Trends in Food Science & Technology 119 (2022) 45–56

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Trends in Food Science & Technology

journal homepage: www.elsevier.com/locate/tifs

Organocatalytic esterification of polysaccharides for food applications:

A review
K.V. Ragavan a, b, Oswaldo Hernandez-Hernandez c, Mario M. Martinez d, **,
Tomy J. Gutiérrez e, 1, *
a
Agro-processing and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Thiruvananthapuram, 695019, India
b
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India
c
Institute of Food Science Research (CIAL, CSIC-UAM), C/ Nicolas Cabrera, 9, Madrid, 28049, Spain
d
Department of Food Science, CiFOOD Multidisciplinary Center, Aarhus University, Agro Food Park 48, Aarhus N, 8200, Denmark
e
Grupo de Materiales Compuestos Termoplásticos (CoMP), Instituto de Investigaciones en Ciencia y Tecnología de Materiales (INTEMA), Facultad de Ingeniería,
Universidad Nacional de Mar del Plata (UNMdP) y Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Colón 10850, B7608FLC, Mar del Plata,
Buenos Aires, Argentina

A R T I C L E I N F O A B S T R A C T

Keywords: Background: The esterification of carbohydrate polymers for food applications has been extensively investigated
Dietary fiber and reviewed. Despite this, the ability of esterified carbohydrate polymers as dietary fiber, as well as bio-based
Esterified starches food packaging material makes this research area still of great interest. However, many of the reagents used
Food packaging
during esterification lead to moderate to severe environmental pollution.
Green chemistry
Resistant starch
Scope and approach: The objective of this review manuscript was to provide an overview of the reaction mech­
Short-chain fatty acids anisms of organocatalytic esterification of carbohydrate polymers destined for food applications.
Key findings and conclusions: Organocatalytically esterified polysaccharides (OEPs) have generally been synthe­
sized via green catalyst-assisted esterification reactions, with the main objective of grafting short-chain fatty
acids (SCFAs), simple organic acids and small hydrophobic moieties onto the backbone of carbohydrate poly­
mers. These SCFA-grafted OEPs, including SFCA-grafted starch, escape digestion and can efficiently deliver
SCFAs in the lower gut. SCFA-grafted OEPs can also influence colonic bacteria and derived catabolites in a
manner that provides cardiometabolic benefits. OEPs can also be used for the development of food packaging
with improved hydrophobicity and thermal stability. Remarkably, their degree of substitution (DS) underlies
their improved functionality as dietary compounds and/or food contact materials, with DS values between 0.01
and 0.2 when OEPs are designed for human consumption. It should be noted that the DS of the OEPs is limited by
the steric hindrances related to the structure of the native carbohydrate polymers and the grafted functional
group, as well as the reaction conditions.

strategies for grafting moieties onto the polymeric backbone or even

generating intra- or inter-molecular covalent crosslinking of carbohy­
1. Introduction
drate polymeric chains (Ludwig, Hu, Tappy, & Brand-Miller, 2018;
Valdes, Walter, Segal, & Spector, 2018; Zhong, Godwin, Jin, & Xiao,
Polysaccharides are abundant and versatile natural carbohydrate
2020). With this in mind, manufacturing novel carbohydrate polymers
polymers, which have been used for different food applications ranging
with fine-tuned functionalities still remains an important challenge for
from foodstuffs to food packaging materials (Valencia, Zare, Makvandi,
the food and packaging industries which, in turn, cannot afford dis­
& Gutiérrez, 2019). Interestingly, carbohydrate molecules have hy­
regarding environmental concerns. In this sense, new synthetic
droxyl groups available to react with other chemical groups, unlocking

* Corresponding author. Research Institute in Materials Science and Technology, Faculty of Engineering, National University of Mar del Plata and National Sci­
entific and Technical Research Council (CONICET), PO Box B7608FLC, Colón 10850, Mar del Plata, Buenos Aires, Argentina.
** Corresponding author. Department of Food Science, CiFOOD Multidisciplinary Center, Aarhus University, Agro Food Park 48, Aarhus N, 8200, Denmark.
E-mail addresses: mm@food.au.dk (M.M. Martinez), tomy.gutierrez@fi.mdp.edu.ar (T.J. Gutiérrez).
URL: https://www.tomy-j-gutierrez.com (T.J. Gutiérrez).
1
https://www.tomy-j-gutierrez.com.

https://doi.org/10.1016/j.tifs.2021.11.028
Received 14 April 2021; Received in revised form 5 November 2021; Accepted 25 November 2021
Available online 27 November 2021
0924-2244/© 2021 Elsevier Ltd. All rights reserved.
K.V. Ragavan et al.
Abbreviations
CO2 Carbon dioxide
DESs Deep eutectic solvents
DMSO Dimethyl sulfoxide
DS Degree of substitution
EmimOAc 1-ethyl-3-methylimidazolium acetate
FTIR Fourier transform infrared
HPLC High-performance liquid chromatography
K2CO3 Potassium carbonate
NMR Nuclear magnetic resonance
OEPs Organocatalytically esterified polysaccharides
SCFAs Short-chain fatty acids
XRD X-ray diffraction
DP Degree of polymerization
DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
pathways based on ‘green chemistry’ are increasingly being addressed
for the industrial manufacture of carbohydrate polymer derivatives with
the purpose of minimizing or suppressing the formation of toxic or
dangerous substances emitted into the environment from of a chemical
reaction, as well as reducing the consumption of energy, solvents, and
costs associated with reagents and substrates (feedstock) (Herniou–Ju­
lien, Mendieta, & Gutiérrez, 2019; Merino, Gutiérrez, & Alvarez, 2019;
Merino, Mansilla, Gutiérrez, Casalongué, & Alvarez, 2018). This
emerging perspective of chemistry (green chemistry) fits well with the
focus given to this review, which is based on a framework of twelve
principles that have been well discussed by other authors (Anastas &
Eghbali, 2010; Antenucci, Dughera, & Renzi, 2021). It is worth noting
that the manufacture of organocatalyzed carbohydrates is becoming
more widespread as an alternative synthetic route compared to con­
ventional synthetic routes for obtaining sustainable materials.
The hydroxyl groups of carbohydrates can form esters with organic
and some inorganic acids in the presence of a suitable base (e.g. sodium
hydroxide) or heavy metal-containing catalysts (BeMiller, 2018). Thus,
the use of a large number of solvents and/or toxic heavy
metal-containing catalysts has limited, for a long time, the manufacture
of organocatalytically esterified polysaccharides (OEPs) for food appli­
cations, whether for foodstuffs or food contact materials (or both). In
this regard, the synthesis of carbohydrate polymer derivatives by means
of organocatalysis-assisted esterification reactions using green catalysts
is promising (Crabtree, 2013a,b,c), since toxic catalysts, reagents and
solvents are not required to obtain high yields of OEPs under diverse
reaction conditions (Mahrwald, 2015a,b; Williams & Galan, 2017).
Although there are many review papers covering green reactions for
carbohydrate esterification (Aguilera, Tanchoux, Fochi, & Bernardi,
2020; Bjelić, Hočevar, Grilc, Novak, & Likozar, 2020; Faísca Phillips,
2014; Kamber et al., 2007; Mahé, Brière, & Dez, 2015; Meninno, 2020;
Pan & Ganguly, 2019; Song & Zheng, 2017), esterification using
naturally-occurring donors and organocatalysts, which are of particular
importance for the food industry, has received less attention. The
objective of this review article was to provide a perspective of the re­
action mechanisms and additional functionalities of food-grade OEPs.
2. Organocatalytically esterified polysaccharides (OEPs)
Polysaccharides (carbohydrate polymers) are the largest components
in biomass, non-toxic, inexpensive and are available in a large number of
molecular sizes and shapes and in a variety of chemical and physical
properties. The hydroxyl groups of carbohydrates can form esters with
carboxylic acids in the presence of a suitable catalyst. In the following
sections, commonly used structural and reserve polysaccharides in the
food industry, will be individually discussed for their potential
46
Trends in Food Science & Technology 119 (2022) 45–56
enhancement as functional materials for food and food packaging ap­
plications through organocatalytic esterification. The reaction mecha­
nisms involved in the synthesis of OEPs have already been well-reviewed
and discussed by other authors elsewhere (Aguilera et al., 2020; Bjelić
et al., 2020; Faísca Phillips, 2014; Kamber et al., 2007; Mahé et al.,
2015; Meninno, 2020; Pan & Ganguly, 2019; Song & Zheng, 2017).
Nevertheless, the type of organocatalyst, degree of substitution (DS),
and functional properties, among others, are some hot spots that will be
discussed in this review, since they can determine their potential in food
applications (Table 1).
2.1. OEPs from cellulose
Cellulose (general chemical formula - (C6H10O5)n) is a ubiquitous
natural polymer, major structural constituent of algal, bacterial and
plant cells, and rich in hydroxyl groups. Cellulose is a homopolymer
composed of D-glucose units linked by a β-glycosidic bond between the
C1 and C4 carbon of adjacent monomers (Gutiérrez & Alvarez, 2017a),
and therefore, can be categorized as dietary fiber (as it cannot be
digested by humans). Keeping its molecular structure in view, cellulose
derivatives can be obtained by using highly reactive modifiers or via
efficient catalysis (Kakuchi et al., 2015). However, the production of
cellulose esters on an industrial scale by catalysis has two important
challenges: 1) cellulose, being a rigid molecule, can rarely be dissolved
in the reaction solvent, which generally justifies the use of a dissolving
agent to increase the DS and 2) catalysis in acidic media causes partial
depolymerization of cellulose into shorter fragments, which hinders the
performance of long-length cellulose esters.
It is worth noting that cellulose has six different polymorphs, which
can be obtained according to the molecular environment. The poly­
morph I (structure most found in nature) is not very reactive and neither
accessible to enzymes (Rongpipi, Ye, Gomez, & Gomez, 2019). For this
reason, polymorphic changes in cellulose can determine its derivatiza­
tion. For example, Gan et al. (2020) reported tetramethyl
guanidine-assisted catalysis for the polymorphic conversion of I to II of
cellulose under a carbon dioxide (CO2) atmosphere at 50 ◦ C using DMSO
as a solvent, thus obtaining a more open and reactive polymorphic II
structure.
One of the objectives of the synthesis of OEPs is to increase the
prebiotic effect of these macromolecules, since their beneficial effect on
health is well known. In particular, cellulose can be grafted by short-
chain fatty acids (SCFAs) via organocatalysis-assisted esterification re­
actions. This technological alternative has allowed to increase the con­
centration of SCFAs (e.g. acetic acid, propionic acid and butyric acid)
that can be released and produced in the gut during the fermentation
process by probiotic bacteria. These SCFAs can then be absorbed by the
gut and pass into the bloodstream, thus allowing the reduction of
cholesterol levels in people suffering from hypercholesterolemia
(Gutiérrez, 2018b; Gutiérrez & Tovar, 2019, 2021). SCFA-grafted OEPs
have even shown positive effects in the prevention of colorectal cancer
(Nielsen et al., 2019). With this in mind, Kakuchi et al. (2015) synthe­
sized cellulose triacetate from cellulose by using 1-ethyl-3-methylimida­
zolium acetate (EmimOAc – imidazole-based ionic liquid) as a dual
reagent: catalyst and solvent at 80 ◦ C (Fig. 1A). As a result, a high DS
value (2.9) was reported by Kakuchi et al. (2015) compared to the
non-organocatalyzed reaction, thereby exhibiting a positive effect on
Gibbs free energy (ΔG), mainly in terms of the reaction kinetics (Fig. 1B)
(Kakuchi et al., 2017). Following Van Nguyen et al. (2017) and Suzuki
et al. (2018, 2020), EmimOAc can act as an organocatalyst via trans­
esterification from cellulose to obtain cellulose acetate. EmimOAc can
also help to break the inter- and intramolecular hydrogen-bonding in­
teractions of cellulose, thus obtaining DS values around 3. A similar
study was also carried out by Xu et al. (2018) who evaluated the dual
performance (catalyst and solvent) of DBU for obtaining cellulose ace­
tate, cellulose propionate and cellulose butyrate from cellulose in the
presence of CO2 and DMSO under relatively mild reaction conditions,
K.V. Ragavan et al. Trends in Food Science & Technology 119 (2022) 45–56

Table 1
Reaction conditions and main findings for the synthesis of OEPs for food applications.
Polysaccharide Polysaccharide source Organocatalyst Donor agenta Reaction OEPs/DS/Yield Main findings References
(substrate) conditions
Solvent or
reaction
medium/
reaction time/
reaction
temperature

Cellulose Bacterial cellulose Tartaric acid Acetic or Acetic or Acetylated Hydrophobic cellulose Ávila Ramírez,
from propionic propionic bacterial nanofibers based on Suriano,
Gluconacetobacter anhydride anhydride/8 h/ cellulose/0.45/- organic acids. Cerrutti, and
xylinus NRRL B-42 120 ◦ C Foresti (2014)
Avicel PH-101 (degree EmimOAc (also Isopropenyl EmimOAc/24 h/ Cellulose acetate/ Fast and highly efficient Kakuchi et al.
of polymerization acting as an acetate 80 ◦ C 2.96/- cellulose acetate (2015)
(DP): 105) activating agent) formation.
Bacterial cellulose Citric acid Acetic Acetic Acetylated High-temperature citric Ávila Ramírez,
from anhydride anhydride/3 h/ bacterial cellulose acid-catalyzed acetylation. Gómez Hoyos,
Gluconacetobacter 120 ◦ C nanoribbons/ Arroyo, Cerrutti,
xylinus NRRL B-42 0.47/- and Foresti
(2016)
Cellulose nanocrystals Citric acid Acetic Acetic Acetylated Solvent-free citric acid- Ávila Ramírez,
from microcrystalline anhydride anhydride/3 h/ nanocellulose based surface acetylation. Fortunati,
cellulose 120 ◦ C crystals/0.34/- Kenny, Torre,
and Foresti
(2017)
Avicel PH-101 EmimOAc Isopropenyl EmimOAc and Cellulose The transesterification Kakuchi et al.
acetate dimethyl acetate/-/79.7% reaction mechanism was (2017)
sulfoxide suggested.
(DMSO)/18 h/
80 ◦ C
Avicel PH-101 (DP: EmimOAc Isopropenyl EmimOAc and Cellulose acetate/ The transesterification Van Nguyen
105) acetate DMSO/30 h/ 2.95/- reaction mechanism was et al. (2017)
80 ◦ C suggested. Reuse of
organocatalysts for
multiple cycles.
Microcrystalline 1,8-diazabicyclo Vinyl benzoate, CO2, DBU and Cellulose Low temperature Chen et al.
cellulose (DP: 240) [5.4.0]undec-7- vinyl pivalate DMSO/4 h/ benzoate/2.6/- transesterification. (2018)
ene (DBU) and vinyl 25 ◦ C
laurate
Bagasse EmimOAc Isopropenyl EmimOAc and Cellulose Cellulose triacetate Suzuki et al.
(Lignocellulosic acetate DMSO/0.5 h/ triacetate/2.98/- obtained from bagasse was (2018)
biomass) 80 ◦ C comparable with the
cellulose triacetate derived
from Avicel.
Cotton cellulose pulp DBU Acetic, butyric DBU, CO2 and Cellulose Synthesis of mixed Xu et al. (2018)
(DP: 700) or propionate DMSO/2 h/ propionate and cellulose esters using ionic
anhydrides 80 ◦ C cellulose butyrate/ liquids.
2.85 and 2.89/-
Bacterial cellulose Citric acid Acetic Acetic Acetylated Polylactic acid/acetylated Ávila Ramírez,
from anhydride anhydride/5 h/ bacterial bacterial cellulose Cerrutti, Bernal,
Gluconacetobacter 120 ◦ C cellulose/0.61/- nanocomposite films with Errea, and
xylinus NRRL B-42 improved optical and Foresti (2019)
mechanical properties.
Microcrystalline EmimOAc Vinyl acetate EmimOAc/2 h/ Cellulose Synthesis of cellulose Chen et al.
cellulose from cotton 90 ◦ C triacetate/2.86/- triacetate with a higher (2019)
(DP:137) reaction rate.
Sugarcane bagasse EmimOAc Isopropenyl EmimOAc and Cellulose acetate/ Direct green synthesis and Suzuki, Yada,
acetate DMSO/5 h/ 2.8–2.9/≤ 50% fractionation of cellulose Hamano, Wada,
50 ◦ C acetate from sugarcane and Takahashi
bagasse. (2020)
Starch Native corn starch Tartaric acid Acetic Acetic Starch acetate and Acetated and butyrylated Tupa,
anhydride and anhydride/7 h/ starch butyrate/ starches with DS from 0.06 Maldonado,
butyric acid 120 ◦ C 1.23 and 1.45/- to 1.54, prepared via Vázquez, and
Butyric acid/2.5 simple direct solvent-free Foresti (2013)
h/120 ◦ C organocatalytic.
Native corn starch Tartaric acid Acetic Acetic Cellulose starch/ High DS starches. Tupa, Ávila
anhydride anhydride/3 h/ 2.93/- Ramírez,
130 ◦ C Vázquez, and
Foresti (2015)
Four commercial Tartaric acid Butyric acid Butyric acid/5 Butyrylated Product characterization Nielsen, Canibe,
starches with different h/120 ◦ C starch/2.41/- by NMR and in vitro and Larsen
amylose/amylopectin fermentation studies. (2018)
ratios
Native and gelatinized L-tartaric acid Propionic acid Propionic acid/ Organic acid-catalyzed
corn starch 5 h/130 ◦ C synthesis for type 4
(continued on next page)

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Table 1 (continued )
Polysaccharide Polysaccharide source Organocatalyst Donor agenta Reaction OEPs/DS/Yield Main findings References
(substrate) conditions
Solvent or
reaction
medium/
reaction time/
reaction
temperature

Propionated resistant starch Tupa, Arroyo,

starch/0.46 and production: acetylated and Herrera, and
0.69/- butyrylated starches. Foresti (2018)
Four commercial Tartaric acid Acetic, Acid/anhydride/ Acetic, propionic Organically esterified Imre and
starches with different propionic and 1–16 h/130 ◦ C and butyric starches using tartaric acid Vilaplana (2020)
amylose/amylopectin butyric acid starch/2.0/- as a green catalyst.
ratios
β-Glucans β-Glucan from oats N,N′ -carbonyl-di- Methyl DMSO/16 h Fatty acid β-glucan Dispersion of curcumin in Chen, Liu, Ye,
imidazole decanoate, (activation)/ ester/ water with the help of fatty and Zhao (2014)
methyl 60 ◦ C 0.0297–0.0309 acid β-glucan ester.
octanoate and DMSO/4 h
methyl (acylation)/
hexanoate 70 ◦ C
Dextrin, pullulan and EmimOAc Isopropenyl EmimOAc and Acetylated Reusability of the Van Nguyen
xylan acetate DMSO/0.5 h/ dextrin, pullulan organocatalysts for et al. (2017)
80 ◦ C and xylan/2.94, multiple cycles.
2.99 and 1.88/-
a
Donor chemical reagent of the functional moieties to be grafted.

Fig. 1. Panel A) Reaction for obtaining organocatalytically esterified cellulose using EmimOAc/DMSO mixed solvent system. Reproduced with permission from
Kakuchi et al. (2015). Panel B) Enthalpic changes associated to the green chemistry reaction kinetics proposed for obtaining organocatalytically esterified cellulose
via transesterification reactions in the absence (upper pathway) and presence (lower pathway) of ionic liquids. Rec: reagents, Pro: reaction product, 1TS1: transition
state in the absence of ionic liquids, 1TS2: transition state in the presence of ionic liquids, 1Int1: first intermediate compound and 1Int2: second intermediate
compound. Reproduced with permission from Kakuchi et al. (2017). Panel C) Catalytic cycle proposed for obtaining organocatalytically esterified cellulose by using
L-tartaric as green catalyst. Adapted with permission from Ávila Ramírez et al. (2014). (For interpretation of the references to color in this figure legend, the reader is
referred to the Web version of this article.)

thus resulting in high DS values. According to Wei, Kumar, and Banker
(1996), this method has the additional advantage of an insignificant
degradation of cellulose compared to catalyzed reactions from cellulose
by using EmimOAc. An important point to highlight is the recovery
capacity of the catalysts (DBU and EmimOAc) from the reaction medium
(Van Nguyen et al., 2017). However, the catalyst recovery process is
laborious, requires solvents, and multiple steps are required, thus
limiting its potential application on an industrial scale.
It is worth noting that the donor agent (donor chemical reagent of the
functional moieties to be grafted) also affects the synthesis of the OEPs.

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In particular, acetic, butyric and propionic acids are typically used as
donor agents for the development of OEP-based dietary fiber, while
other donor agents such as vinyl acetate can be used for the synthesis of
organocatalyzed cellulose assisted by DBU or EmimOAc intended as
food contact materials (food packaging) (Fig. 2) (Chen et al., 2018,
2019). Despite the advantages of the synthesis of OEPs, the obtaining of
unwanted by-products of the reaction, unreacted reagents and the effi­
cient recovery of the catalysts are still points worthy of further investi­
gation in order to guarantee food quality and safety (Lalanne-Tisné,
Mees, Eyley, Zinck, & Thielemans, 2020). For this reason, the hetero­
geneous catalysis of OEPs through the use of supercritical fluids, or solid
phase reactions using catalysts or reagents supported and immobilized
on polymers or mesoporous particles such as zeolites can be suggested
instead of the frequently employed homogeneous catalysis, since the
direct contact between chemical reagents and desired OEPs can be
limited, as well as the formation of side reaction products (unwanted
reaction by-products) can potentially be reduced. Therefore, the con­
ditions of heterogeneous catalysis could favor obtaining OEPs of high
quality and purity in terms of the desired physicochemical, toxicological
and nutritional properties (Peng, Lin, Li, & Yang, 2011; Ragavan, Egan,
& Neethirajan, 2018; Simon & Li, 2012; Sudarsanam et al., 2018;
Tzschucke et al., 2002).
It is also important to note that citric and tartaric acids have been
used as efficient green organocatalysts to obtain cellulose derivatives via
the surface transesterification reaction of cellulose, using either acetic
acid, hexadecanoic acid (palmitic acid - C16:0) or propionic acid as
donor agents (acylant), thus resulting in more hydrophobic cellulose
derivatives compared to unmodified cellulose (native), which have DS
values varying from 0.25 to 0.73 (Ávila Ramírez et al., 2014, 2016,
2017, 2019; Hafrén & Córdova, 2005). Nonetheless, citric acid has
proven to be more effective as a green organocatalyst than tartaric acid
(Ávila Ramírez et al., 2016), and those cellulose derivatives obtained
with high DS values could be used as compatible natural fillers in blends
made from hydrophilic polymers in order to obtain food packaging
materials with improved chemical and mechanical properties (Ávila
Ramírez et al., 2019). According to Ávila Ramírez et al. (2019, 2017,
2016, 2014), the method used by them allows obtaining sustainable and
eco-friendly organocatalyzed cellulose derivatives by using citric or
tartaric acid, since acid residues can be neutralized and washed with
little water, and the crystalline structure of the cellulose is not altered

Fig. 2. Panel A) EMIMOAc-catalyzed esterification reaction to obtain cellulose acetate from cellulose, showing their respective Fourier transform infrared (FTIR)
and nuclear magnetic resonance (NMR) spectra. Panel B) X-ray diffraction (XRD) patterns, DS values and illustration of structural changes from cellulose during the
advancement of the EMIMOAc-assisted organocatalytic reaction for obtaining cellulose acetate. Reproduced with permission from Chen et al. (2019).

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K.V. Ragavan et al. Trends in Food Science & Technology 119 (2022) 45–56

(Fig. 1C).
Another factor of special importance for obtaining organocatalyti­
cally esterified cellulose is the use of deep eutectic solvents (DESs), since
they can improve the solubility of cellulose in the reaction media, thus
acting as co-catalysts of the reaction. In summary, the reaction kinetic is
accelerated and the DS values could potentially be higher compared to
the use of conventional solvents. In this context, a significant advance
towards the green chemistry route to obtain organocatalytically esteri­
fied cellulose for food applications could be expected through the use of
natural DESs, such as choline chloride, choline dihydrogen citrate and
some enzymes (Deng, Han, Hu, Zheng, & Liu, 2019; Zdanowicz &
Johansson, 2016).
2.2. OEPs from starch
Starch is one of the most abundant polymer carbohydrates in nature
after cellulose and lignin (Herniou–Julien et al., 2019), and it is
responsible for a large portion of daily dietary caloric intake (Gutiérrez
& Tovar, 2021; Martinez, 2021), thus explaining its relevance within the
food industry. Starch theoretically has three available hydroxyl groups
located at the C2, C3 and C6 positions capable of being esterified by
carboxylic acids, or carboxylic acid anhydrides or chlorides (donor
chemical reagents) (maximum DS = 3.0) (Fig. 3) by using bases (e.g.
sodium hydroxide) or inorganic salts as catalysts. Nevertheless, the
amount of functional moieties that can be grafted onto the starch are
limited by this type of catalyst. In addition, large amounts of wastewater
and reaction by-products are issues of great concern in terms of envi­
ronmental and food safety, thus limiting their availability to be mar­
keted as a feedstock. This has also justified the use of green
organocatalysts aimed at the synthesis of esterified starches, mainly
using acetic, butyric and propionic acids as donor agents (acylant). In
this sense, acetylated, butyrylated or propionylated starches can in­
crease the value of starch as dietary fiber (resistant starch) (Tupa et al.,
2018), as they can resist amylolysis of the small gut (Annison, Illman, &
Topping, 2003). These modified starches can thus be considered as
prebiotic with potential health benefits (Annison et al., 2003), since
upon reaching the large gut, they can, for example, be fermented by
butyrogenic bacteria that are present in the Firmicutes and not in the
Bacteroidetes (Hamaker & Tuncil, 2014), thus releasing and/or gener­
ating beneficial SCFAs (Annison et al., 2003; Gutiérrez, 2018a,b). This is
especially important considering that the consumption of SCFAs from
the diet is rapidly absorbed in the proximal gut, and a smaller fraction
(~40%) reaches the large gut (Illman et al., 1988; Macfarlane, Gibson, &
Cummings, 1992). This fact was particularly confirmed by Clarke et al.
(2011), who demonstrated that cooked and esterified high-amylose corn
starch from butyric anhydride (DS = 0.25, measured by 13C NMR), and
using 1-methylimidazole as an organocatalyst, allowed the release of
about 50 mmol/day of butyrate in the gastrointestinal tract from a daily
intake of 40 g of butyrylated starch. Remarkably, ~57% of the butyrate
grafted onto the starch was released in the large gut. Thus, the manu­
facture of organocatalyzed starches using green chemistry shows
promising potential for promoting health benefits through dietary
compounds, and clearly highlights the need for further research in this
field.
Food grade esterified (acetylated, butyrylated and propionylated)
starches synthesized by green organocatalysts such as α-hydrox­
ycarboxylic acids (e.g. citric, lactic and tartaric acids) and amino acids
(e.g. aspartic acid, glutamic acid and proline) have been shown to
selectively yield modified starches of diverse DS values under mild re­
action conditions, thus reducing the amount of reaction by-products
(Domínguez de María, 2010; Imre & Vilaplana, 2020). The DS values
can also be easily controlled through the reaction time and amount of
catalyst (Di Filippo, Tupa, Vázquez, & Foresti, 2016; Imre & Vilaplana,
2020; Tupa et al., 2013, 2015). The aforementioned green catalysts for
the manufacture of SCFA-grafted starches can be extracted from natural
resources or produced on a large scale via biotechnology routes in a
simply and cost-effectively (Domínguez de María, 2010). These aspects
reveal the sustainability of the synthesis of organocatalyzed starches for
food applications. With this in mind, Tupa et al. (2013) synthesized
acetylated and butyrylated starches via tartaric acid-organocatalyzed
esterification reactions by using acetic anhydride and butyric acid as
donor agents at 120 ◦ C, resulting in DS values between 0.06 and 1.54. An
increase in the DS values (up to 2.93) was also found by these authors
(Tupa et al., 2013), due to the increase in the concentration of the
catalyst. It is worth mentioning that Tupa et al. (2013) determined the
DS values by back titration. According to Nielsen et al. (2018), the DS
values obtained by back titration can be overestimated between 31 and
91% compared to the determination of the DS values by NMR. Taking
into account Volant et al. (2020), this occurs due to the inability of back
titration to distinguish between carboxylic acid species and related side
groups. Another suitable methodology to determine DS is by
high-performance liquid chromatography (HPLC), since the exact nature
and quantity of the side groups linked to the starch substrate can be well
determined (Imre & Vilaplana, 2020). However, the determination of DS

Fig. 3. Starch esterification by using (A) acids and (B) anhydrides. Adapted with permission from BeMiller (2018) and Imre and Vilaplana (2020).

50
K.V. Ragavan et al.
values is preferable by solid-state 13C NMR, since information about the
amorphous and crystalline structure can also be provided (Volant et al.,
2020). This is a key point that must be considered for future research by
other authors. Despite this technical detail, the liquid phase containing
the catalyst and the unreacted donor agent residues can be effectively
recovered and reused for other synthesis cycles (Imre & Vilaplana,
2020).
Other naturally-occurring dicarboxylic acids (fumaric and maleic
acid), hydroxy mono- (glycolic and lactic acid), di- (malic and tartaric
acid) and tricarboxylic (citric acid) acids have also been used by Imre
and Vilaplana (2020) as green catalysts for obtaining acetylated corn
starch from acetic anhydride or acid (donor agents). As a result, Imre
and Vilaplana (2020) reported higher catalytic activity from citric and
tartaric acids, thereby reaching DS values between 0.62 and 0.85
(measured by HPLC). These DS values are similar to those acetylated
starches by conventional methods using aqueous alkaline solutions as
catalysts (Imre & Vilaplana, 2020). This demonstrates the effectiveness
of green organocatalyst-assisted esterification reactions. Imre and Vila­
plana (2020) also found that esterification with an anhydride results in
the formation of the respective acid as a by-product, while esterification
with acid causes the elimination of water (Fig. 3), thus yielding starches
with different structural arrangements. Specifically, the water released
due to the acid-organocatalyzed esterification reactions can plasticize
the starch and break the inter- and intramolecular hydrogen bonds
induced by the progressive replacement of the –OH groups, thus the
eventual crystalline granular loss of the starch is expected. This could
improve the exposure of the hydroxyl groups to the donor agent, and
therefore, accelerate the rate of the esterification reaction. Notwith­
standing, inadequate starch functionality can also be caused when
granular starches are desired. In addition, the use of acids as donor
agents compared to their anhydride analogs can also result in greater
molecular fragmentation of starch, and as a result, greater participation
of the catalyst (tartaric acid) in starch substitution reactions (Imre &
Vilaplana, 2020; Nielsen et al., 2018).
The nature of the starch substrate also affects the efficiency of the
green catalyst-assisted esterification reactions. Following Imre and
Vilaplana (2020), amylose is more reactive than amylopectin in this type
of reactions. However, the reactivity of the starch substrate in this type
of reactions really depends on the recalcitrant nature (crystallinity) of
the starch used (Luo & Shi, 2012). At the molecular level, the starch
substrate has three positions capable of being esterified: C2, C3 and C6,
which have the following increasing order of reactivity: C3 < C2 < C6.
This order of reactivity can be explained as follows: a primary –OH
group is found at the C6 position of the starch substrate, which is less
sterically hindered compared to the secondary –OH groups located at
the C2 and C3 positions (Xu, Miladinov, & Hanna, 2004), while the –OH
group located at the C2 position is more reactive than the –OH group
located at C3, due to its proximity to hemiacetal. Hence, the structure of
the starch can critically affect the efficiency of the reaction and DS. A
similar effect on reactivity in organocatalysis-assisted esterification re­
actions occurs through the use of long-chain carboxylic acids (donor
agents), since the steric hindrances govern this type of reaction (Liu,
Lotero, & Goodwin, 2006).
Other organocatalyzed starches can also be synthesized by using
enzymes as green organocatalysts. However, the semicrystalline struc­
ture of starch must first be disrupted with hot water or an organic sol­
vent (e.g. DMSO) in order to improve the reaction rate (Xu et al., 2004).
In this context, pro-ecological solvents such as ionic liquids (e.g.
1-N-butyl-3-methylimidazolium chloride) are ideal for breaking the
intramolecular hydrogen bonds from starch, thus increasing its reac­
tivity (Gilet et al., 2018). These solvents have unique properties such as
low melting points, low vapor pressure, non-flammability and recycla­
bility. Nonetheless, the reaction in ionic liquids may turn out to be less
efficient than other organocatalyzed reactions, since more by-products
are generated, as well as more feedstock and energy may be required.
In addition, the high cost of ionic liquids is an important problem that
51
Trends in Food Science & Technology 119 (2022) 45–56
must be previously solved to achieve its industrial scaling. More
recently, natural DESs have also been suggested as pro-ecological sol­
vents for the synthesis of organocatalytically esterified starch. For
example, Zdanowicz and Johansson (2016) observed that the use of
choline chloride and choline dihydrogen citrate as natural DESs allowed
the crosslinking of starch chains. Meanwhile, Deng et al. (2019) syn­
thesized starch decanoate, starch laurate and starch palmitate by using
choline chloride, Novozyme 435 (immobilized lipase) and polyethylene
glycol 400 (PEG 400), as natural DES, catalyst and phase transfer agent,
respectively. As a result, the obtained OEPs exhibited DS values varying
from 0.07 to 0.19, and showing minimal starch degradation. Deng et al.
(2019) also observed that the crystalline structure of starch was altered
by the use of natural DES, as well as the starches obtained had lower
temperatures and enthalpies of crystallization than native starch.
Organocatalysis-assisted crosslinking reactions using octoates have
also proven to be efficient for obtaining organocatalyzed starches
(Gutiérrez & Alvarez, 2017b,c,d; Herniou–Julien et al., 2019). However,
the United States Food and Drug Administration (USFDA, 2020a) has
only approved the employ of this type of catalysts for obtaining food
contact materials (food packaging), but its use should not exceed 1% of
catalyst by weight of material. It should be noted that this field of
research has been less studied, probably due to the relatively recent
authorization for the use of this type of catalyst.
2.3. OEPs from mixed-bond glucans
Mixed-bond β-glucans are commonly referred to as β-glucans. They
are one of the most used and well-characterized functional poly­
saccharides in food applications. β-glucans containing β-(1 → 3) and
β-(1 → 6) bonds are mainly isolated from the cell walls of cereals, pri­
marily barley and oat, whereas those encompassed by β-(1 → 3) and β-(1
→ 4) bonds are isolated from yeast cell-walls (Zhu, Du, & Xu, 2016). Oat
β-glucans were successfully esterified by Chen et al. (2014) using three
different acyl donors (methyl decanoate, methyl hexanoate and methyl
octanoate), and employing 1,1-carbonyldiimidazole as a catalyst, which
is considered a green reagent (Métro, Martinez, & Lamaty, 2017). Ac­
cording to Chen et al. (2014) the DS values were not affected by the acyl
chain length. Higher DS values could, however, be obtained, previously
solubilizing the β-glucans, which has typically been achieved through
the use of toxic organic solvents such as DMSO. Nonetheless, ionic liq­
uids and physical treatments involving high temperature, pressure or
radiation have made it possible to reduce the use of these polluting
substances. For example, Liu et al. (2020) increased the water solubility
of yeast β-glucans by up to 75%, as a result of the cleavage of the
H-bonds of β-glucans through the use of EmimOAc (dual reagent: cata­
lyst and solvent) and a high-pressure treatment (24,000 psi). Interest­
ingly, despite the high pressure applied, the ionic liquid used did not
undergo any chemical alteration and can thus be recycled for further
reactions. Other glucans such as pullulan and dextrin have also been
successfully acetylated using EmimOAc as a dual reagent: catalyst and
solvent (Van Nguyen et al., 2017). It is worth noting that esterified
β-glucans have been shown to increase the swelling power and bile acid
binding capacity of digesta, with possible benefits for cholesterol
metabolism (Joyce, Kamil, Fleige, & Gahan, 2019). Acetylation of
β-glucan can also reduce the hardness and adhesiveness of native
β-glucan, which is useful for the development of functional beverages
(De Souza et al., 2015).
2.4. OEPs from other polysaccharides
The term gums usually encompasses complex polysaccharides widely
used in the food industry for their ability to form gels (or alter rheo­
logical properties) at a low concentration (Barak, Mudgil, & Taneja,
2020). Gums are obtained primarily from plants (e.g. guar gum and
locust bean gum), microorganisms (e.g. xanthan gum), and algae (e.g.
alginate and carrageenan). Different modifications have been carried
K.V. Ragavan et al.
out on gums as reviewed by Rana et al. (2011) and Liu, Shim, Tse, Wang,
and Reaney (2018). However, no modifications have been reported
using green organocatalysts. Many of the works have been focused on
the use of an eco-friendly catalyst, but most of them are metal-based or
toxic. For example, Simões et al. (2020) synthesized stable
starch-xanthan hydrogels as potential functional food additive carriers
by using citric acid and sodium hypophosphite, as crosslinking agent
and catalyst, respectively, in order to improve their mechanical prop­
erties. A similar study was done by Hamcerencu, Desbrieres, Khoukh,
Popa, and Riess (2008) who synthesized unsaturated esters of gellan
gum using N’-[3-(dimethylaminopropyl)]-N-ethylcarbodiimide hydro­
chloride as a catalyst, to also be potentially destined as functional food
carriers.
Pectins are heterogeneous polysaccharides, which are mainly found
in the cell walls of fruits and vegetables. These polysaccharides are
composed of up to 17 different monosaccharide units and can contain
more than 20 different bonds, which are principally ester or glycosidic
(Muñoz-Almagro, Montilla, & Villamiel, 2021). The most abundant
structures present in pectins are homogalacturonan and rhamnoga­
lacturonan I and II, which are fundamentally composed by D-galactose,
galacturonic acid, L-arabinose and L-rhamnose (Roman et al., 2021). The
structures of pectins vary widely in terms of their degree of esterification
by acetyl and/or methyl groups depending on the plant source, this
being one of the distinctive characteristics of pectins. Very few studies
have reported the modification of pectin via organocatalyzed reactions.
Most of the works have been carried out using metal-based or toxic
catalysts, mainly potassium carbonate (K2CO3). For example, Mon­
fregola, Leone, Vittoria, Amodeo, and De Luca (2011) grafted fatty acids,
such as palmitic, oleic and linoleic anhydride onto the high methoxyl
pectin structure (70–75%) extracted from apple by using K2CO3 as a
catalyst. These authors concluded that the structure of fatty acids plays
an important role on the DS values obtained: the length of the acyl chain
affects DS values more than the presence of unsaturations (Monfregola
et al., 2011). It is also worth noting that double-derived pectins (fatty
acid-grafted and quaternized pectin) were obtained by Calce, Petricci,
Saviano, and De Luca (2017) using K2CO3 as a catalyst. These authors
reported antimicrobial properties from the materials synthesized, due to
quaternary alkyl ammonium moieties. However, these compounds were
unstable and can cause scaling (Calce et al., 2017).
It is also noteworthy that mixed-bond glucans and heterogeneous
polysaccharides are structurally very diverse. Therefore, their reaction
mechanisms are highly unpredictable compared to the reaction mech­
anisms given on cellulose or starch when used as a substrate for the
production of OEPs. In this sense, computational chemistry and molec­
ular modeling could reveal structural bottlenecks for a better under­
standing of OEP manufacturing.
Fig. 4. OEPs from starch for food applications depending on its DS. Adapted with permission from Imre and Vilaplana (2020).
52
Trends in Food Science & Technology 119 (2022) 45–56
3. Applications of OEPs and future perspectives
OEPs have been primarily targeted as intentionally added food ad­
ditives for the development of functional foodstuffs or food packaging,
depending on their DS: low DS values for functional foods and high DS
values for the manufacture of food packaging (Fig. 4) (Imre & Vilaplana,
2020). In particular, OEPs with a high DS and substituted with non-polar
functional groups can lead to the obtaining of biobased polymers with a
chemical character relatively more similar to those derived from pe­
troleum. A marked improvement in water vapor and oxygen barrier
properties could thus be expected compared to natural polysaccharides
(Zdanowicz & Johansson, 2016), which in turn could increase the shelf
life of packaged foodstuffs, as well as reduce their waste (Gutiérrez &
Álvarez, 2017). The scientific community working in the food packaging
area is thus encouraged to evaluate the suitability of these alternatives,
even considering one-step processes such as reactive
extrusion-processed polysaccharides (Gutiérrez & Valencia, 2021; Her­
niou–Julien & Gutiérrez, 2021; Imre, García, Puglia, & Vilaplana, 2019).
On the other hand, the impact of food grade OEPs on the release and
colonic production of SCFAs has been largely overlooked. Hence, in vitro
and in vivo studies are needed in order to elucidate the nutritional value
of OEPs. It should be noted that there are still no specific laws or norms
that regulate the manufacture of OEPs intended for the food industry.
However, the criteria indicated above for the potential applications of
OEPs is based on the maximum DS allowed by the USFDA (2020b) for
esterified starches without the use of catalysts, or using inorganic cat­
alysts. Therefore, the synthesis conditions, the type of solvent, as well as
the reactivity of the donor agent and the carbohydrate polymer substrate
are key points for the desired application.
Although noble metal-based catalysts are efficient transformers, they
are not economical, often lose their activity due to impurities, and
impose recyclability challenges. Thus, organocatalysts are increasingly
used as alternatives for metal-based catalysts in most catalytic reactions.
Citric, fumaric, glycolic, lactic, maleic, malic and tartaric acids, as well
as some amino acids (e.g. aspartic acid, glutamic acid and proline) have
proven to be green catalysts for the synthesis of targeted OEPs for the
food industry, since according to the USFDA (2020c,d,e,f,g,h,i,j) all
these substances are “generally recognized as safe when used in accor­
dance with good manufacturing or feeding practice”. Nonetheless, the
use of malic acid has been regulated by the USFDA (2020j) with a
maximum limit allowed between 0.7 and 6.9%, depending on the type of
food manufactured: gelatins, puddings, and fillings (0.8%), jams and
jellies (2.6%), chewing gum (3.0%), soft candy (3.0%), nonalcoholic
beverages (3.4%), processed fruits and fruit juices (3.5%), hard candy
(6.9%) and all other food categories (0.7%).
OEPs are manufactured mainly by grafting SCFAs onto the structure
of native carbohydrate polymers to yield acetylated, butyrylated and
propionylated carbohydrate polymers. Its potential applications are
K.V. Ragavan et al.
limited by the DS values of the OEPs: low DS values (maximum DS =
0.2) for functional foods and high DS values for the manufacture of food
contact materials (maximum DS = 3). In special, citric and tartaric acids
have proven to be the most suitable green catalysts for obtaining OEPs
with high DS values. Finally, the kinetic aspects of the organocatalysis-
assisted esterification reactions are governed by 1) the steric hindrances
associated with both the native carbohydrate polymer substrate and the
donor agents (functional group to be grafted) and 2) the use of DESs and
ionic liquids. Although, natural DESs are increasingly preferred as sol­
vents and co-catalysts for the manufacture of OEPs instead of toxic
organic solvents (Bjelić et al., 2020), since they can increase the solu­
bility of the reactants via hydrogen bonding, as well as aid in the sepa­
ration and purification of the reaction products through relatively
simple steps. This is in accordance with the principles of green chemistry
(Dai, van Spronsen, Witkamp, Verpoorte, & Choi, 2013).
Declaration of interest statement
The authors declare no conflict of interest.
CRediT authorship contribution statement
K. V. Ragavan wrote sections 2 and 2.1. O. Hernandez-Hernandez
wrote sections 2.3 and 2.4. M. M. Martinez wrote section 2.2. T. J.
Gutiérrez wrote sections 1 and 4, and conceived the manuscript. T. J.
Gutiérrez and M.M. Martinez coordinated the work, and edited and
corrected the final version of the manuscript. All authors read and
approved the submitted manuscript.
Acknowledgments
K. V. Ragavan and M. M. Martinez would like to thank the Natural
Sciences and Engineering Research Council of Canada (NSERC) [grant
number 401499] for financial support. O. Hernandez-Hernandez has
received funding from the European Union’s Horizon 2020 research and
innovation program (grant agreement GLYCO-WAY No 843950). M. M.
Martinez would also like to thank the Aarhus University Research
Foundation (AUFF Starting Grant) for financial support. T. J. Gutiérrez
would like to thank the Consejo Nacional de Investigaciones Científicas
y Técnicas (CONICET), Universidad Nacional de Mar del Plata (UNMdP)
and Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT)
(grant PICT-2017-1362) for financial support. T. J. Gutiérrez would also
like to thank Dr. Mirian Carmona-Rodríguez for her valuable
contribution.
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Tupa, M., Maldonado, L., Vázquez, A., & Foresti, M. L. (2013). Simple organocatalytic
route for the synthesis of starch esters. Carbohydrate Polymers, 98(1), 349–357.
https://doi.org/10.1016/j.carbpol.2013.05.094 K.V. Ragavan obtained his Ph.D. in Engineering sciences
Tzschucke, C. C., Markert, C., Bannwarth, W., Roller, S., Hebel, A., & Haag, R. (2002). (Food Technology) from CSIR-Central Food Technological
Modern separation techniques for the efficient workup in organic synthesis. Research Institute, Mysore (India), with the best Ph.D. scholar
Angewandte Chemie International Edition, 41(21), 3964–4000. https://doi.org/ award. Later, he went on to work as a Postdoctoral researcher
10.1002/1521-3773(20021104)41:21<3964::aid-anie3964>3.0.co;2-3 at the University of Guelph, Canada, for 3 years, the last of
United States Food and Drug Administration (Usfda). (2020a). Indirect food additives: which under the supervision of Mario M. Martinez for the
Adhesives and components of coatings. Retrieved March 14, 2021, from https://www. development of plant-based meat analogs. Ragavan also
accessdata.fda.gov/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm?fr=175.300&Search worked as a sessional lecturer at the University of Guelph and
Term=fumaric acid. as an Assistant Professor at Amity University, India teaching
United States Food and Drug Administration (Usfda). (2020b). Food additives permitted Bioengineering and Food engineering courses. Currently,
for direct addition to food for human consumption. Retrieved March 14, 2021, from Ragavan is working as a scientist at CSIR-National Institute for
https://www.accessdata.fda.gov/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm? Interdisciplinary Science and Technology, Thir­
fr=172.892. uvananthapuram, India, and as an Assistant Professor in AcSIR-
United States Food and Drug Administration (Usfda). (2020c). Substances generally New Delhi. His research interests include new product development emphasizing sus­
recognized as safe. https://www.accessdata.fda.gov/scripts/cdrh/cfdocs/cfcfr/CFR tainable plant-based products and food analysis.
Search.cfm?fr=582.5017. (Accessed 1 November 2021).
United States Food and Drug Administration (Usfda). (2020d). Direct food substances
affirmed as generally recognized as safe. Retrieved https://www.accessdata.fda.gov
/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm?fr=184.1033. (Accessed 1 November Oswaldo Hernandez-Hernandez achieved his Ph.D. in Food
2021). Science in 2012 from the Autonomous University of Madrid
United States Food and Drug Administration (Usfda). (2020e). Food additives permitted (Spain) and the Institute of General Organic Chemistry (IQOG-
for direct addition to food for human consumption. Retrieved https://www.acc CSIC), working on the development of novel analytical tech­
essdata.fda.gov/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm?fr=172.350&SearchTerm niques to characterize functional carbohydrates. He completed
=fumaric%20acid. (Accessed 1 November 2021). his education in food science as postdoctoral fellow in the
United States Food and Drug Administration (Usfda). (2020f). Substances generally Department of Pure and Applied Biochemistry at the University
recognized as safe. Retrieved https://www.accessdata.fda.gov/scripts/cdrh/cfdocs of Lund (Sweden). His research has been recently recognized
/cfcfr/CFRSearch.cfm?fr=182.1045. (Accessed 1 November 2021). by the Spanish Fellowship for Young Researchers and the EU
United States Food and Drug Administration (Usfda). (2020g). Direct food substances Fellowship Program. His professional expertise stems from
affirmed as generally recognized as safe. Retrieved https://www.accessdata.fda.gov straddling both academia and the private sector. Currently, he
/scripts/cdrh/cfdocs/cfcfr/cfrsearch.cfm?fr=184.1061. (Accessed 1 November works on validating new methodologies to evaluate the di­
2021). gestibility of novel carbohydrates by mimicking the small in­
United States Food and Drug Administration (Usfda). (2020h). Secondary direct food testinal conditions and their properties to modulate the gut microbiota, with a special
additives permitted in food for human consumption. Retrieved https://www.access focus on their structure-function relation. He is currently Visiting Researcher Fellow at
data.fda.gov/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm?fr=173.45. (Accessed 1 Barile Lab at the University of California-Davis (USA).
November 2021).
United States Food and Drug Administration (Usfda). (2020i). Substances generally
recognized as safe. Retrieved https://www.accessdata.fda.gov/scripts/cdrh/cfdocs
/cfcfr/CFRSearch.cfm?fr=582.5650. (Accessed 1 November 2021). Mario M. Martinez obtained his PhD in Chemistry from the
United States Food and Drug Administration (Usfda). (2020i). Substances generally University of Valladolid (Spain). Later, he has worked as a
recognized as safe. Retrieved https://www.accessdata.fda.gov/scripts/cdrh/cfdocs Postdoctoral Research Fellow at Purdue University’s Depart­
/cfcfr/CFRSearch.cfm?fr=582.1099. (Accessed 1 November 2021). ment of Food Science (USA). In August 2017, he became
United States Food and Drug Administration (Usfda). (2020j). Direct food substances Tenure Track Assistant Professor at the College of Engineering
affirmed as generally recognized as safe. Retrieved https://www.accessdata.fda.gov and Physical Science (CEPS), University of Guelph (Canada),
/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm?fr=184.1069. (Accessed 1 November where was awarded the CEPS Assistant Professor Research
2021). Excellence Award for his outstanding research productivity in
Valdes, A. M., Walter, J., Segal, E., & Spector, T. D. (2018). Role of the gut microbiota in the fields of Food Engineering and Health-Promoting Com­
nutrition and health. BMJ, 361, k2179. https://doi.org/10.1136/bmj.k2179 pounds. In April 2020, he joined the Department of Food Sci­
Valencia, G. A., Zare, E. N., Makvandi, P., & Gutiérrez, T. J. (2019). Self-assembled ence at Aarhus University (Denmark) as Tenure Track Assistant
carbohydrate polymers for food applications: A review. Comprehensive Reviews in Professor, from where he was awarded the Young Scientist
Food Science and Food Safety, 18(6), 2009–2024. https://doi.org/10.1111/1541- Research Award by the Cereals & Grains Association (USA) and
4337.12499 the Early Research Award from the Ontario government. Mario is also Adjunct Assistant
Van Nguyen, Q., Nomura, S., Hoshino, R., Ninomiya, K., Takada, K., Kakuchi, R., et al. Professor at the Whistler Center for Carbohydrate Research (Purdue University, IN, USA)
(2017). Recyclable and scalable organocatalytic transesterification of since September 2019. M. Martinez’ research group is centered on understanding mo­
polysaccharides in a mixed solvent of 1-ethyl-3-methylimidazolium acetate and lecular structure-function relationships of dietary carbohydrates and associated metabo­
dimethyl sulfoxide. Polymer Journal, 49(11), 783–787. https://doi.org/10.1038/ lites and the mesoscale structuring of food biopolymers into food and bio-based food
pj.2017.49 packaging materials. His research also aims at providing refinery approaches of starchy
Volant, C., Gilet, A., Beddiaf, F., Collinet-Fressancourt, M., Falourd, X., Descamps, N., and lignocellulosic biomass into functional polymeric streams.
et al. (2020). Multiscale structure of starches grafted with hydrophobic groups: A
new analytical strategy. Molecules, 25(12), 2827. https://doi.org/10.3390/
molecules25122827
Wei, S., Kumar, V., & Banker, G. S. (1996). Phosphoric acid mediated depolymerization
and decrystallization of cellulose: Preparation of low crystallinity cellulose — a new
pharmaceutical excipient. International Journal of Pharmaceutics, 142(2), 175–181.
https://doi.org/10.1016/0378-5173(96)04673-x
Williams, R., & Galan, M. C. (2017). Recent advances in organocatalytic glycosylations.
European Journal of Organic Chemistry, (42), 6247–6264. https://doi.org/10.1002/
ejoc.201700785, 2017.
Xu, Y., Miladinov, V., & Hanna, M. A. (2004). Synthesis and characterization of starch
acetates with high substitution. Cereal Chemistry, 81(6), 735–740. https://doi.org/
10.1094/cchem.2004.81.6.735
Xu, Q., Song, L., Zhang, L., Hu, G., Chen, Q., Liu, E., et al. (2018). Synthesis of cellulose
acetate propionate and cellulose acetate butyrate in a CO2/DBU/DMSO system.
Cellulose, 25(1), 205–216. https://doi.org/10.1007/s10570-017-1539-8
Zdanowicz, M., & Johansson, C. (2016). Mechanical and barrier properties of starch-
based films plasticized with two-or three component deep eutectic solvents.
Carbohydrate Polymers, 151, 103–112. https://doi.org/10.1016/j.
carbpol.2016.05.061
Zhong, Y., Godwin, P., Jin, Y., & Xiao, H. (2020). Biodegradable polymers and green-
based antimicrobial packaging materials: A mini-review. Advanced Industrial and
Engineering Polymer Research, 3(1), 27–35. https://doi.org/10.1016/j.
aiepr.2019.11.002
Zhu, F., Du, B., & Xu, B. (2016). A critical review on production and industrial
applications of beta-glucans. Food Hydrocolloids, 52, 275–288. https://doi.org/
10.1016/j.foodhyd.2015.07.003

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K.V. Ragavan et al. Trends in Food Science & Technology 119 (2022) 45–56

Tomy J. Gutiérrez has a degree in chemistry (Geochemical

option) from the Central University of Venezuela (UCV)
(December 2007), a degree in education (Chemical mention)
from the same university (UCV, July 2008), has a specialization
in International Negotiation of Hydrocarbons from the Na­
tional Polytechnic Experimental University of the National
Armed Force (UNEFA) - Venezuela (July 2011). He also has a
Master’s and PhD degree in Food Science and Technology ob­
tained in October 2013 and April 2015, respectively, both from
the UCV. He has also PhD studies in Metallurgy and Materials
Science from the UCV and postdoctoral studies at the Research
Institute in Materials Science and Technology (INTEMA). Dr.
Gutiérrez has been a professor - researcher at the UCV both at
the Institute of Food Science and Technology (ICTA) and the School of Pharmacy at the
same university. It is currently an adjunct researcher in the INTEMA - National Scientific
and Technical Research Council (CONICET), Argentina. Dr. Gutiérrez has at least 20 book
chapters, 50 publications in high-impact factor international journals and 7 published
books. He has been a lead guest editor of several international journals such as Journal of
Food Quality, Advances in Polymer Technology, Current Pharmaceutical Design and Frontiers in
Pharmacology. He is also an editorial board member of several international journals such
as Food and Bioprocess Technology (2019 Impact Factor 3.356) and Journal of Renewable
Materials (2019 Impact Factor 1.341), from April and June 2019, respectively, among
others. Dr. Gutiérrez today is developing a line of research in nanostructured materials
based on polymers (composite materials), which are obtained on a pilot scale to be
transferred to the food, agricultural, pharmaceutical and polymer industries. It is also a
collaborator of international projects between Argentina and Brazil, Canada, Colombia,
Denmark, France, India, Italy, Portugal, Spain, Sweden and Venezuela.

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