considering more and more sun care products
are claiming infrared (IR) protection, it is
important to standardize the parameters by
which they are evaluated.

• Since IR-A and IR-B are the most implicated


in skin damage, a test method was developed
based on these wavelengths, as described here.

Reproduction in English or any other language of


| www.CosmeticsandToiletries.com
44 Reproduction in English or any other language of all or part of this all or part
article of this prohibited.
is strictly article is strictly
© 2017 prohibited.
Allured Business Media. Vol. 132, No. 9 | October 2017
© 2017 Allured Business Media.

CT1710_Testing_Miksa_fcx.indd 44 9/20/17 9:34 AM


Are Your
Sunscreens
Infra-ready?
New In vitro Method Puts
Data Behind the Claims
Elise Delamour, Sébastien Miksa and Dominique Lutz
HelioScreen Labs, Creil, France

T
protection. Indeed, research has highlighted
the potentially harmful effects of IR, includ-
ing: inflammation; heat damage; photoaging
via the up-regulation of matrix metallopro-
teinase-1 (MMP-1) expression in fibroblasts;
oday, sun protection is degeneration of nuclear DNA (nDNA) and
generally accepted as mitochondrial DNA (mtDNA); the formation of
a part of everyday life. free radicals; etc.1–4
This is due in part to the On the contrary, some research demon-
increased incidence in the strates IR radiation can benefit humans.
number of skin cancers, It shows energizing properties, which are
as well as awareness campaigns. As such, more useful in health care for blood circulation and
and more consumers demand efficient sun to boost healing. Moreover, a recent study
protection. They expect sunscreens to provide demonstrates that IR radiation helps to better
good UV protection, since overexposure to prepare skin for upcoming insults, includ-
UVB (290 nm to 320 nm) and UVA (320 nm ing UV-induced sunburn, and can be used to
to 400 nm) leads to sunburn, premature prompt photo-preventive measures.5 It may
skin aging and, potentially, the development therefore be the case that similar to UV, the
of cancer. devil is in the dose, and relative protection can
They also look for sun protection with be effective regardless of the benefits or detri-
added characteristics, such as infrared (IR) ments IR has on skin.

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Are Your Sunscreens Infra-ready?

IR protection factors should be comparable


between products and provide the balance of
UV, visible and IR protection within
a single product.

Considering that more and more sun care Substrate Selection


products are claiming IR protection and in light
For the described tests, two types of
of the precautionary principle, it is important
substrates were used: molded polymethyl
for product developers to standardize the
methacrylate (PMMA) plates with one rough-
parameters by which their products are tested
ened face, for measurements from 290 nm to
to substantiate this claim. As such, an in vitro
700 nma; and quartz plates with one smooth
method is required that can assess the IR
face, for measurements from 700 nm to
protection of sunscreens; this was the focus of
3,000 nm. For this last range, quartz plates were
the present work.
chosen to avoid saturating the measurements
According to the International Commis-
with background noise. The application area
sion on Illumination (CIE), IR radiation can
on these two substrates measured more than
be divided into three bands: IR-A (700 nm to
23 cm². To conserve the reproducibility of test
1,400 nm), IR-B (1,400 nm to 3,000 nm) and
measurements, all surface topography param-
IR-C (3,000 nm to 1 mm).6 Since IR-A and IR-B
eters of the molded plates were controlled with
are the most implicated in skin damage, an IR
an ad hoc profilometer and complied with the
protection test method was developed focused
specifications described in the ISO 24443:2012
on these wavelengths. The resulting approach is
standard (In Vitro UVA-PF Determination).8
described here.
Roughness was previously identified as an
important factor for the reproducibility of
Test Formulas absorbance curve shapes.9–11
To perform the assessment, 25 products from
different companies were tested (see Table 1). Sunscreen Application
These comprised different forms—i.e., cream,
Before sunscreens were applied to test
milk, emulsion, oil, alcoholic spray, stick, etc.;
substrates, they were stored at 25°C for 24 hr
and different levels of protection, ranging
and shaken to assure good homogenization.
between SPF 6 and 50+ (per European Recom-
To obtain a constant and homogeneous layer,
mendation 2006 on the efficacy of sunscreen
the thicknesses and amounts of the products
products and the claims made relating thereto).7
spread were adjusted for the roughness of the
substrates. Thus, a quantity of 1.3 mg/cm²
was applied to molded PMMA plates whereas
0.75 mg/cm² was applied to quartz plates. In
both cases, samples were deposited in nine spots
The mass and premium sun protection using a 1-mL syringe.
market is projected to reach U.S. $9.3 billion
worldwide by 2020. This growth is driven in Automated Spreading
part by demand for full-spectrum protection. Immediately after deposition, products were
spread by means of an automated deviceb whose
robotic arm performs precise and repeatable
Source: Euromonitor International
circular and linear strokes with controlled
pressure. At the top of this arm, a silicone finger

a
Helioplate HD6, HelioScreen

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is used to mimic the human finger to allow for better
spreading in terms of reproducibility.12

Drying Time
After products were spread, they were allowed to dry
and set for 15 min at 25°C ± 2.0°C. During this drying
process, the temperature of the product was controlled
and maintainedc. Indeed, the influence of temperature
on results during in vitro sunscreen testing has also
been demonstrated.13

Sample Irradiation
To assess the photostability of products, it is neces-
sary to perform an irradiation step. And to simulate

b
HD-Spreadmaster, HelioScreen
c
HD-Thermaster, HelioScreen

Table 1. Sunscreens Selected for IR Study

Product Form Labelled SPF


P1 Cream 30
P2 Milk 30
P3 Alcoholic spray 50
P4 Cream 20
P5 Stick 50+
P6 Cream 50+
P7 Colored cream 50+
P8 Cream 50+
P9 Colored cream 30
P10 Stick 30
P11 Milk 30
P12 Oil 6
P13 Cream 20
P14 Cream 50+
P15 Alcoholic spray 50
P16 Foundation 30
P17 Foundation 30
P18 Milk 30
P19 Milk 50
P20 Cream 50+
P21 Oil 30
P22 Foundation 20
P23 Cream 50
P24 Cream 15
P25 Cream 50

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Are Your Sunscreens Infra-ready?

a typical absolute UV exposure dose, rather from 400 nm to 700 nm, and an IR spectropho-
than a dose proportional to the SPF number or tometerg for measurements from 700 nm to
UVA-PF, a fixed dose is preferred; in fact, this 3,000 nm.
approach has been proposed according to exist-
ing in vitro methods recognized worldwide.14 Mathematical Adjustments
For this purpose, a solar simulator was used to Using the described measurements, a total
expose samples to 800 J/m²-eff—equivalent to 4 spectrum of the tested products between 290 nm
minimal erythema doses (MEDs), where 1 MED and 3,000 nm is obtained. However, to correlate
is equal to 200 J/m²-eff. with in vivo methods and take the different
substrates and spectrophotometers used into
Transmittance consideration, some mathematical adjustments
Measurements are necessary.
To assess the SPF and UVA protection factor Calculated in vitro SPF versus measured
(UVA-PF), and the critical wavelength (CW) of a in vivo SPF: The first adjustment is to align
sunscreen, the transmittance of a product must the in vitro SPF calculated according to the UV
be measured by means of a spectrophotometer. spectrum measured (see Equation 2) with the
For the present work, the absorbance amounts in vivo SPF value. For this, the initial absor-
used were in the UV, visible, IR-A and IR-B bance curve values are multiplied by a scalar
ranges, as shown in Equation 1. value, C, until the in vitro calculated SPF values
are equal to the in vivo measured SPF. This is
A(l) = log[T(l)] Eq. 1 accomplished in an iterative calculation process:

Here, A is the absorbance of the tested prod- l = 400 nm


∫ E(l) × I(l) × dl)
uct; T is the transmittance of the tested product l = 290 nm
SPFIn vitro =
expressed as a percentage; and l is the wave- l = 400 nm
∫ E(l) × I(l) × 10-A (l) × dl
length with an interval of 1 nm. To assess the
0
l = 290 nm
entire UV, visible, IR-A and IR-B range, different Eq. 2
spectrophotometers and substrates were used,
depending on the wavelength being measured. Here, E(l) is the erythema action spectrum
To obtain the UV spectrum, measurements (CIE-1987); I(l) is the spectral irradiance
were performed from 290 nm to 400 nm using received from the UV source (SSR for SPF
a UV spectrophotometerd. For the visible, IR-A testing); A0(l) is the mean monochromatic
and IR-B spectrums, two approaches were used, absorbance of the test product layer before
with or without an integrating sphere. The UV exposure; and dl is the wavelength step (1
function of an integrating sphere is to spatially nm). The initial absorbance values multiplied
integrate diffuse reflectance and illuminate by the C value become the adjusted sunscreen
samples with the complete spectrum and/or absorbance curve.
collect scattered transmission light. Without an The calculation of the adjusted in vitro
integrating sphere, considering optical geometry SPF, or SPFIn vitro, adj, and determination of the
and sample/device positioning, all the measured coefficient of adjustment, C, are described in
light from a sample could be missed, leading to Equation 3.
a variance in the results. Thus, this study also
provided a comparison in terms of the absence l = 400 nm
∫ E(l) × I(l) × dl
or presence of an integrating sphere inside l = 290 nm
SPFIn vivo = SPFIn vitro, adj =
the spectrophotometer. l = 400 nm
∫ E(l) × I(l) × 10-A (l) × C × dl
l = 290 nm
0

For the present study, the first approach


was to use a UV, visible and near-infrared (NIR) Eq. 3
spectrophotometere including an integrating
sphere. The second approach was to use a Again, E(l) is the erythema action spectrum
visible spectrophotometerf for measurements (CIE-1987); I(l) is the spectral irradiance
received from the UV source (SSR for SPF
d
UV-2000S, Labsphere Inc.
e
V-770 UV-Visible/NIR Spectrophotometer, Jasco
f
Cary 60 UV-Vis, Agilent Technologies
g
Spotlight 400 FT-IR Imaging System, Perkin-Elmer

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Product application, spreading and dry time were considered in order to test claims.

testing); A0(l) is the mean monochromatic or IR ranges, it is not necessary to calculate


absorbance of the test product layer before UV the Ratio(x). Indeed, if the same appliances are
exposure; C is the correlation coefficient; and dl used, i.e., spectrophotometer and substrate, no
is the wavelength step (1 nm). mathematical adjustments are necessary.
Equipment variations: Other adjustments
were made for differences in test equipment
∑A
used. For this step, a Ratio(x) is calculated Ratio(x) =
a1
Eq. 4
∑Aa2
between one part of the absorbance curve
already adjusted for the UV range (Aa1) and
∑A
the second curve for the visible range (Aa2) Ratio(y) =
a3
Eq. 5
∑Aa4
(see Equation 4). Following this first step, the
same logical principle is applied between the
absorbance for the visible range (Aa3) and for Here, Aa1 is the absorbance from 395 nm
the IR range (Aa4) to calculate the Ratio(y) (see to 400 nm in the adjusted UV range; Aa2 is the
Equation 5). absorbance from 395 nm to 400 nm in the
However, note that if the same spectropho- visible range; Aa3 is the absorbance from 695 nm
tometer is used to measure the UV, visible and/ to 700 nm in the adjusted visible range; and Aa4

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Are Your Sunscreens Infra-ready?

is the absorbance from 695 nm to 700 nm in the Calculating IR Protection


infrared range. After these two ratios are cal-
Based on the adjusted spectrum, different IR
culated, they are multiplied to the absorbance
protection factors can be calculated. One factor
values corresponding to the range requiring
should provide an indication regarding a level
adjustment (see Equations 6 and 7).
of sun protection with which products can be

A1 Vis = A0 Vis × Ratio(x) Eq. 6 compared. A second factor should provide an
indication of the balance between the UV, visible
A1 IR = A0 IR × Ratio(y) Eq. 7 and IR protection provided.
Percent of IR stopped by the product (%IR):
Here, A1 Vis is the absorbance mean between For the first factor, initially the idea was to use
400 nm and 700 nm after mathematical adjust- the irradiance curve of the sun15 to measure
ments per substrate and per wavelength; A0 Vis is an IR Protection Factor (IR-PF). However,
the absorbance mean initially measured from calculating the %IR is preferred because it is
400 nm to 700 nm per substrate and per wave- more dynamic for the values obtained, being
length; A1 IR is the absorbance mean between more sensitive to the small differences that
700 nm and 2,500 nm after mathematical have a large impact on the final value. In fact,
adjustments per substrate and per wavelength; contrary to the IR-PF, the %IR does not factor
and A0 IR is the absorbance mean initially in the irradiance curve; instead, it indicates the
measured between 700 nm and 2,500 nm per IR percentage stopped by the tested product. In
substrate and per wavelength. other words, it is the percentage of IR absorbed
All things considered, and after mathemati- or reflected by the product.
cal adjustments, Figure 1 shows an example of Thus, the higher the percentage, the more
the final absorbance spectrum between wave- the product protects the skin against IR. This
lengths 290 nm to 3,000 nm for product P17. factor can be calculated separately for %IR-A

Figure 1. Absorbance spectrum of product P17 after adjustments

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and %IR-B; or, for IR-A and IR-B combined Similar to %IR, it is also possible to dif-
(%IR), only the wavelengths (l1 and l2) change ferentiate the CW for IR-A only (lIRA-CW) (see
(see Equations 8 and 9). Equation 10) or IR-A and IR-B together (lIR-CW)
∑T1 IR l1 to l2 (see Equation 11). The IRA-CW is equal to 90%
%Transmittance IR = Eq. 8 of the area under the absorption curve of the
n
total area between 290 nm and 1,400 nm. On
%IR = 100 − %Transmittance IR Eq. 9 the other hand, the IR-CW is equal to 90% of the
area under the absorption curve of the total area
Here, T1 IR is the mean of the transmittance between 290 nm to 2,500 nm. Following this
per substrate and wavelength; n is the number mathematical principle, IR-CW can be named
of transmittance measurements; for total IRB-CW as these are equal.
%IR (i.e., %IR-A and %IR-B combined): l1 is
equal to 700 nm and l2 is equal to 2,500 nm; lIR-CW l = 1,400 nm
lIRA-CW = ∫ A1 IRl• dl = 0.9 × ∫ A1 IR l • dl
for %IR-A only: l1 is equal to 700 nm and l2 is l = 290 nm l = 290 nm

equal to 1,400 nm; for %IR-B only: l1 is equal to Eq. 10


1,400 nm and l2 is equal to 2,500 nm.
Critical wavelength extended to IR (IR-
CW): The IR-CW is based on the same principle lIR-CW l = 2,500 nm
lIRA-CW = ∫ A1 IRl• dl = 0.9 × ∫ A1 IR l • dl
as the CW. However, instead of staying in the UV l = 290 nm l = 290 nm

band, this wavelength is extended to the visible Eq. 11


and IR bands.16, 17 This factor gives an indication
of the balance between UV, visible and Here, A1 IR l is the mean of the absorbance
IR protection. measurements after mathematical adjustments

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Are Your Sunscreens Infra-ready?

per plate and wavelength; and l is the wave- for each IR protection factor were calculated
length with an interval of 1 nm. The 25 products as follows, taking the integrating sphere
described previously (see Table 1) were into account:
tested and their %IRs were calculated. Results
obtained with and without an integrating sphere %IR ≥ 10%; %IRA ≥ 12.5%; and %IRB ≥ 10%
are presented in Table 2.
IR-CW ≥ 1,200 nm; IRA-CW ≥ 900 nm; and
Method Selectivity and
IRB-CW ≥ 1,200 nm
Discussion
To ensure any method is credible and can According to these parameters, only four
distinguish between products, it must demon- products of the 25 tested—P16, P17, P20 and
strate reasonable selectivity. For this method, an P22—demonstrated IR protection efficacy (see
80–90% level of selectivity was set and the limits Table 2). Adjustments to the chosen criteria

Table 2. Results Obtained for IR-PFs With and Without Integrating Sphere

With an integrating sphere Without an integrating sphere


PRODUCT
REFERENCE IRA-CW IR-CW* IR-CW*
%IRA %IRB %IR %IRA %IRB %IR IRA-CW
(nm) (nm) (nm)
P1 3.1 2.1 2.7 497 610 24.1 14.5 20.3 1,099 1,398
P2 3.8 2.6 3.3 577 719 12.4 8.8 10.9 989 1,318
P3 < 0.1 < 0.1 < 0.1 376 374 10.0 7.5 9.0 885 1,189
P4 6.4 4.8 5.8 837 1,155 22.1 14.6 19.1 1,134 1,468
P5 7.8 4.6 6.5 779 978 18.4 12.5 16.1 1,029 1,351
P6 5.1 4.2 4.8 612 830 18.6 16.0 17.6 1,064 1,452
P7 10.5 6.6 9.0 836 1,081 31.5 25.4 29.1 1,139 1,519
P8 5.6 4.6 5.2 644 894 14.3 12.3 13.5 998 1,380
P9 1.0 1.4 1.2 386 392 23.0 20.0 21.8 1,166 1,554
P10 < 0.1 < 0.1 < 0.1 374 373 4.4 5.0 4.7 718 1,189
P11 2.5 2.3 2.4 453 593 8.7 5.5 7.4 889 1,149
P12 0.0 1.4 0.6 374 371 1.6 0.3 1.1 513 557
P13 < 0.1 < 0.1 < 0.1 377 377 12.0 11.5 11.8 1,056 1,470
P14 < 0.1 < 0.1 < 0.1 361 354 4.2 3.1 3.8 557 709
P15 < 0.1 < 0.1 < 0.1 374 371 4.8 5.9 5.3 656 1,107
P16 37.3 18.5 29.9 1,089 1,340 49.4 24.3 39.5 1,115 1,352
P17 44.9 26.3 37.5 1,106 1,405 65.7 45.8 57.8 1,174 1,505
P18 < 0.1 < 0.1 < 0.1 376 374 22.7 20.4 21.8 1,165 1,562
P19 19.0 8.1 14.7 940 1,134 18.8 6.6 14.0 921 1,054
P20 13.5 11.4 10.8 915 1,216 30.5 28.5 29.7 1,175 1,580
P21 < 0.1 < 0.1 < 0.1 373 367 5.4 13.3 8.5 731 2,280
P22 28.9 16.2 23.8 1,086 1,384 38.9 23.9 32.5 1,220 1,561
P23 1.0 1.1 1.0 382 385 12.3 10.4 11.6 981 1,368
P24 1.8 1.9 1.9 398 495 15.4 13.3 14.6 1,111 1,505
P25 3.6 2.9 3.3 521 709 14.1 10.5 12.7 996 1,345

*IR-CW is equal to IRB-CW

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Products providing IR protection were mainly
colored, allowing one to assume the pigments
may have an influence on IR protection.

could improve these results, although it is on the IR absorbance was calculated; internally,
important to consider key aspects that may be it was concluded there is no significant influence
affecting these results. For example, the fixed of this parameter on the IR-CW factor.
limits could indeed be too selective; the panel Finally, according to Table 2, it can be
of products may actually only include four with observed that the products providing IR pro-
real IR protection; or all the selected products tection were mainly colored, allowing one to
may provide IR protection but in terms of assume the pigments may have an influence on
biological effects rather than absorbance. IR protection in terms of physical effects only.
Moreover, for the IR-CW, we can assume that Indeed, some inactive ingredients are capable
if the tested product absorbs greatly in the vis- of absorbing and/or scattering visible and/or IR
ible range, its IR-CW will be superior or equal to radiation; such as iron oxides, titanium dioxide,
the fixed limit, even if the product does not show zinc oxide, boron nitride, bismuth oxychloride,
efficient IR protection. To check this hypothesis, nylon-12, lithium magnesium sodium silicate,
the relative influence of the visible absorbance magnesium aluminium silicate, polyacrylamide,

Figure 2. Repeatability assessments

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Are Your Sunscreens Infra-ready?

Only four products showed


IR absorbance but other
means of IR protection
must be considered, such
as biological efficacy.

silica, boron nitride, etc.17 Moreover, from these This product passed the criteria limit with an
results, it seems there is no link between the integrating sphere and failed it without an inte-
level of SPF and IR protection. In fact, products grating sphere. Why? Considering its formula,
P9 and P17 both had an SPF of 30 but %IRs of a high quantity of several inactive ingredients
1.0% and 37.5%, respectively. could explain this difference.
Furthermore, limits of selectivity can be On the contrary, product P7 passed the
set without consideration for the integrating criteria limit without an integrating sphere and
sphere. These are as follows: failed with an integrating sphere. This differ-
ence can be explained either because values
%IR ≥ 25%; %IRA ≥ 30%; and %IRB ≥ 20% are borderline, as far as the limits, or perhaps
a scattering effect is being missed, which leads
IR-CW ≥ 1,500 nm; IRA-CW ≥ 1,100 nm; and to an overestimate of IR protection. Taken
IRB-CW ≥ 1,500 nm together, the integrating sphere is therefore
strongly recommended to avoid any overestima-
According to these parameters, it is interest-
tion of IR protection values or false positives.
ing that just three products—P17, P20 and
P22—exhibited IR protection according to Repeatability and
transmittance measurements with or without
an integrating sphere. And in either case, with Reproducibility
or without the integrating sphere, one product Credible methods must also be repeatable
seems to behave differently: product P16. and reproducible by others under the same

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conditions, e.g., laboratory, equipment, method, still maintains a %CV of less than 20%; in this
etc., with the same products. A moderate and case for all IR factors, as previously described.
reasonable variation, or coefficient of variation Thus, the same tests were performed by differ-
(%CV), should fall below 20%, which in this ent operators, with different appliances and at
case must be evaluated for all %IR values. For different times. Again, five products were tested
this purpose, five products were tested three but by three different operators in under several
times with the same operator and under the different test conditions. The %CV obtained for
same conditions to evaluate the repeatability each product and each IR protection index are
of the method. The %CV obtained for the three illustrated in Figure 3.
assays with each product and each %IR value According to the data, this test method was
are shown in Figure 2. deemed reproducible since the maximum %CV
Here, the fixed objective achieved a %CV of obtained was 14.6%; although it is worth noting
less than 20%. Indeed, the maximum CV was variations in results depended upon the prod-
19.5%, for product P10. Interestingly, the %CV ucts tested. Indeed, some were more difficult to
mainly depended upon the product tested; test, such as product P14.
products P10 and P14, for example, gave more
varied results between the different assays. Conclusions
This difference in terms of %CV is mainly This study shows the development of an
due to the composition of the product that innovative in vitro method to assess the IR
change their physical-chemical parameters protection provided by sun care products.
(superficial tension, rheology, density, volatil- First, sample products are spread onto molded
ity, etc.) and its ability to be spread over the PMMA and quartz plates, and these substrates
substrate, creating a more or less uniform film. are irradiated. The transmittance of UV, visible
Reproducibility is another parameter and IR wavelengths are measured using various
crucial to the validation of a method. A method spectrophotometers, then mathematical adjust-
is considered reproducible when the same ments are made to correlate with in vivo values
method is used under different conditions and and to obtain product absorbance spectrums

Figure 3. Reproducibility assessments

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Are Your Sunscreens Infra-ready?

between 290 nm and 2,500 nm. According to this spectrum, the %IR and
the IR-CW can be calculated to obtain the final IR protection value for
each product.
To be credible and selective enough, an 80–90% selectivity limit was
set among all the tested products. This resulted in just four of the 25
sunscreens tested, i.e., an 84% selectivity, exhibiting results to substanti-
ate claims for IR protection. In fact, using an integrating sphere, this
method showed test products exhibited IR protection when their %IR
was greater or equal to 10% (%IRA ≥ 12.5% and %IRB ≥ 10%), and the
IR-CW was greater or equal to 1,200 nm (IRA-CW ≥ 900 nm and IRB-CW
≥ 1200 nm). If one of these criteria (%IR and IR-CW) was not met, the
product was not deemed to demonstrate IR protection. Furthermore,
IRA or IRB protection could be separately claimed if both criteria (%IRA
and IRA-CW or %IRB and IRB-CW, respectively) were met.
In addition, the importance of the integrating sphere was dem-
onstrated so as to avoid any overestimation of IR sun protection.
Nevertheless, without an integrating sphere, other criteria limits could
also be used to claim IR protection.
To validate this method, it had to be repeatable and reproducible with
%CV of less than 20% for all IR protection factors. These objectives were
achieved, as the maximum %CV for repeatability and reproducibility
were 19.4% and 14.6%, respectively.
Furthermore, all color-containing products in the described tests
showed positive results for IR protection. This seems to indicate pig-
ments may improve IR protection in physical terms. This study also
highlights the fact that SPF levels had no influence on levels of IR protec-
tion. Additional tests should therefore be performed to assess whether
the fixed limits were too strict; the panel of products selected indeed
comprised only a few IR-protective; or if the selected products provided
IR protection via biological effects.
Based on the described method, a standardized logo should be
proposed to be append product packaging. This will inform consumers
that the product provides IR protection in accordance with a future
international harmonization.

Acknowledgements: The authors wish to thank Alexandre Lauer, Delphine Roger, Axelle Casanova and
Mary Sinoquet, of Chanel Parfum Beauté–Pantin, for their support; and Rudy Camart for performing a
portion of the tests.

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56 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Testing_Miksa_fcx.indd 56 9/20/17 9:34 AM


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5. VC Gonzalez, AC Beheregaray, BM Peres, ES Sallis, AS Varela, Jr,


and GS Trindade, Histopathological analysis of UVB and IR interac-
tion in rat skin, Photochem Photobiol 91(4) 895-900 (Jul/Aug 2015)
doi: 10.1111/php.12435
6. Commission Internationale de l’Éclairage (CIE), available at
www.techniques-ingenieur.fr/base-documentaire/electronique-
automatique-th13/fondamentaux-de-l-optique-42448210/
commission-internationale-de-l-eclairage-cie-r86 (Accessed Aug 30,
2017)
7. Commission of the European Communities, Commission recom-
mendation of 22 September 2006 on the efficacy of sunscreen
products and the claims made relating thereto, available at http://
eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:32006H0
647&from=EN (Accessed Aug 30, 2017)
8. Determination of sunscreen UVA photoprotection in vitro, ISO
24443:2012, available (for purchase) at www.iso.org/stan-
dard/46522.html (Accessed Aug 30, 201)
9. L Ferrero, M Pissavini, A Dehais, S Marguerie and L Zastrow, Impor-
tance of substrate roughness for in vitro sun protection assessment,
Int J Cos Sci 9(2) (Apr/Jun 2006)
10. M Pissavini, S Marguerie, A Dehais, L Ferrero and L Zastrow,
Characterizing roughness: A new substrate to measure SPF, Cosm
& Toil 124(9) (Sep 2009)
11. S Miksa, D Lutz and C Guy, In vitro/vivo SPF correlation and repeat-
ability according to substrate, Cosm & Toil 128(9) (Sep 2013)
12. S Miksa, D Lutz and C Guy, In vitro UV testing—Robot vs. human
spreading for repeatable, reproducible results, Cosm & Toil 128(10)
(Oct 2013)
13. S Miksa, D Lutz and C Guy, UV transmission assessment: Influence
of temperature on substrate surface, Cosm & Toil 128(7) (Jul 2013)
14. S Miksa, D Lutz and C Guy, Dynamic photostability test method for
additional sunscreen claims, Cosm & Toil 131(1) (Jan/Feb 2016)
15. ASTM G173-03, Reference Spectra Derived from SMARTS v.2.9.2,
available (for purchase) at www.astm.org/Standards/G173.htm
(Accessed Aug 30, 2017)
16. A Duev, G Kelm, RR Wickett and OV Dueva-Koganov, Are SPF and
critical wavelength sufficient to measure efficacy of sunscreen prod-
ucts against sun induced skin damage? Monographic Supplement
Series: Sun Care, HP&C Today 8(4) (Jul/Aug 2013)
17. OV Dueva-Koganov, A Duev, R Tumer and S Micceri, In vitro
evaluation of potential protection provided by topical products
against full solar and visible plus infrared radiation, HP&C Today 9(2)
(Mar/Apr 2014)

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Formulating | C&T ®

L
KEY POINTS
• Passion fruit seed extract is shown to exhibit
antioxidant, skin whitening and sun protection
capabilities in color cosmetics.

• This novel, natural and sustainable source for


cosmetic actives demonstrates a near totality
of claims for formulators and marketers.

Want More On Makeup?


Check out page DE1 of the October digital edition
to find out more about Multifunctional Cosmetics.

Reproduction in English or any other language of


60 | www.CosmeticsandToiletries.com all or part of this article is strictly prohibited. Vol. 132, No. 9 | October 2017
© 2017 Allured Business Media.

CT1710_Formulating_Lourith_fcx.indd 60 9/20/17 5:16 PM


LEVELING
LEVELING
LEVELING
LEVELING
LEVELING
UP
UP
UP
UP
UP Passion Fruit Drives Color Cosmetics Into New Dimensions
Nattaya Lourith and Mayuree Kanlayavattanakul
School of Cosmetic Science, Mae Fah Luang University,
Chiang Rai, Thailand
Jiraporn Chingunpitak
School of Pharmacy, Walailak University, Nakhon Si Thammarat, Thailand

P
assion fruit is well-known as exhibit-
ing an attractive, exotic flower and
characteristic flavor. Its fresh or
processed fruit is highly sought for
health benefits and used in functional
beverages and health drinks. The soft,
edible pulp of this fruit contains tiny
seeds that comprise up to 25% of its fresh weight. These
seeds, along with the peels, are dumped as waste during
juice extraction; they account for more than 75% of the
discarded waste. Therefore, in parallel with increasing
demand for the fruit, the waste portion and residues from
industrial processing of the fruit are also increasing.
In relation, the demand for sustainable, eco-friendly
and natural products including cosmetics is widespread;
although transforming agri-food industry by-products
into specialty ingredients for cosmetics poses challenges.

Vol. 132, No. 9 | October 2017


Reproduction
in English Cosmetics
or any other language of all or part of this article is strictly prohibited. © 2017 Allured Business Media. & Toiletries® | 61

CT1710_Formulating_Lourith_fcx.indd 61 9/20/17 5:16 PM


Leveling Up

Passion fruit seed extract offers a natural


mutifuntional ingredient option, for which
demand continues to grow.

However, the two industries could be more natural multifunctional ingredient option, for
beneficially integrated; indeed, the antioxidant which demand continues to grow and research
polyphenols of passion fruit seed extract1–3 have is exhaustively conducted.6
been reported to exhibit UV filtering capabili-
ties.4, 5 Extract Preparation and
As such, the feasibility of by-products Standardization
from passion fruit processing for cosmetic
Passion fruit seeds from a juice process-
applications motivated the present work. Color
ing factory were extracted1 and assessed for
cosmetics are generally a statement of youth
antioxidant activity by means of the 2,2'-azino-
and give users the pleasure of manipulating
bis(3-ethylbenzothiazoline-6-sulphonic acid)
their appearance to project a positive percep-
(ABTS) assay; a, a-diphenyl-b-picrylhydrazyl
tion of themselves. Furthermore, makeup
(DPPH) method; and ferric reducing ability
incorporating multiple benefits, such as sun
of plasma (FRAP) assay—as well as inhibitory
protection, is preferred by consumers. This
effects against the melanogenesis enzyme
article, therefore, explores the development
tyrosinase. The extracts were quality controlled
of color cosmetics containing a prepared and
by total phenolic content (TPC) using the Folin-
standardized passion fruit seed extract for
Ciocalteu assay.
added antioxidant, skin whitening and sun
The polyphenols were characterized by high-
protection effects.
performance liquid chromatography (HPLC),
Formulas including a liquid foundation and
and the extracts were successfully separated
concealer mousse were developed and tested for
by eluting with a solvent system consisting
quality in terms of efficacy, safety and stabil-
of acetonitrile (AcCN) (A) and 3% aq. acetic
ity, as described. While in today’s formulas,
acid (AcOH) (B) with the following gradient:
organic or physical sunscreens such as TiO2 are
0–3 min 100% B; 3–5 min 85% B; 5–10 min 80%
often used—which has a dual pigment func-
B; 10–15 min 75% B; 15–20 min 70% B; and
tion, although it ineffectively matches Asian
20-30 min 50% B at a flow rate of 1 mL/min.
skin tones—passion fruit seed extract offers a
Fingerprints of the extracts were thereafter
obtained and the phenolic constituents were
analyzed in a comparison with standards. Sun
protection efficacy in terms of in vitro SPF
analysis also was evaluateda and compared with
benzophenone (BP3) and octyl methoxycinna-
The global color market is expected to reach mate (OMC).2
U.S. $77.7 billion in 2020, driven in part by
demand for organic products and increasing Test Formulas and
health awareness; e.g., sun protection. Skin Compatibility
Base liquid foundation and concealer
Source: Markets and Markets mousse formulas (see Formula 1) without the
extract were then developed and evaluated for
stability by centrifugation (3,500 rpm, 30 min)

a
SPF-290 F, Optometrics LLC

62 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Formulating_Lourith_fcx.indd 62 9/19/17 5:40 PM


IFSCC
Plenary Lecture
Challenge to Irreversibility: Aging Revolution
Dr. Sang Chul PARK (DGIST, Korea)

Conference 2017 Keynote Lectures


Skin Biology: New and Alternatives I
24th Conference of the International Federation Skin Biology: New and Alternatives - Utilizing Skin Microbiome
Knowledge in Cosmetic Product Development
of Societies of Cosmetic Chemists
Dr. Nava DAYAN (Skin Science and Research, USA)

October 23-25, 2017 Skin Biology: New and Alternatives II


Stratum Corneum as an Excellent Indicator
Grand InterContinental Hotel, Seoul, Korea Reflecting Skin Conditions
Dr. Tetsuji HIRAO (Chiba Institute of Science, Japan)

Formulations: Innovation & Conversion


Research, Evaluation and Industrialization of
On-site Registration from Active Substance Delivery Systems

September 1, 2017 Dr. Qiang XIA (Southeast University, China)

Active Material: Organic & Natural


www.ifscc2017.com Oxidoreductase Reactions for Cosmeceutical Production from
Soy Bean Products
Dr. Byung-Gee KIM (Seoul National University, Korea)

Cosmeceuticals: Novel & Innovation


Interaction of Free Radicals with Antioxidants in Human Skin:
Conclusions for Sun Protection
Dr. Jürgen LADEMANN (Center of Experimental & Applied Cutaneous
Physiology, Germany)

Color Cosmetics & Hair Care, Skin Barrier


Phytosphingosine and Its Derived Ceramides; Their Versatile Roles
on 'Bricks & Mortar' Formation in Stratum Corneum
Dr. Chang Seo PARK (Dongguk University, Korea)

Cosmetic Science:
Beauty, Convergence
and Creativity

CT16_ad_template.indd 1 9/12/17 3:42 PM


Leveling Up

and by seven heat-cool cycles (4°C ± 2°C for Statistical analysis: All data is presented
24 hr; and 45°C ± 2°C for 24 hr, each cycle). The as the mean ± SD. The parameters were
passion fruit seed extract was then incorporated compared and analyzed using one sample t-test
at 0.1% and 0.3%,1 and the formulas were tested and ANOVA testing with a significance level of
for various effects. Those with appropriated p < 0.05.
SPFs were finally re-assessed for stability, upon
which the pH and sun protection abilities, i.e., Results and Discussion
SPF, Boots star rating and critical wavelength, The passion fruit seed extract was prepared
were recorded.1, 3 by a concise and feasible method from an
Primary skin irritation test: Skin com- industrial practice. Notably, ethyl acetate frac-
patibility with the developed sun protectant tion selected from the crude extract was shown
products was assessed in 20 Thai female volun- as the best candidate active.1 The obtained
teers, all of whom indicated wearing makeup extract had a yield of 1%, which was further
daily. The single-application closed patch test quality controlled in terms of ABTS, DPPH and
was approved by the ethical committee of Mae FRAP assays, as shown in Figure 1.
Fah Luang University prior to enrollment. Antioxidant effects: The extract’s antioxida-
The sample (20 µL) was patched on the volar tive effects were proven by ABTS and DPPH,
forearms of the volunteers for 24 hr using Finn with an inhibitory concentration at 50% (IC50)
chambers (8 mm). Severity of skin irritation of 6.6 µg/mL and 4.4 µg/mL. This anti-free radi-
was graded from 0-4 and calculated into MII cal capability was equivalent to that of 1 mM
(Means Irritation Index) at which < 0.2 was FeSO4 at 2,018.9, whereas those of ascorbic
interpreted as non-irritation. The assessment acid were 3.4, 2.7 and 6,214, respectively.
was undertaken in a comparison with water Considering these activities were prepared from
(negative control) and 0.1% sodium lauryl a crude source, the extract shows promise for
sulfate (positive control) in parallel.1, 3 application in eco-friendly cosmetics; although

Formula 1. Test Products

Foundation Concealer Mousse


C30-45 Alkyl Dimethicone Caprylyl Methicone
PEG-9 Dimethicone Squalane
Cyclopentasiloxane Isostearyl Isostearate
Cyclopentasiloxane (and) Dimethicone Crosspolymer Dimethicone
Titanium Dioxide Talcum
Yellow Iron Oxide-treated Silicone Titanium Dioxide (and) Hydrated Silica (and) Hydrogen
Dimethicone
Black Iron Oxide-treated Silicone Titanium Dioxide
Red Iron Oxide-treated Silicone Yellow Iron Oxide-treated Silicone
Polymethylsilsesquioxane Red Iron Oxide-treated Silicone
Caprylyl Methicone Black Iron Oxide-treated Silicone
Water (Aqua) Dimethicone (and) Cetearyl Dimethicone
Crosspolymer
Propylene Glycol Cyclopentasiloxane (and) Dimethicone Crosspolymer
NaCl Jojoba Oil
Propylene Glycol (and) Diazolidinyl Urea (and)
Methylparaben (and) Propylparaben Beeswax
Triethanolamine Propylene Glycol (and) Diazolidinyl Urea (and)
Methylparaben (and) Propylparaben
Propylene Glycol Propylene Glycol

64 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Formulating_Lourith_fcx.indd 64 9/19/17 5:40 PM


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Leveling Up

Figure 1. Antioxidant and anti-tyrosinase activities of the passion fruit seed extract in
comparison with standards

Figure 2. SPF of the passion fruit seed extract, bench sun protectants and passion fruit
makeup products

66 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Formulating_Lourith_fcx.indd 66 9/19/17 5:40 PM


Passion fruit
concealer mousse provided
a Boots star rating of 4
and a critical wavelength
higher than 370 nm.

the activity of the passion fruit seed extract results for cytotoxicity at the highest concentra-
against free radicals was almost two times less tion of 50 µg/mL.2
potent than standard ascorbic acid. However, Sun protection: As noted, the antioxidant
these levels are feasible to control during the polyphenols in passion fruit seed extract have
manufacturing practice. been identified as promising candidates as UV
Skin hyperpigmentation: In addition, the absorbers for cosmetics.4, 5 Accordingly, the sun
potency of passion fruit seed extract to treat protection potential of the extract was exam-
skin hyperpigmentation was examined in vitro ined in vitro by SPF analysis in a comparison
by comparing its anti-tyrosinase activity with with BP3 and OMC, each at 1% in propylene
that of the standard, kojic acid. The extract glycol. Indeed, the extract produced an SPF,
showed skin-lightening capabilities, as evi- albeit less than that of BP3 and OMC, but its
denced by inhibitory effects against mushroom efficacy was superior to Tanaka, a traditional
tyrosinase of 39.932% ± 0.078%, although sunscreen used in Myanmar (see Figure 2).7, 8
it was less potent than kojic acid (77.665 Test formulas: Once the test extract was
± 0.507%). characterized, base formulas were developed
Quality control: The extract was thereafter and challenged for stability. Those that passed
quantified on its active principles in terms of the centrifugation test were moved on to heat-
total phenolic content and shown to contain cool cycle testing. Consequently, two makeup
58.280 ± 1.146 g GAE/100 g extract. After products—a liquid foundation and concealer
HPLC analysis, quercetin was identified as the mousse, two commonly used product formats—
major polyphenol, followed by rosmarinic, were developed incorporating the passion fruit
chlorgenic and gallic acids; 0.301 ± 0.011 µg/g seed extract at 0.1% and 0.3%.
extract, 0.191 ± 0.015 µg/mg extract, 0.088 ± The final concealer mousse was significantly
0.003 µg/g extract and 0.070 ± 0.006 µg/mg (p < 0.005) superior in SPF to the liquid founda-
extract, respectively.2 tion (see Figure 2), with an SPF greater than
Irritation potential: The extract’s safety 15—the recommended level of protection for
was assessed in vero cells and showed negative everyday application, e.g., via color cosmetics.

Vol. 132, No. 9 | October 2017 Cosmetics & Toiletries® | 67

CT1710_Formulating_Lourith_fcx.indd 67 9/19/17 5:40 PM


Leveling Up

It is noteworthy that the increase in passion slightly acidified but within in an acceptable
fruit seed extract from 0.1% to 0.3% did not range for cosmetics (see Figure 3). Further-
demonstrate a significant effect on SPF. more, the SPF, Boots star rating and critical
These resulting passion fruit concealer wavelength were maintained, confirming the
mousse formulas, with a Boots star rating of stability of the passion fruit concealer mousses.
4 and critical wavelength higher than 370 nm, Irritation tests: Lastly, for economic
highlight the broad sun protection capabilities reasons, and since the 0.1% and 0.3% formulas
these formulas have against UVB and UVA.3 demonstrated equal sun protection-capabilities,
Furthermore, the formulas containing pas- preliminary safety assessments were under-
sion fruit seed extract gave better results than taken on the 0.1% passion fruit mousse. It was
those containing other natural sun protection found to be compatible with skin, since none of
extracts; e.g., 10% everlasting flower, hawthorn the volunteers showed any positive reactions;
and elderberry extracts; 10% green coffee oil;9, 10 MII ratings = 0, similar to water. Its safety was
or the aforementioned Tanaka products.6, 7 therefore in harmony with the in vitro cell
Final formula stability: Finally, the pas- culture assessment, confirming the product’s
sion fruit concealer mousses exhibiting SPF safety for daily application as a sun protection
protection were assessed for stability similarly makeup product (data not shown).2, 3
to before, i.e., via centrifugation followed by
a heat-cool cycle. The compatibility of the Conclusions
passion fruit seed extract with other cosmetic Passion fruit seed is underlined here as an
ingredients was confirmed and the passion ecological source for safe and efficient cosmetic
fruit concealer mousses were stable in terms of actives that can combat the adverse effects
physical and chemical properties, i.e., texture, of UV radiation in skin. The recovery of this
appearance, pH and sun protection capacity. specialty cosmetic ingredient could become
After the heat-cool cycle (HC), the appear- a fruitful integration between agri-business
ance and texture of the products conformed to and the cosmetics industry. The described
their initial (INT) state, although their pH was operational protocol for preparing the extract

Figure 3. Stability and properties of the passion fruit concealer mousse

68 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Formulating_Lourith_fcx.indd 68 9/19/17 5:40 PM


Active passion fruit seed extract could flow into multifunctional decorative cosmetics.

and controlling and standardizing its quality 6. N Lourith and M Kanlayavattanakul, Removal methods and
evaluation of removal of makeup products, in eds AO Barel,
is feasible for the industrial practice, as per M Paye and HI Maibach, Handbook of Cosmetic Science
the formulation. and Technology, 4th edn, CRC Press, Boca Raton, Fl (2014)
The application of passion fruit seed extract pp 453-457
as a prototype photo-protectant makeup 7. M Kanlayavattanakul and N Lourith, Thanaka loose powder
and liquid foundation preparations, HPC Today (7) 30-32
product could flow to mainstream decorative (2012)
cosmetic consumers and especially fit consum- 8. M Kanlayavattanakul and N Lourith, Sunscreen liquid
ers’ passion and preference for active cosmetics foundation containing Naringi crenulata powder, Adv Mat
derived from sustainable or renewal sources. Res (506) 583-586 (2012)
9. A Jarzycka, A Lewińska, R Gancarz and KA Wilk, Assess-
ment of extracts of Helichrysum arenarium, Crataegus
References monogyna, Sambac nigra in photoprotective UVA and
1. Thailand Patent No. 11910, M Kanlayavattanakul and UVB; Photostability in cosmetic emulsions, J Photochem
N Lourith, Preparation of passion fruit seed extract, Photobiol B Biol (128) 50-57 (2013)
(Sep 1, 2016) 10. BG Chiari et al, Synergistic effect of green coffee oil and
2. N Lourith and M Kanlayavattanakul, Antioxidant activities synthetic sunscreen for health care application, Ind Crop
and phenolics of Passiflora edulis seed recovered from juice Prod 52 389-393 (2014)
production residue, J Oleo Sci (62) 235-240 (2013)
3. N Lourith, M Kanlayavattanakul and J Chingunpitak, Devel-
opment of sunscreen products containing passion fruit seed
extract, Braz J Pharm Sci (53) e16116 (2017) C&T Webcasts
4. R Stevanato, M Bertelle and S Fabris, Photoprotective Find current and upcoming webcasts at
characteristics of natural antioxidant polyphenols, Regul www.CosmeticsandToiletries.com
Toxicol Pharmacol (69) 71-77 (2014)
5. OV Zillich, U Schweiggert-Weisz, P Eisner and M Kerscher,
Polyphenols as active ingredients for cosmetic products, Intl
J Cosmet Sci (37) 455–464 (2015)

Vol. 132, No. 9 | October 2017 Cosmetics & Toiletries® | 69

CT1710_Formulating_Lourith_fcx.indd 69 9/19/17 5:40 PM


Formulating | C&T ®

Face Care Formulary


NATURAL GLOW W/O MULTICULTURAL
ECO-CONSCIOUS FACE POLISH UNDER-EYE CONCEALER
(AAK) BROAD-SPECTRUM, SPF 50+
This multitasking skin cleanser dissolves and removes skin impurities, gently exfoliates
the skin’s surface, stimulates microcirculation and leaves the skin radiant and glow-
(Croda)
ing while delivering nourishing plant-based lipids. The formula features Akogel as a This multicultural, under-eye concealer with SPF is the perfect remedy for dark
sustainable alternative to petrolatum; natural ingredients (CPAI): 96%. circles. Sensasil PCA assists in spreadability and delivers a long-lasting silky after-
feel. The high SPF is achieved using Solaveil XT-300 in the oil phase, Solaveil XT-40W
A. Water (aqua) qs to 100.00% w/w
in the water phase and SolPerForm 100, which creates even coverage. Available in a
Glycerin 5.00
light, medium and dark shades, this under-eye concealer is suited for any ethnicity.
Citric Acid 0.15
Benzyl Alcohol 0.50 A. PCA Dimethicone (Sensasil PCA, Croda) 2.00% w/w
Potassium Sorbate 0.15 PEG-30 Dipolyhydroxystearate (Cithrol DPHS, Croda) 2.00
Sodium Benzoate 0.20 Ricinus Communis (Castor) Seed Oil 4.00
Sodium Stearoyl Lactylate 1.00 Hydrogenated Castor Oil 1.00
Xanthan Gum 1.00 PPG-15 Stearyl Ether (Arlamol PS15E, Croda) 3.00
B. Hydrogenated Vegetable Oil (Akogel, AAK) 7.00 B. Titanium Dioxide (and) Caprylic/Capric Triglyceride (and)
Hydrogenated Vegetable Oil 3.00 Polyhydroxystearic Acid (and) Stearic Acid (and) Alumina
Shea Butter Ethyl Esters (Lipex SheaLight, AAK) 3.00 (Solaveil XT-300, Croda) 7.00
Glyceryl Stearate Citrate 3.00 Caprylic/Capric Triglyceride (and) Titanium Dioxide (and)
Glyceryl Stearate 2.50 Polyhydroxystearic Acid (and) Aluminum Stearate (and)
C. Polylactic Acid 3.50 Alumina (Solaveil CT-300, Croda Europe Ltd.) 22.00
D. Fragrance (parfum) 0.60 C. Water (aqua) 30.60
Glycerin 2.00
Procedure: In A, premix biogums with glycerol and add them to water, while vigor-
ously mixing. Heat A and B separately to 75°C. Merge phases and start mixing Hydrolyzed Wheat Protein/PVP Crosspolymer/Water
with medium speed. Homogenize. Cool to 30°C while stirring. Add C to AB. Blend (aqua) (SolPerForm 100, Croda) 2.00
thoroughly. Add D. Mix well. Titanium Dioxide (and) Water (aqua) (and) Polyglyceryl-2
Caprate (and) Sucrose Stearate (and) Simmondsia
Chinensis (Jojoba) Seed Oil (and) Stearic Acid (and)
Alumina (and) Glyceryl Caprylate (and) Squalane
(Solaveil XT-40W, Croda Europe Ltd.) 4.00
Magnesium Sulfate Hepta-Hydrate 1.00
PROTECTIVE SUN OIL D. Caprylic/Capric Triglyceride (Crodamol GTCC, Croda) 12.00
CI 77499 (SunPURO Black Iron Oxides, Sun Chemical Corp.) 0.60
(Lucas Meyer Cosmetics) (SunPURO Red Iron Oxides, Sun Chemical Corp.) 1.20
This sun protection oil features MeliNOIL, a sunless tanning agent, and imparts an SPF CI 77492 (SunPURO Yellow Iron Oxides, Sun Chemical Corp.) 5.00
10 in vitro. The non-greasy formula protects and nourishes the skin. E. Phenoxyethanol 0.60
A. Prunus Amygdalus Dulcis (Sweet Almond) Oil 7.50% w/w 100.00
Ethylhexyl Salicylate 5.00 Procedure: Add A to main beaker and heat to 80-85°C with slow propeller mixing
Simmondsia Chinensis (Jojoba) Seed Oil 15.00 until fully melted and uniform. Combine D and pass on a #3 roller mill until fully
Caprylic/Capric Triglyceride 7.50 dispersed and free of striations (prepare D @ 150%, to account for loss while
Phospholipids (and) Glycine Soja (Soybean) Oil (and) processing). In a side beaker, add B and heat to 80-85°C. When A, B and D
Glycolipids (and) Glycine Soja (Soybean) Sterols are at 80-85°C, combine BD and add to A, then start medium speed propeller
(Amisol Trio, Lucas MeyerCosmetics) 2.00 mixing, while maintaining temperature at 80-85°C. In another side beaker, add C
Triheptanoin 8.90 with propeller mixing and heat to 80-85°C until uniform (adjust speed accordingly
Cetyl Ethylhexanoate 35.10 to disperse CT-40W). When ABD and C are at their appropriate temperatures and
uniform, pour C into ABD very slowly with high speed propeller mixing (adjust
Butyl Methoxydibenzoylmethane 3.00
speed accordingly, as batch viscosity will gradually increase as the water phase
Octocrylene 5.00
is incorporated). After all of C is transferred, continue mixing until uniform and
Ethylhexyl Methoxycinnamate 5.00 cool batch to RT. At 35°C, add E and continue mixing until uniform. At RT, stop
B. Fragrance (parfum) 0.80 mixing and check specifications.
Tocopherol (and) Helianthus Annuus (Sunflower) Seed Oil
(Vitapherole E1000, VitaeNaturals) 0.20
Isopropyl Palmitate (and) Lecithin (and) Water (aqua) (and)
Acetyl Hexapeptide-1 (MeliNOIL, Lucas Meyer Cosmetics) 5.00
100.00 C&T Face Care Formulary
Procedure: Prepare A and heat at 70-80°C under slow stirring. When mixture is ho- Click here for more face care formulas,
mogeneous, cool under medium stirring. Add B (one by one) below 40°C. exclusively featured in our Digital Edition!

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Advertiser Index | C&T ®

October 2017 | Volume 132, number 9

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www.biosiltech.com InVitro International Siltech
5 30
invitro@invitrointl.com www.siltechpersonalcare.com
Centerchem, Inc. www.invitrointl.com
C4
cosmetics@centerchem.com Society Of Cosmetic Chemists
65
www.centerchem.com Lipotec, LLC www.scconline.org
C3
salesoffice@lipotec.com
Clariant International Ltd. www.lipotec.com Sytheon Ltd.
3 37
info@clariant.com info@sytheonltd.com
www.personalcare.clariant.com Lipotrue www.sytheonltd.com
51
info@lipotrue.com
Colonial Chemical, Inc. www.lipotrue.com Vevy Europe SpA
59 39
www.colonialchem.com info@vevy.com
Lubrizol Advanced www.vevy.com
57
Excellentia International Materials, Inc.
71
sales@excellentiaint.com www.lubrizol.com/personalcare Wacker Chemie AG
9
www.excellentiaint.com www.wacker.com
Lucas Meyer Cosmetics
7
Givaudan Active Beauty info@lucasmeyercosmetics.com Welch Holme & Clark Co., Inc.
C2 28
noam.activebeauty@givaudan.com www.lucasmeyercosmetics.com www.welch-holme-clark.com
www.givaudan.com
Mibelle AG Biochemistry
13
Grant Industries info@mibellebiochemistry.com
1
info@grantinc.com www.mibellebiochemistry.com
www.grantinc.com

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CT1710_Advertiser_Index_fcx.indd 72 9/20/17 11:42 AM


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CT17_House_Ad_FP.indd 1 2/20/17 12:53 PM
Market Intelligence | C&T ®

KEY POINTS
• Multifunctional cosmetics that deliver skin
benefits are not only here to stay, but expected
to grow significantly in several categories.

• Anti-pollution is certain to continue trending as


skin care bridges into cosmetics.

MORE
THAN
MAKEUP Multifunctionality Speaks Volumes*

G
*Adapted with permission from Global Cosmetic Industry

Lisa Doyle
Contributing Author, reat news for cosmetic brands and
Global Cosmetic Industry their loyal following: the BB and
CC creams that have recharged the
beauty-meets-skin-care business
are just the tip of the iceberg.
Multifunctional cosmetics
that deliver skin benefits are not only here to stay, but are expected
to grow significantly in several categories. For instance, the global

Reproduction in English or any other language of


DE1 | www.CosmeticsandToiletries.com all or part of this article is strictly prohibited. Vol. 132, No. 9 | October 2017
© 2017 Allured Business Media.

CT1710_DE_Mrkt_Rprt_fcx_even.indd 8 9/26/17 9:58 AM


“There’s a real opportunity for the beauty
industry to take more action to help protect
our skin against harmful airborne toxins.”

organic personal care market is projected to There also exist vast market opportunities
grow to nearly $25.7 billion by 2025, largely due in the West, which has been slower to adopt
to the impact of multifunctional products. anti-pollution claims. According to a recent
“...[M]ultifunctional ingredients are very survey of 2,000+ Americans, conducted by
powerful,” said Pauline Martin, global com- Morning Consult on behalf of H2O+ Beauty,
munications and events manager, Givaudan 66% of people still do not protect their skin
Active Beauty. “They allow for formulations against pollution. Furthermore, 62% of women
with a high degree of added value, and overall would be more likely to purchase products if
they claim multiple benefits for products while they protected the skin against environmental
rationalizing the cost in use.” pollutants, compared with 55% of men.
Keep an eye on the following trends that “The data indicates a serious rift between
experts say will impact multifunctional cosmet- general awareness of the damage that pollution
ics in 2017 and beyond. can cause to your skin, and the understanding
that you can shield your skin from harm with
Anti-pollution Color certain products,” said Joy Chen, CEO of H2O+
Anti-pollution and environmental skin pro- Beauty. “There’s a real opportunity for the
tection are certain to continue trending as skin beauty industry to take more action to help pro-
care bridges into cosmetics—especially in light tect our skin against harmful airborne toxins.”
of growing disposable incomes of populations Ingredient suppliers are responding to this
surging in the high-pollution markets of India opportunity with new innovations; for example,
and Asia. In recent years, Lancôme launched its BASF’s PatcH2O hydra-protect technology,
successful City Miracle CC Cream, touting it as based on the association of three film-forming
having been tested in some of the world’s most biopolymers—pullulan, alginate and hyaluronic
polluted cities. acid—and a hydrating complex of glycerin,
serine, trehalose and urea.
“PatcH2O offers an efficient
technical solution to meet the
needs of two rapidly expanding
markets: hydration and anti-
pollution ingredients,” explained
Manasi Chavan, Ph.D, BASF’s
technical service team manager
for personal care in North
America.
“This unique, patent-applied
technology forms a hydric bar-
rier that significantly protects
skin from cytotoxicity and
oxidative stress that are induced,
respectively, by PM2.5 and BaP.
This technology offers immedi-
Via a partnership with E-Ink, the Texen branch of ate, long-term and sustained
PSB Industries has brought interactive smart tech into hydration benefits.”
cosmetic packaging.

Vol. 132, No. 9 | October 2017 Cosmetics & Toiletries® | DE2

CT1710_DE_Mrkt_Rprt_fcx_even.indd 9 9/26/17 9:58 AM


Color Out Loud

Givaudan’s Neurophroline,
which is extracted from the seeds
of the wild indigo plant, is also engi-
neered to fight pollution’s ill effects
on the skin.
“Neurophroline blocks cortisol
production and promotes the
release of relaxing neuropeptides,
offering anti-aging, anti-pollution
and antioxidant properties in the
skin,” said Martin.
“In addition, the ingredient has
been shown to quickly recover skin HCP’s Push and Pull lipstick is a versatile pack applicable for lipstick, contouring,
luminosity, improve skin color, strobing and color-correcting.
reduce redness and completely
recover tired-looking skin in
one month.”

“For many makeup brands, innovation is


driven by consumers’ appetite for more active
makeup with an immediate ‘wow’ effect and
additional skin care benefits.”

Argan-infused Beauty said Chavan. “With its high content of flavo-


noids, it is an excellent antioxidant ingredient
Super ingredient argan oil has been working
that protects the skin against three types of
its way out of the niche and into the main-
pollution to inhibit
stream beauty market for more than a decade,
ROS and RCS
expanding from skin care: e.g., Moroccanoil
(reactive carbonyl
Pure Argan Oil, Vita Liberata Passionflower
species) induction,
& Argan Dry Oil Broad Spectrum SPF 50 and
along with inhibiting
Josie Maran Whipped Mud Mask Collection; to
IL-8 release. And, in
hair care, including: Moroccanoil Treatment,
addition to protect-
Madison Reed Root Touch Up, and Bumble and
ing against pollution,
Bumble Hairdresser’s Invisible Oil; as well as
Arganyl protects
color cosmetics: Too Cool For School Dinoplatz
elastin and collagen
Lip Balm, Bite Beauty Line and Define Lip
from degradation.”
Primer, and Urban Decay Brow Beater Micro-
Lady Burd
fine Brow Pencil.
Cosmetics’ Miracle
Ingredient suppliers are responding to
Beauty Oil exempli-
this dynamic with ethical ingredient innova-
fies how argan oil
tions. For example, since 2011, BASF has
is leveraged to its
been partnering with women’s cooperatives in
full potential.
Morocco to bring argan-based ingredients into
personal care.
“Arganyl, a leaf extract high in flavonoids,
has excellent antioxidant properties, along with Lady Burd Cosmetics’
the ability to inhibit MMP and collagenase to Miracle Beauty Oil leverages
argan oil to its full potential.
help preserve the skin’s extracellular matrix,”

DE3 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_DE_Mrkt_Rprt_fcx_even.indd 10 9/26/17 9:58 AM


“Skin oils are not new to skin care, but they “The pack is operated by pushing the lipstick
have become extremely popular—with good at one end of the pack, which then allows
reason,” said Tanya Diaz, product developer at access to the lipstick at the other end,” said
Lady Burd. Stephanie Rowntree, product manager, HCP.
“Miracle Beauty Oil contains a blend of oils “The brand Cover FX used our Push & Pull
such as argan oil, marula oil, black currant lipstick for their innovative Click Stick, a cus-
seed oil and more, which are packed with fatty tomizable beauty tool that empowers makeup
acids and vitamin antioxidants. It can be mixed connoisseurs to conveniently customize their
into foundations to add a boost of radiance and makeup wardrobe. This clever product offers a
life, helping makeup look more like naturally choice of 36 global shades of Correct, Cover or
beautiful skin.” Enhance Clicks to upload into the Click Stick,
transforming it into the perfect portable tool to
Look on the Bright Side correct, conceal, contour, highlight, strobe and
Finally, as the emphasis on skin care in Asia illuminate the complexion.”
gradually shifts from whitening to brightening, And, via a partnership with E-Ink, the Texen
the goal of healthy, radiant skin is being shared branch of PSB Industries has brought interac-
around the world, illuminating new opportuni- tive smart technology into cosmetic packaging.
ties for savvy color effects ingredient suppliers. Using near-field communication, a miniature
“Ronaflair pigments provide numerous ben- screen embedded into a makeup compact and
efits, including opacity, transparency, soft focus case can connect to an enabled smartphone
effects, skin adhesion, color correction, texture and provide tutorials, tips and product details
improvement and increased mattifying for less on-demand to the end user—taking multifunc-
‘caking’ in eyeshadows and powders,” explained tionality to a new level.
Phil Linz, EMD’s manager of cosmetic applica- As Massard noted, “For many makeup
tions. “They also provide that illumination and brands, innovation is driven by consumers’
radiance to formulas, which is so essential to appetite for more active makeup with an
many of today’s products.” immediate ‘wow’ effect and additional skin
Brightenyl from Givaudan also aids illumi- care benefits.”
nation to skin. According to Martin, “Brightenyl
is a bio-boosted, skin-brightening, pore-reduc-
ing and color-correcting active that protects
and perfects skin’s complexion by restoring its
healthy and natural tone.”
Meanwhile, Sensient Technologies has intro-
duced Sensibright Dual White WD, a novel TiO2
pigment coated with skin-brightening active
ingredients. Sebastien Massard, Sensient’s
marketing manager for North America, said,
C&T Daily Newsletter
“This hybrid product provides immediate skin
whitening due to its pigment content, but also Get the latest from Cosmetics & Toiletries
delivered straight to your inbox every day!
progressively releases illuminating active ingre-
dients—alpha arbutin and licorice extract—for http://www.CosmeticsandToiletries.com/newsletter
long-term efficacy.”

Innovative Applicators
When it comes to multifunctional cosmetics,
it’s not just what a product does that mat- C&T Webcasts
ters—it’s also how it’s accessed and what the Find current and upcoming webcasts at
package can do. HCP’s Push and Pull lipstick, www.CosmeticsandToiletries.com
for example, is housed in a versatile pack
applicable for lipstick, contouring, strobing and
color-correcting.

Vol. 132, No. 9 | October 2017 Cosmetics & Toiletries® | DE4

CT1710_DE_Mrkt_Rprt_fcx_even.indd 11 9/26/17 9:58 AM


EXPANDED Face Care Formulary

C. Linoleamidopropyl PG-Dimonium Chloride Phosphate


ESSENTIAL DEFENSE Dimethicone (Arlasilk PLN, Croda) 1.00
FACIAL MOISTURIZER WITH D. Phenoxyethanol (and) Ethylhexylglycerin
(euxyl PE 9010, schulke) 0.60
BROAD-SPECTRUM SPF E. Polysorbate 20 (Tween 20, Croda) 0.20
(BASF Corporation) Fragrance (parfum) 1.00
100.00
This supercharged, anti-pollution moisturizer also provides broad-spectrum UV
protection. Mariponics PSR, a marine algae extract, helps to protect against pollution Procedure: Add A in the main beaker and heat to 60°C while propeller mixing. When
and maintain skin’s vitality. Z-Cote LSA is a sun protection ingredient that is naturally a clear solution is achieved, start cooling to RT. At 50°C, premix B and solubilize
derived from the earth’s crust and provides a physical barrier against aggressive UVA and add to A while propeller mixing until uniform. When uniform, add C to the
and UVB radiation damage. Finally, Emulgade Sucro Plus is a natural-based emulsi- main beaker and continue mixing until uniform. At 40°C, add D to the main bea-
fier that improves formulation stability. This moisturizer’s multi-action age defenders ker and continue mixing until uniform. At 30°C, premix E and add to main beaker
intercept damage before it starts. while continuing to mix until uniform. At RT, stop mixing and check specifications.

A. Water (aqua) 56.45% w/w


Sclerotium Gum 2.00
Disodium EDTA 0.10 BROAD-SPECTRUM,
Polyurethane-39 1.00
B. PEG-8 3.00 WATER-RESISTANT, SPF 25+
Magnesium Aluminum Silicate 0.60 DAILY FACIAL MOISTURIZER
Xanthan Gum 0.35
C. Polyglyceryl-3 Distearate 1.50 (DuPont Tate & Lyle Bio Products)
Cocoglycerides 1.00 This light-feeling, w/o formulation spreads well, covers evenly and has built-in water
Vegetable Oil (and) Hydrogenated Vegetable Oil (and) resistance, enhanced by the use of two emollients with excellent barrier character-
Euphorbia Cerifera (Candelilla) Wax (Cegesoft VP, BASF SE) 0.50 istics. Combining organic and inorganic sunscreen actives, along with placement
Polymethylsilsesquioxane 1.00 of the actives in both the aqueous and emollient phases, allows for a high SPF with
Sucrose Polystearate (and) Cetyl Palmitate a relatively low level of actives. The formula achieves protection beyond broad-
(Emulgade Sucro Plus, BASF Corporation) 0.75 spectrum, with a critical wave length of 377.8 nm. The success of the formulation is
Ceteareth-20 1.75 attributed to Zemea propanediol, which keeps the water-soluble actives in solution
Hydrogenated Polyisobutene 6.00 through the evaporation process upon application to the skin.
Propylheptyl Caprylate 2.00 A. Water (aqua) 54.60% w/w
Pentaerythrityl Distearate 2.00 Caprylhydroxamic Acid (and) Caprylyl Glycol (and) Glycerin
Zinc Oxide (and) Triethoxycaprylylsilane (Z-Cote LSA, (Spectrastat, INOLEX) 0.80
BASF Corporation) 8.00 Benzophenone-4 2.00
Ethylhexyl Methoxycinnamate 6.00 B. Propanediol (Zemea propanediol, DuPont Tate & Lyle Bio
Dibutyl Adipate 2.00 Products) 10.00
D. Water (aqua) (and) Pentylene Glycol (and) Butylene Glycol Phenylbenzimidazole Sulfonic Acid (Eusolex 232,
(and) Algae Extract (and) Yeast Extract (Mariponics EMD Chemicals Inc.-RONA Cosmetic Business Unit) 3.00
PSR R11009, BASF Corporation) 3.00 C. Triethanolamine qs
E. Phenoxyethanol (and) Ethylhexylglycerin D. Titanium Dioxide (and) Water (aqua) (and) Polyglyceryl-2
(euxyl PE 9010, schulke) 1.00 Caprate (and) Sucrose Stearate (and) Simmondsia
F. Citric Acid qs Chinensis (Jojoba) Seed Oil (and) Stearic Acid (and)
100.00 Alumina (and) Glyceryl Caprylate (and) Squalane
Procedure: Combine A and start mixing until dissolved. Pre-mix B and add to A. (Solaveil XT-40W, Croda) 3.00
Allow gel to form, then heat to 75-80°C. Combine C and while mixing heat to E. Acetylated Hydrogenated Vegetable Glyceride 15.00
75-80°C, homogenize 30 sec to 1 min (until uniform) to disperse D. Add CD to Polyglyceryl-3 Polyricinoleate 2.50
AB while homogenizing, homogenize until uniform (2-3 min). Transfer to propeller Caprylic/Capric Triglyceride (and) Titanium Dioxide (and)
mixing and start cooling. At 35°C or less add E, mix well, then add F. Check pH, Polyhydroxystearic Acid (and) Stearic Acid (and) Alumina
and if necessary adjust to between 7.00 and 7.50 (Solaveil AT-300, Croda) 3.00
Zinc Oxide (and) Caprylic/Capric Triglyceride (and)
Polyhydroxystearic Acid (and) Triethoxycaprylylsilane
(Xperse 201, EverZinc) 3.00
MAKE IT LAST Octyldodecyl Citrate Crosspolymer 3.00
MAKEUP SETTING SPRAY F. Silica Dimethyl Silylate 0.10
100.00
(Croda) Procedure: Add B to A. Add C until AB is clear. Add D with propeller stirring. Add
Designed to deliver exceptional makeup-extending benefits, this clear formulation ABCD to E very slowly with propeller stirring. Add F with propeller stirring. Ho-
leaves the face feeling refreshed and comfortable. It holds makeup in place all day mogenize until glossy.
with film-forming technology made comfortable by Crodamol STS, which detacki-
fies and works in synergy with Arlasilk PLN to deliver silky formulation aesthetics.
A. Water (aqua) 76.70% w/w
Alcohol 8.00
Poloxamer 407 (Synperonic PE/F127, Croda) 1.50
PVP (PVP K-15, K-30, K-60, K-90 and K-120,
Ashland Specialty Ingredients) 3.00
B. Polysorbate 20 (Tween 20, Croda) 7.50
PPG-3 Benzyl Ether Myristate (Crodamol STS, Croda) 0.50

DE5 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

CT1710_Sun_Formulary_fcx_even.indd 72 9/26/17 9:44 AM


Procedure: Prepare A and B separately. Add A to B and homogenize using a suit-
AFTER-SUN able dispersion unit. Add C. Mix until smooth and uniform; properties @ 25°C:
MOISTURIZING LOTION appearance = shiny, white gel cream; viscosity (10 rpm, Brk, RVDV-E, T-B, after
24 hr at RT; mPa∙s) = 16,000–19,000; pH = 6.0–7.0.
(Floratech)
This light, soothing after-sun lotion provides a moisturizing treatment to dry, sun-baked
skin. The product features Florasun 90 (high-oleic sunflower oil) and jojoba esters,
which reduce redness and improve barrier function. This sun care product may be #KBEAUTY FACIAL SHEET MASK
marketed as natural, botanical and renewable. (Kemin)
A. Water (aqua) qs 100.00% w/w Include some #kbeauty in consumers’ routines with this facial sheet mask. Soaked
B. EDTA (Versene 100, NA2, The Dow Chemical Company) 0.01 in a fresh and fluid, jelly emulsion infused with lutein, the fiber mask wraps perfectly
1,3-Butylene Glycol (Butylene Glycol, Celanese Corp.) 4.00 around facial contours for intense penetration of the actives to refresh stressed skin
Preservatives qs after all day blue light exposure.
C. Jojoba Esters (Floraesters 20, Floratech) 1.00
Jojoba Esters (Floraesters 30, Floratech) 1.00 A. Water (aqua) 88.32% w/w
Helianthus Annuus (Sunflower) Seed Oil (Florasun 90, Disodium EDTA 0.03
Floratech) 10.10 B. Glycerin 3.00
Glyceryl Stearate (and) PEG-100 Stearate Hydroxyethylcellulose 0.10
(Arlacel 165, Croda) 2.50 Acrylates/C10-30 Alkyl Acrylate Crosspolymer
Sorbitan Oleate (Arlacel 80, Croda) 0.50 (Pemulen TR-1 Polymer, Lubrizol Advanced Materials, Inc.) 0.22
Tocopheryl Acetate 0.50 C. Sodium Hydroxide 0.05
D. C13-14 Isoparaffin (and) Laureth-7 (and) D. Glycerin (and) Glycine Soja (Soybean) Seed Extract
Polyacrylamide (Sepigel 305, Seppic) 1.60 (Lysofix Liquid, Kemin) 1.50
E. Panthenol 0.50 1,3-Butylene Glycol 4.00
Aluminum Starch Octenylsuccinate (Dry-Flo PC, E. Helianthus Annuus (Sunflower) Seed Oil (and) Rosmarinus
AkzoNobel, Personal Care) 2.00 Officinalis (Rosemary) Leaf Extract (Rosamox, Kemin) 0.20
Fragrance (parfum) qs Persea Gratissima (Avocado) Oil 0.50
Simmondsia Chinensis (Jojoba) Seed Oil 1.00
Procedure: Heat A to 75°C with moderate propeller agitation; add B to A in order. Carthamus Tinctorius (Safflower) Seed Oil (and) Xantophyll
Combine and heat C to 75°C with moderate propeller agitation. Slowly add C to (proposed) (FloraGLO Lutein Topical , Kemin) 0.10
AB with rapid propeller agitation at 75°C. Mix until uniform prior to cooling. At 60°C,
F. Hydroxyacetophenone 0.50
add D to ABC with moderate propeller agitation. Mix until batch is homogeneous.
Phenoxyethanol 0.18
Cool batch to 45°C. At 45°C, add E in order and agitate until uniform. Cool to RT.
PEG-60 Hydrogenated Castor Oil 0.30
100.00
Procedure: Charge A in the main vessel. Premix B and add to A. Hydrate for 30 min.
LIFT ME GEL CREAM Neutralize with C and add premixed D. Heat ABCD and E to 80°C. Add heated E
to ABCD and homogenize for 3 min. Continue slow mixing and maintain temp for
(The Hallstar Company) 20 min. Begin to cool to 45°C, add premixed F and homogenize again for 1 min.
Continue to slow mix for until smooth and uniform.
This soothing face cream is enriched with antioxidant Eurol BT and provides non-
stop daily hydration to delay signs of aging caused by loss of moisture. Olivem 2020
refreshes and cools the skin upon application. Oléos Lift Oléoactif reduces the ap-
pearance of fine lines and improves skin density. A combination of Sensolene and
Biochemica camellia tea oil provides deep hydration to support healthy skin elasticity. DEEP MOISTURE FACIAL
Oléos, based in France, is a recently acquired part of Hallstar. SHEET MASK
A. Water (aqua) qs to 100.00% w/w
(Kemin)
Glycerin 3.00
Betaine 0.40 This smart facial sheet mask is soaked in a transparent, soft gel loaded with Lysofix
Olea Europaea (Olive) Leaf Extract (and) Water (aqua) Liquid to provide intense and deep moisture to skin. This must-have treatment is
(Eurol BT, The Hallstar Company) 0.25 tailored to effectively improve consumers’ skin barriers for stronger skin, ready to face
Trisodium Ethylenediamine Disuccinate 0.30 city aggressions. Immediately after peeling off the mask, the skin seals in moisture
B. Camellia Oleifera Seed Oil (Biochemica Camellia Tea Oil, and reveals a fresh, supple, smooth and firm look. This deep moisture mask is a
The Hallstar Company) 2.50 minimal formula that can be used as a base for formulations targeting other functions
Ethylhexyl Olivate (Sensolene, The Hallstar Company) 2.00 if different actives are added.
Carthamus Tinctorius (Safflower) Seed Oil (and) Astragalus A. Water (aqua) 34.64% w/w
Membranaceus Root Extract (and) Ubiquinone (and) Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.18
Tocopherol (and) Spilanthes Acmella Flower/Leaf/Stem Triethanolamine 0.18
Extract (Oléos Lift Oléoactif, The Hallstar Company) 1.00 B. Water (aqua) 53.38
Bisabolol 1.00 Glycerin 3.00
Preservatives qs Disodium EDTA 0.04
Lecithin (and) Tocopherol (and) Ascorbyl Palmitate (and) Xanthan Gum 0.10
Citric Acid (Aperoxid TLA, Biochim Srl) 0.05 C. 1,3-Butylene Glycol 6.00
Ethylhexyl Olivate/Sodium Acrylates Copolymer/ Glycerin (and) Glycine Soja (Soybean) Seed Extract
Polyglyceryl-4 Olivate (Olivem 2020, The Hallstar Company) 2.00 (Lysofix Liquid, Kemin) 1.50
C. Cyclomethicone 8.00 D. Hydroxyacetophenone 0.50
Cyclopentasiloxane (and) Dimethiconol (Silsoft 1215 HV, Phenoxyethanol 0.18
Momentive Performance Materials Inc.) 2.00 PEG-60 Hydrogenated Castor Oil 0.30
Dimethicone/Dimethicone/Vinyl Dimethicone Crosspolymer 100.00
(KSG-16, Shin-Etsu Chemical Co. Ltd.) 1.00

Vol. 132, No. 9 | October 2017 Cosmetics & Toiletries® | DE6

CT1710_Sun_Formulary_fcx_even.indd 73 9/26/17 9:44 AM


EXPANDED Face Care Formulary

Procedure: Prepare A by hydrating for 30 min and neutralizing the polymer. Weigh Procedure: In a mixer, introduce A and heat to 80°C. Add B. Stir to obtain a homog-
B into the main vessel and mix to hydrate gums for 15 min. Add A to B and enous blend. Separately in the heater, introduce C and heat to 75°C. When AB
heat to 80°C while mixing. Maintain temp for 20 min. Begin to cool to 70°C, and C have reached the required temperatures, pour the content of the heater
add pre-mixed C to AB, and continue to mix. At 45°C, add D and mix until cool slowly into the mixer. Mix for 10 min until homogenous and allow to cool. At 30°C,
and transparent. introduce D to ABC. Empty out at 28/30°C.

SHIMMERING PLUM EXFOLIATING


PROTECTIVE SUN OIL FACE CREAM
(Lucas Meyer Cosmetics) (Naturochim S.A.S.)
This protective sun oil is non-greasy and protects and nourishes the skin. NAT Gascony Plum Butter brings to this cream a soft, melting texture and a delicately
sweet, candy-like aroma. Nat Gascony Plum Scrub 40 utilizes a perfectly appropriate
A. Prunus Amygdalus Dulcis (Sweet Almond) Oil 7.50% w/w
particle size for facial exfoliation.
Ethylhexyl Salicylate (Eusolex OS, Merck KGaA) 5.00
Simmondsia Chinensis (Jojoba) Seed Oil 15.00 A. Water (aqua) 56.70% w/w
Caprylic/Capric Triglyceride 7.50 Glycerin 5.00
Phospholipids (and) Glycine Soja (Soybean) Oil (and) Xanthan Gum 0.50
Glycolipids (and) Glycine Soja (Soybean) Sterols B. Potassium Palmitoyl Hydrolyzed Wheat Protein (and)
(Amisol Trio, Lucas Meyer Cosmetics) 2.00 Glyceryl Stearate (and) Cetearyl Alcohol
Triheptanoin (Dermofeel TC-7, Dr. Straetmans Chemische (Phytocream 2000, Sinerga SpA) 5.00
Produkte GmbH) 8.90 Hydrogenated Prunus Domestica Seed Oil (and) Prunus
Cetyl Ethylhexanoate (Schercemol CO Ester, Lubrizol Domestica Seed Oil (NAT Gascony Plum Butter,
Advanced Materials, Inc.) 34.10 Naturochim S.A.S.) 6.00
Butyl Methoxydibenzoylmethane (Eusolex 9020, Merck KGaA) 3.00 Cetearyl Alcohol (Lanette O, BASF SE) 1.00
Octocrylene (Uvinul N-539 T, BASF AG) 5.00 Cetyl Alcohol (Lanette 16, BASF SE) 2.00
Ethylhexyl Methoxycinnamate (Eusolex 2292, Merck KGaA) 5.00 Dicaprylyl Carbonate (Cetiol CC, BASF SE) 5.00
B. Fragrance (parfum) 0.80 Caprylic/Capric Triglyceride (Myritol 318, BASF SE) 12.00
Tocopherol (and) Helianthus Annuus (Sunflower) Seed Oil Glyceryl Undecylenate 0.50
(Vitapherole E1000, VitaeNaturals) 0.20 C. Dehydroacetic Acid (and) Benzyl Alcohol
Isopropyl Palmitate (and) Lecithin (and) Water (aqua) (and) (Geogard 221, Lonza Consumer Care) 0.80
Acetyl Hexapeptide-1 (MeliNOIL, Lucas Meyer Cosmetics) 5.00 D. Prunus Domestica Seed Powder (Nat Gascony Plum Scrub 40,
Synthetic Fluorphlogopite 1.00 Naturochim S.A.S.) 5.00
100.00 E. Fragrance (parfum) 0.50
100.00
Procedure: Prepare A and heat at 70-80°C under slow stirring. When mixture is
homogeneous, cool under medium stirring. Add B (one by one) below 40°C. Procedure: Prepare A. In a mixer, heat the purified water to 80°C. Add A. Shake up
to obtain a homogeneous mix. Separately in a heater, mix B and heat to 75°C.
When A and B reach the required temperatures, introduce the blend from the
heater slowly into the mixer. Mix for 10 min until homogeneous and allow to cool.
NIGHT FACE & EYE CREAM MASK At 50°C, add C to AB. Mix for 5 min until homogeneous and add D to ABC. At
40°C add E to ABCD . Mix for 5 min and adjust the pH to 5.6 with 10% sodium
(Naturochim S.A.S.) hydroxide or 50% citric acid.
This cream can be used as a mask to treat both face and eye contours. It contains
premium organic argan butter and natural and organic argan wax, which impart
body to creams while acting as emollient and moisturizing agents. The organic
deodorized pomegranate oil is rich in conjugated fatty acids, mainly punicic acid, SUPER HYDRATING
that show strong anti-inflammatory properties and is therefore recommended for
mature and tired skin.
PLUMPING FACE MASK
(Shin-Etsu Chemical Co. Ltd.)
A. Water (aqua) 64.70% w/w
Propanediol 5.00 A. Dimethicone/PEG-10/15 Crosspolymer/Dimethicone
Sorbitol 3.00 (KSG-210, Shin-Etsu Chemical Co. Ltd.) 5.00% w/w
Inulin 3.00 PEG-8 Dimethicone (KF-6017, Shin-Etsu Chemical Co. Ltd.) 0.10
B. Ammonium Acryloyldimethyltaurate/VP Copolymer Cyclopentasiloxane 10.00
(Aristoflex AVC, Clariant Int. Ltd.) 0.80 B. Water (aqua) 63.50
C. Potassium Palmitoyl Hydrolyzed Wheat Protein (and) Glyceryl Glycerin 10.00
Stearate (and) Cetearyl Alcohol (Phytocream 2000, Propylene Glycol 5.00
Sinerga SpA) 6.00 1,3-Butylene Glycol 5.00
Argania Spinosa Kernel Oil (and) Hydrogenated Argania Sodium Citrate 0.20
Spinosa Kernel Oil (Premium Organic Argan Butter, Sodium Chloride 0.50
Naturochim S.A.S.) 3.00 Phenoxyethanol 0.70
Hydrogenated Argania Spinosa Kernel Oil (NAT Organic C. Blue Lake No. 1 qs
Argan Wax, Naturochim S.A.S.) 1.00 100.00
Dicaprylyl Carbonate (Cetiol CC, BASF SE) 10.00 Procedure: Combine A using a dispersing blade and mix until homogeneous. Com-
Punica Granatum Seed Oil (NAT Organic Deodorized bine B in a separate vessel and mix well until dissolved. Using a steady stream,
Pomegranate Oil, Naturochim S.A.S.) 2.50 add B to A and mix for 1 min to 3 min. Storage in a plastic container is preferred.
Tocopherol 0.40
Glyceryl Undecylenate 0.50
D. Fragrance (parfum) 0.10
100.00

DE7 | www.CosmeticsandToiletries.com Vol. 132, No. 9 | October 2017

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