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Vietnam National University

Ho Chi Minh City University of Technology


Office for International Study Program
FACULTY OF CHEMICAL ENGINEERINGS

Instructor: Le Xuan Tien


Group – CC01

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GROUP MEMBER
1. Đoàn Bá Thịnh 1852200
2. Lê Ngọc Anh 1852229
3. Văn Thị Thanh Thanh 1852737
4. Lê Khải Vinh 1852873
5. Nguyễn Hoàng Huy 1852030
6. Đặng Hung Quốc Long 1852516
7. Nguyễn Thị Mỹ Châu 1852278
8. Hồ Lê Minh Quân 1852188
9. Lê Nhật Quang 1852693
10. Hoàng Hữu Quốc 1852702
11. Hoàng Gia Hân 1852355
12. Nguyễn Mạnh Hoàng 1852383

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CONTENTS
6. Background of
1. Types of pepper
Piperine
2. Background of
7. Physical properties
pepper

3. Pepper production 8. Extraction

4. Quality standard 9. Purification

5. Components of
10. Identification
black peppercorn
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01.
TYPES OF
PEPPER

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1.1. INTRODUCTION

o Peppercorns have different varieties,


colors, intensity and flavor profiles.

o The commonly found trio of black,


white and green peppercorn come
from the same flowering vine. While
other types come from other plants.

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1.2.1. BLACK PEPPER

Odor & flavor hot, pungent taste with


mouldy and rancid smell

Color brownish to dark


brownish or blackish

about 2.5 – 7 mm with


Size
globular shape and
wrinkled pericarp
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Production process

01 02 03

Unripe (still- Cook the drupes Dry in the sun or


green) drupes are briefly in boiling by machine for
harvested water several days 7
1.2.2. WHITE PEPPER
very aromatic with brighter,
Odor & flavor
sharper and more herbaceous
taste than BP

Color matt grey to brownish to pale ivor


white

Size about 2 – 6 mm with globular


shape and smooth surface

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Production process

Soak in water for 10


days, leading to
fermentation

01 03
02
Fully ripe drupes are Dry and remove the
harvested pericarps (skin)

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1.2.3. GREEN PEPPER

pungent odor with milder taste Odor & flavor


than black pepper

green, greenish or dark Color


greenish

about 2 – 6 mm with globular shape


Size
with or without wrinkled pericarp

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Production process

01 02
Unripe Quickly dehydrated to preserve
drupes are color by using sulfur dioxide,
harvested canning or freeze-drying
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1.2.4. LONG PEPPER
hot and sweet flavor, more Odor & flavor
pungent than black pepper

green (immature) to stained pink Color


(mature) to dark black (dried)

about 2 – 5 cm long with drupe small,


arranged in the flower spike forming a Size
ompact fruiting, welded, reminiscent of black
catkins and hard 12
Production process

Repeatedly dry in
the sun for 4 – 5
days

01 03
02
Unripe spikes Dried spikes are
are gathered stored in moisture
proof container
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1.2.5. PINK PEPPER
mild, sweet and quite
Odor & flavor
pungent but not peppery
flavor

Color
pinkish red

Size very small berry, similar in


appearance to a peppercorn
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Production process

01 02
Collect the Dry and remove the
peppercorn pericarps (skin) to reveal
berries the pink seed inside
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1.2.6. SZECHUAN PEPPER
very aromatic, with a scent of
Odor & flavor
anise and a sweet fresh citrus
flavor

Color
browny-red

appearance and size similar


Size
to black pepper, but with a
split-open browny-red husk
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Production process

01 02
Collect the pepper Dry and collect the
at the end of the thin pink husk not
summer the seed
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Piperine
Type of pepper or berry Botanical name Country
content

Black peppercorn Piper nigrum Sri Lanka 6.3%

CONTENT TABLE
Green peppercorn Piper nigrum India 5.6%

1.3. PIPERINE
Red peppercorn Piper nigrum India 4.3%

Red peppercorn Piper nigrum Vietnam 3.4%


(Phu Quoc pepper)

White peppercorn Piper nigrum Cameroon 7.0%


(Penja pepper)

White peppercorn Piper nigrum Sri Lanka 6.6%

Piper longum Indonesia 3.7%


Long pepper

Piper retrofactum Vietnam 4.5%


Red long pepper
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Why we choose black pepper to extract piperine?

o Contain 2% – 7% piperine, certain report suggest up to 9%


piperine in black pepper.

o Require only drying process, no additional decortication of


outer pericarps (compared to whiter pepper)

“ The removal of outer pepper skin by


soaking into water can make the “
bioactive compound leached out.
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02.
BACKGROUND
OF
PEPPER

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BLACK PEPPER PRODUCTION MARKET
In the world

o Cultivated in the
tropics of South Asia
and Southeast Asia.

o Highly regarded as a
condiment since 2000 BCE.

o Referred to as "black gold" and used as a


form of commodity money.
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BLACK PEPPER PRODUCTION MARKET
In the world
o The legacy of this trade that recognize the term "peppercorn rent"
as a token payment for taxes and levies..

Black pepper from India's Malabar A depiction of Calicut, India published in 1572
region during Portugal's control of the pepper trade 22
BLACK PEPPER PRODUCTION MARKET
In the world

“ Black pepper accounts for about


of the world’s spice trade today. 1/5 “

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BLACK PEPPER PRODUCTION MARKET
In Viet Nam

o One of the world leader o A traditional cash crop, and almost of


countries in the the black pepper produced is
production of black exported to other countries all over
pepper. the world.

2018 The world's largest producer and exporter of black peppercorns.

262,658 36% of the world total


(tons)
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TOP AREA PRODUCING PEPPER 2018 TOP AREA PRODUCING PEPPER 2018 (HECTARES)
(HECTARES)
1%
1%
3% 1%
Others 4%
3000 5%
Madagascar 29%
4000
7%
Cambodia 6700
Malaysia 17437
China 20000
Brazil 27730 23%
Sri Lanka 36221 26%
Indonesia 117500
India 134280
Viet Nam 148744
0 50000 100000 150000 200000 Viet Nam India Indonesia Sri Lanka Brazil
Column2 Column1 Series 1 China Malaysia Cambodia Madagascar Others

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03.
PEPPER
PRODUCTION
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Procedure of pepper production
Spiral density
Cleaning classification Drying

01 02 03 04 05 06 07

Harvest Classification Washing Cooling


& & Weighing
Separation Microbiological Packing
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4.1. HARVEST

o Dry immediately or stack


about 2 – 3 days and dry once

o Drying process depends on


dose

o The process ends up


completely after about 3 to 4
days in sunny day.

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4.2. CLEANING
o Put raw pepper into a
submerged feed hopper and
transferred to the sieve of
impurities through a bucket.

o It can separate about 90 % of


impurities (mostly dust) mixed in
pepper.

o Raw material pepper, after


leaving the sieve, has diameter
between 2.5 - 6.5 mm. https://www.youtube.com/watch?v=xlI2RPoBp3o
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4.3. CLASSIFICATION & SEPARATION
o Pepper is conveyed by a bucket to the
reverse sieve for classification.

o Size graded pepper is put into 4


containers and can mix peppercorn to
finished product for export of further
processing.

o Pepper is fed into an aerodynamic sorting


device to remove light and porous
peppercorns.
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4.4. DRY SPIRAL SEPARATOR
Pepper after cleaning, sorting by size, separating
gravel and aerodynamic sorting still differ in
shape: deformed or round or still mixed with
pepper stalks feed it into the sorter.

https://www.youtube.com/watch?v=ovQv70S3Z48 31
4.5. WASHING AND MICROBIOLOGICAL TREATMENT
(with steam or ultraviolet rays)

To remove the most harmful microorganisms, salmonella:

o Use steam with a pressure from 2 - 3 kg/cm2 with


temperature of 1200 – 1400 oC to spray on
pepper in the shortest time (about 20 - 40 s).

o The pepper particles are passed through a line of


direct irradiation with an ultraviolet lamp with
wavelengths from (200 to 280 nm).

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4.6. DRYING

o The drying system uses two


continuous supply layer drying
towers, including two layers: the
input layer and the drying layer.

o The pepper drying capacity is


adjusted in accordance with the
raw material moisture to achieve
high efficiency.
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4.7. COOLING – WEIGHING - PACKING
o The pepper is put into a cooling tank and the pepper
is passed through the catador to separate impurities.

o The pepper is then fed into a spiral shaped sorter


(2nd time).

o Pepper product is put into storage tanks, or the


automatic weighing system as required, automatically
controlled from 30 - 60 kg, the permissible error is
±45g/50kg, the productivity is 200 bags/hour.

https://www.youtube.com/watch?v=3Wit0nKmxC8
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04
QUALITY STANDARD

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Vietnam Black Pepper Quality Standard
BLACK PEPPER

Dried peppercorns with complete


skin (Piper nigrum L.)

NON – PROCESSED (NP) SEMI – PROCESSED (SP)

has not been cleaned, has been cleaned but not


processed or graded processed or graded

not for sale, and does not satisfy the requirements of the standard
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Vietnam Black Pepper Quality Standard
GROUND BLACK PEPPER
BLACK PEPPER PROCESSED
(Gray pepper)

Black pepper is ground into


Pepper has been processed powder without any other
(cleaned, sorted, processed, …) substance and satisfies the
standard requirements

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Quality Standard

Major import countries Different grades of black pepper

Depending on the weight or


United States of America,
volume, the non-processed or
China, India, Pakistan, United
semi-processed pepper is
Arab Emirates, Germany, Egypt,
divided into 4 categories:
Netherlands, Philippines,
grade 1, grade 2, grade 3 and
United Kingdom,…
special grade (Chu Se pepper)

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4.1. Flavor requirements

NO

o odor
o strange taste
SPICY SMELL o molds
o insects
o magnifying glass

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4.2. Physical and Chemical requirements
Physical specifications

Required specifications
Black pepper NP or SP
Criteria Processed
Special
Grade 1 Grade 2 Grade 3 pepper
grade

1. The percentage of Extraneous matter


0.2 0.5 1.0 1.0 0.2
is no more than

2. The percentage of light berry is no


2 6 10 18 2.0
more than

3. The percentage of pinhead and


2.0 2.0 4.0 4.0 1.0
broken berry is no more than

4. Gram/litters is no less than 600 550 500 450 600


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4.2. Physical and Chemical requirements
Chemical specifications

Required specifications
Criteria Black pepper Processed Ground
NP or SP Black Pepper Pepper

1. Density is no more than: 13.0 12.5 12.5

2. The percentage of dried ashed is no more than: 7.0 6.0 6.0

3. The percentage of dried non-volatile either extracts is not less than: 6.0 6.0 6.0

4. Evaporation, % (ml/100g) by dry matter, not less than: 2.0 2.0 1.0

5. The percentage of piperine is no less than: 4.0 4.0 4.0

6. Insoluble Ash in acids, % is no more than: – – 1.2

7. Raw coarse, is no more than: – – 17.5


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4.2. Physical and Chemical requirements

Microbiological specifications

Criteria Limitation

1. Coliform, The quantity in 1g black pepper 102

2. E.coli, The quantity in 1g black pepper 0

3. Salmonella, The quantity in 25g black pepper 0

4. S.aureus, The quantity in 1g black pepper 102

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Quality Standard

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Quality Standard
Export Quality Spice must adhere to EU regulation no. 1881/2006 for
Aflatoxins/Ochratoxins and EU regulation concerning Maximum Residue Levels
on pesticides: no. 396/2005

Piper Gr/lt Bulk Volatile Oil Extraneous Mycotoxins ppb


Nigrum Density (VO) matter
Aflatoxin (B1 + B2 +
< 10
Grade 1 > 550 > 2% < 1.0% G1 + G2)
Aflatoxin B1 <5
Grade 2 > 500 > 2% < 1.5%
Ochratoxin A total < 15
Grade 3 > 450 > 1.8% < 2.0%

Grade 2 is also defined as FAQ: Fair Average Quality 1 ppb = 1μg/kg

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05.
COMPONENTS
OF BLACK
PEPPERCORN
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Contains much vitamin C Proteins
compared with tomatoes 25.5 %

Carbohydrate Fiber
37.4 % 23.6 %

0.66 % K Moisture
0.20 % Ca 4.7 %
0.16 % P
0.16 % Mg
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Essential oil Pungent compounds

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Oleoresin

o Oleoresin is a viscous liquid or semi-solid


material derived by extraction

o Concentrated produce that is obtained by


solvent extraction.

o Contain all the flavoring ingredients (related


to taste and smell) soluble in that particular
Black pepper solvent.
Oleoresin
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Pericarp (hull)

2.4 % piperine

Main compounds:
monoterpenes
38 volatile flavor
sesquiterpenes; their
compounds
oxygenated forms

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Kennel of black pepper
Extracted from
leaves and seeds

volatile oil Caryophyllene (19.12 %)


2-5 % Limonene (9.74 %)
Camphene (8.44 %)

Piperine (69.3 %)
oleoresin Alkaloids Piperyline (4 %)
5-9 % Piperanine (4 %)
Piperetine (12.9 %)
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BACKGROUND
06.
OF PIPERINE

51
INTRODUCTION

o Bitter - tasting

o Nitrogen - containing

o Ends with i - n - e

Ex: Caffein, Nicotine, Morphine…

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Revolutionary bonus

Evolving to be pungent to
defense from the attack of
microbial fungus and other
fruit-eating mammals.

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PIPERINE
There are four isomer form of piperine

Piperine Isopiperine

Chavicine Isochavicine
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PIPERINE
TRPV1
Heat
Protons
extracellular

The mechanism
of spiciness

Vanilloids intracellular

Cam/Ca2+

C-terminal
N-terminal
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PIPERINE

o Capsaicin

16 million
(Scoville Heat Units)

o Allyl Isothiocyanate

8000 - 100.000
(Scoville Heat Units)
Capsaicin in Allyl Isothiocyanate
Chili pepper in Wasabi

56
Application

Improved Metabolism

Piperine boosts metabolism


and improved
thermogenesis. This process
increases the body internal
temperature and helps to
breaks down the fat cells.

57
Application

Raised Dopamine and


Serotonin Levels

Dopamine and Serotonin are oftentime


called Happy Chemicals for the brain.
Piperine can help you have more
positive feelings, curbing stress levels,
and give you an overall more positive
experience.

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Application

Increase Biovailability
(main benefits)

People are taking


piperine to increases the
bioavailability of nutrients
like coenzyme Q10,
selenium, beta-carotene,
curcumin….
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Compound that should take with blackpeper

Curcumin Selenium B12

B6 Vitamin A
60
Compound that should not take together with piperine

Lithium Tegretol Rifampin

Dilantin Viramune
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07.
PHYSICAL
PROPERTIES
62
Color and state Yellow crystalline solid

Initially tasteless with


Taste
leaving a burning after taste

Melting point 128 – 130 oC

40 mg/ 1 L(Water)
1 g/ 15 mL (Alcohol)
Solubility
1 g/ 36 mL (Ether)
1 g/ 1.7 mL (Chloroform) Piperine crystal

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08.
EXTRACTION

64
Extraction methods

Modern
method

Conventional Supercritical fluid


method
Ultrasound-
Soxhlet
extraction assisted

Microway-assisted

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SOXHLET EXTRACTION
A schematic representation of a Soxhlet extractor:

6. Siphon top
1. Stirrer bar
7. Siphon exit
2. Still pot
8. Expansion adapter
3. Distillation path
9. Condenser
4. Thimble
10. Cooling water out
5. Solid
11. Cooling water in
(the still pot should not be overfilled and the volume of
solvent in the still pot should be 3 to 4 times the volume of
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the soxhlet chamber)
SOXHLET EXTRACTION

o A defined amount of dry sample is placed in a thimble

o The solvent is heated until its boiling point, and the


generated vapor is condensed

o The solution of the thimble-holder which carries


extracted solutes flows back into the distillation flask.

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SOXHLET EXTRACTION

o High amount of
solvent

Advantage o Possibility of thermal


degradation of
thermal sensitive
bioactive compound
o Simple, low cost

o Frequent contact
between the Disadvantage
material and solvent
in high temperature

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ULTRASOUND-ASSISTED EXTRACTION

Fig. 2 types of Ultrasoung-


assisted extraction.
(A) Ultrasound probe.
(B) Ultrasound sonic.

69
ULTRASOUND-ASSISTED EXTRACTION

o Lack of uniform
energy supplied

Advantage o Difficulty in solvent


renewing

o Need for filtration


o Lower extraction and washing
time
o Better solvent
penetration Disadvantage
o Operate at low
temperature

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MICROWAVE-ASSISTED EXTRACTION

71
MICROWAVE-ASSISTED PROCESS (MAP)

72
o Rapidly heating the solvent
Advantage → reduce time and solvent for extraction
MICROWAVE-
ASSISTED

o Low cost

o Depend on dielectric property of the solvent


Disadvantage
o Need for filtration

o Difficulty in solvent renewing

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ISOLATION PROCESS
Black
pepper corn
- Rotary evaporator
Concentration - 50 oC
- Until ~ 10 mL
Grinding
Ethanol
96%
- 3 time, each
Soxhlet time 2 hours
Oleoresin
extraction - Vigorous
stirring

Filtration - Vacuum

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1. Extraction Tank
2. Agitator
3. Foam Collection
4. Condenser
5. Cooler
6. Oil Water Separator
7. Double Linked Filter
8. Herbal Liquid
Collection Pump

Fig. Multifunctional Extraction Tank


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Fig. Extraction-Concentration system
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09.
PURIFICATION

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METHOD 1 Saturated
sodium
bicarbonate
Oleoresin solution

Dilute
HCl or Mixing - Dropwise addition
H2SO4
Soaking - 30 min
Filtration - Vacuum
DCM Hot
EtOH
- Slowly
Mixing - 3 time, each Recrystallization
- Room temperature
time 100 mL
Organic
Filtration - Vacuum
Aqueous
Disposing

PIPERINE
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METHOD 2
Oleoresin
10%
alcoholic
Filtration - Vacuum
KOH
Saponification Hot
EtOH
- Slowly
Recrystallization
- Room temperature
Filtration - Vacuum

Water Filtration - Vacuum


- Gentle stirring
Filtration - Dropwise
addition
PIPERINE
- In the fridge
Resting
- Overnight
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Fig. Crystallization system

Fig. Crystalline piperine, adapted from Investment Corporation


and Export Import An Phong Dak Nong, Vietnam 80
10.
IDENTIFICATION
81
IDENTIFICATION

Piperine can be characterized by its


melting point in the range from

129 - 130˚C

82
IDENTIFICATION
o High performance liquid chromatographic (HPLC)

Chromatogram of Piperine Chromatogram of Piper Iongum

Fig. HPLC of standard piperine.

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Why Piperine can enhance the
bioavailability of drugs and nutrients?
o Increases the secretion o Focuses and grows the
of bile acids activity of pancreas

o Piperine has a passive diffusion


stimulate digestion, boosts
mechanism, a high apparent
the ability of absorption of
permeability coefficient, and
food and drugs
short clearance time

o Piperine enhances gastrointestinal blood


raises the
flow which causes increased absorption of
blood supply
drugs from the digestive tract 84
Why Piperine can enhance the
bioavailability of drugs and nutrients?

regulate the membrane dynamics by

nonpolar interacting with lipids and hydrophobic


parts of the protein

modify enzyme conformation due to a decrease in the property


of membrane lipids to act as steric constraints to enzyme
proteins, which increases the absorptive surface for drug
85
Why Piperine can enhance the
bioavailability of drugs and nutrients?
o Effect on metabolism process

CYP P450
o Drugs are not metabolism, so
the accumulation of drugs is
increased and excreted slowly
Inhibits the process of
o The bioavailability of drugs is grown oxidation reaction as well as
but the probability of increasing taking part in the conjugate
toxicity in body can take place. reaction of drugs
86
The correlation between
Curcumin and Piperine
o Curcumin dissolves in fat, and as the digestive
system is a rather watery environment, most of
it just ends up being excreted by the body, the
small amount of curcumin that is absorbed is
Turmeric then rapidly metabolism

o Piperine increases the bioavailability of herbal and


conventional drugs such as curcumin Bio-
availability enhancing of curcumin could be due
to preventive effect of piperine on the intestinal
Curcumin and hepatic metabolism of curcumin
87
The correlation between
Curcumin and Piperine

Slow down liver metabolism of


curcumin enough that body can
absorbed it more effectively

01 03
02
Piperine relax the intestinal wall so More curcumin
large molecules like curcumin can is absorbed
pass through and be absorbed
88
The correlation between
Curcumin and Piperine

Curcumin Piperine

anti-inflammatory drugs reducing pain prevents and treats for


(without negative side and temporary rheumatoid and
effects) discomfort osteoarthritis

89
o Black Pepper is a spice o Through some suitable
commonly used in many extraction methods
areas of the world for flavor. and many stages of
It is a source of Piperine - purification, from the
an important component Black Pepper, the pure
in the pharmaceutical Piperine will be
industry. formed.

90
REFERENCE
[1] Tiwari, A., Mahadik, K. R., & Gabhe, S. Y., "Piperine: A comprehensive review of methods of isolation, purification, and biological properties," Medicine in
Drug Discovery, vol. 7, p. 100027, 2020.
[2] Aziz, N. S., Sofian-Seng, N. S. & Mustapha, W. A. W., "Functional Properties of Oleoresin Extracted from White Pepper (Piper nigrum L.) Retting Waste
Water," Sains Malaysiana, vol. 47, no. 9, p. 2009–2015, 2018.
[3] Al-Jasass, F. M., & Al-Jasser, M. S., "Chemical Composition and Fatty Acid Content of Some Spices and Herbs under Saudi Arabia Conditions," The
Scientific World Journal, pp. 1-5, 2012.
[4] C. K. Mathai, "Accumulation pattern of oleoresin and related chemical constituents in black pepper (Piper nigrum) berries during growth and development,"
Qualitas Plantarum Plant Foods for Human Nutrition, vol. 31, no. 1, pp. 3-10, 1981.
[5] Lee, J.-G., Chae, Y., Shin, Y., & Kim, Y.-J., "Chemical composition and antioxidant capacity of black pepper pericarp," Applied Biological Chemistry, vol.
63, no. 1, 2020.
[6] Hammouti, B., Dahmani, M., Yahyi, A., Ettouhami, A., Messali, M., Asehraou, A., Bouyanzer, A. & Warad, I. & Touzani, R., "Black Pepper, the "King of
Spices": Chemical composition to applications," Arabian Journal of Chemical and Environmental Research, vol. 6, no. 1, pp. 12-56, 2019.
[7] Martha Perez Gutierrez, R., Maria Neira Gonzalez, A., & Hoyo-Vadillo, C., "Alkaloids from Piper: A Review of its Phytochemistry and Pharmacology," Mini
Reviews in Medicinal Chemistry, vol. 13, no. 2, pp. 163-193, 2013.
[8] Epstein, W. W., Netz, D. F., & Seidel, J. L., "Isolation of piperine from black pepper," Journal of Chemical Education, vol. 70, no. 7, p. 598, 1993.
[9] Zihan Rahman Khan1, Fatema Moni1, Sharmin, S., Al-Mansur, M. A., Gafur, A., Rahman, O. & Afroz, F., "Isolation of Bulk Amount of Piperine as Active
Pharmaceutical Ingredient (API) from Black Pepper and White Pepper (Piper nigrum L.)," Pharmacology & Pharmacy, vol. 8, no. 7, pp. 253-262, 2017.
[10] Atal, N., & Bedi, K., "Bioenhancers: Revolutionary concept to market," Journal of Ayurveda and Integrative Medicine, vol. 1, no. 2, p. 96, 2010.
[11] K. Srinivasan, "Black Pepper and its Pungent Principle-Piperine: A Review of Diverse Physiological Effects," Food Science and Nutrition, vol. 47, no. 8, p.
735–748, 2007.
[12] Khajuria, A., Thusu, N. & Zutshi U., "Piperine modulates permeability characteristics of intestine by inducing alterations in membrane dynamics: influence
on brush border membrane fluidity, ultrastructure, and enzyme kinetics," Phytomedicine, vol. 9, pp. 224-231, 2002.
[13] Rinwa, P. & Kumar, A., " Piperine potentiates the protective effects of curcumin against chronic unpredictable stress-induced cognitive impairment and
oxidative damage in mice," Brain Res , vol. 1488, p. 38–50, 2012.
[14] G. J. D. J. T. M. M. R. R. &. S. P. Shoba, "Influence of Piperine on the Pharmacokinetics of Curcumin in Animals and Human Volunteers," Planta Medica,
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