1.

Introduction Edible polymers refer to the polymeric materials which can be

consumed by human beings, animals or microorganisms without any noxious effects
towards health. They are categorized into polysaccharides, proteins and lipids, and
have gained increasing application mainly in functional food industries (food
packaging and nutrients protection) and biomedical fields (drug delivery, tissue
engineering and wound dressing) (Ali & Ahmed, 2018b). The important properties of
edible polymers which make them the superior choice over non-biodegradable
petroleum polymers include its biodegradability, biocompatibility and recyclability.
Additionally, they can avoid environmental issues such as reducing contamination,
improve materials recyclability, produce eco-friendly products and provide
sustainability (Shit & Shah, 2014). In food industries, the main reasons for
considering the healthy to eat polymers came into effect with the introduction of new
food product categories, such as healthy, convenient and environment friendly high
quality products. The edible polymers are produced solely from renewable and safe to
eat components; hence are expected to degrade more easily than other polymeric
materials. In biomedical research field, edible polymers have been applied extensively
mainly due to their versatility which provides the large variety of functional and
design requirements for the different tissue types. Moreover, they have the ability to
undergo a wide range of physico-chemical modification for specific tissue
regeneration requirement, which are pleasant for biomedical applications. The
selection of edible polymers for biomedical application is based on material
chemistry, shape structure, molecular weight, hydrophobicity/hydrophilicity,
lubricating property, surface energy, degradation rate, water absorption, erosion
mechanism and solubility (Olatunji, 2015). Besides food industries and biomedical
area, edible polymers have gained great attention in cosmetics, non-
renewable/renewable energy and wastewater treatment (Aboulrous, Mahmoud,
Alsabagh, & Abdou, 2016; Savary, Grisel, & Picard, 2016). The growing interest in
edible polymers than synthetic polymers in the field of cosmetics is due to its ability
to enhance dispersion stability, texture improvement, biodegradability,
biocompatibility with skin and mucus, and sensory performance (Babu, O'Connor, &
Seeram, 2013; Jiang et al., 2019; Savary et al., 2016). In energy applications, edible
polymers have been used as a source of renewable energy, electrolytes for energy
storage devices as well as generators. Additionally, natural polymers are widely
studied for removal of contaminations such as suspended solids, dyes, pesticides,
toxicants, and heavy metals from water. Interest in formulation and application of
nanotechnology/materials in various fields of research has been increased over past
few decades. Different nano-additives have been incorporated into edible polymers
through the novel micro-nano encapsulation methods to improve the properties or to
introduce new functionalities (ArredondoOchoa, Regalado-González, & Martín-
Belloso, 2018). There are several reviews that summarize the research findings of
individual application/form of polymer based edibles. However, to the best of our
knowledge there are limited reviews on the different aspects of properties, preparation
and application of edible polymers. The objective of the present work is to
comprehensively review the recent studies on different sources of raw edible
polymeric materials and different forms of edible polymers (such as particles and
films applied in green and smart textiles) along with their fabrication methods and
functionalization. The recent applications of edible materials in food (films/coating
technologies, active/smart food packaging, functional food coating), biomedicine
(smart drug delivery, wound dressing, tissue engineering, and medical devices); as
well as personal care products, water/wastewater treatment and renewable energies
are also reviewed. The safety and commercial aspects of edible polymer based
products are important, with discussions are performed within this review.

2. Classifications of edible polymers Polysaccharides, lipids and proteins are three

main sources of edible polymers (Table 1). 2.1. Polysaccharides Polysaccharides are
complex carbohydrate macromolecules made up of two or more monosaccharides
linked by glycosidic linkages via condensation reactions (Ali & Ahmed, 2018a). The
physical properties of polysaccharides depend mostly on the monosaccharaides units
shape and linkage. They are insoluble in alcohol and nonpolar solvents, mostly in
white color, tasteless and rarely crystalline. Moreover, they have no optical activity
and must be digested before being absorbed. Polysaccharides are also good energy
preservers, fuel storage molecules, and metabolic intermediates. In food and non-food
industries, they are commercially assessable as stabilizers, thickeners, gelling and
encapsulating agents, and crystallization inhibitors. Polysaccharides have some
excellent features among edible polymers due to their versatile functionalities and
biocompatibility (Ali & Ahmed, 2018b; Hassan, Chatha, Hussain, Zia, & Akhtar,
2018; Pasqui, De Cagna, & Barbucci, 2012; Shit & Shah, 2014). Examples of
polysaccharide based edible polymers include starch, cellulose and its derivatives,
chitosan, pectin, alginate, carrageenan, pullulan etc. Starch, a naturally existing
polysaccharide, is extensively investigated in food industrial applications, because it
has some physical features similar to plastics. It is tasteless, relatively cheap,
abundant, odorless, biologically absorbable, nontoxic, semipermeable to carbon
dioxide, colorless, and oxygen resistant (Hassan et al., 2018). Most starches are
composed of anhydroglucose residues comprising of linear amylase and branched
amylopectin which are from numerous sources like botanical sources such as corn,
wheat, cassava, rice, potato, yam, among others (PiñerosHernandez, Medina-
Jaramillo, López-Có

2.2. Proteins Proteins are biological macromolecules consisting of one or more long
chains of amino acid residues linked together by peptide bonds, which mainly occur
as either fibrous proteins or globular proteins. Fibrous proteins serve as building
blocks of animal tissues and are mainly water insoluble, while globular proteins are
soluble in water, acidic/basic solution and have various functionalities in living body
(Ali & Ahmed, 2018a, 2018b; Hassan et al., 2018). The physicochemical properties of
proteins are highly dependent on the amino acid residues sequence and the relative
quantity of amino acid along the polymer chain (Arndt, 2008). They have optical
activity (due to asymmetry and chirality of amino acids), foam forming and
stabilizing ability, and gel forming ability depending on pH and ions. Chemical
properties of proteins include hydrolysis by acid and enzyme, denaturation by heat,
solvent agitation, and possible functionalization through side chain functional groups.
Different protein based edible polymers such as collagen; gellatin, soy protein, zein,
wheat gluten, whey protein etc have been investigated for individual food packaging,
multilayer food packaging together with non-edible polymers, carrier of
pharmaceutical and oil phases, biomedical application, etc. (Ananey-Obiri et al.,
2018; Farjami, Madadlou, & Labbafi, 2015; Hassan et al., 2018; Kurek, Galus, &
Debeaufort, 2014; Liu & Tang, 2013). 2.3. Lipids Lipids are a large and diverse group
of naturally occurring organic compounds made up of mostly hydrocarbon chains.
They are either liquid or non-crystalline solid, colorless, tasteless, odorless, lighter
than water, insoluble in water, soluble in organic solvents, and poor conductor for
heat and electricity. Due to their hydrophobic and nonpolar nature, they can block
moisture (water) penetration when applied as film or coating materials on food
substances (Pérez-Gago & Rhim, 2014; Rhim & Shellhammer, 2005). Lipids were
primary used as edible films and protective coating to control the water vapour loss in
food packaging (J. J. Kester & Fennema, 1989). The ability of lipid in moisture
transfer depends on its polarity which is determined by the distribution of chemical
groups, length of the aliphatic chains, and the presence/ degree of unsaturation
(Ansorena, Pereda, & Marcovich, 2018). Due to their weak film forming ability, they
are used in combination with polysaccharides and proteins, to produce composite
films with better moisture barrier properties (Bravin, Peressini, & Sensidoni, 2004;
Dehghani, Hosseini, & Regenstein, 2018; Shit & Shah, 2014). Acetylated
monoglycerides, phospholipids, natural wax, mineral oil, vegetable oil, shellac,
terpene, paraffin wax, and surfactants are few lipids based edible polymeric materials
(Ali & Ahmed, 2018b). Different types of waxes are used to block gas/water vapour
transmission on fruit and to improve the surface appearance of foods. Among them,
paraffin and beeswax showed lowest moisture permeability due to their highly
hydrophobic nature (J. J. Kester & Fennema, 1989). 3. Different forms of edible
polymers Edible polymers have been studied and applied as particle form, layer form
(coating or film) or as textile structures (as edible fibers or for modification of non-
edible textile). This category is given in Fig. 1. M. Kouhi, et al. Trends in Food
Science & Technology 103 (2020) 248–263 249 Table 1 Classification of edible
polymers and few examples. Edible polymers Few Examples Common structure
Polysaccharides starch: (C6H10O5)n pectin:(C6H10O7); agar:(C14H24O9); alginate:
(C12H20O12P2); cellulose derivatives:(C6H10O5)n; carrageenan:
(C24H36O25S2−2); chitosan: (C6H11NO4)n xanthan gum:(C35H49O29); guar gum:
(C10H14N5Na2O12P3); gum arabic: (C15H20NNaO4) pullulan:(C6H10O5)n, etc
Proteins Animal based: gelatin, collagen, albumin, milk protein (casein and whey
protein), etc. Plant based: zein, wheat gluten, soy, peanut, pea, nut proteins, etc.
Lipids waxes (beeswax, candelilla, carnauba waxes), phospholipids, fatty acids,
triglycerides, glycolipids, etc Fig. 1. Different preparative forms/structures of edible
polymers. M. Kouhi, et al. T

3.1. Edible particles Edible particles have been widely investigated and employed as
long-term stabilizers in the formulation of Pickering emulsion for fabrication of new
safe food, cosmetic, and pharmaceutical products (Dickinson, 2010; Frelichowska,
Bolzinger, Pelletier, Valour, & Chevalier, 2009; Yang et al., 2017). To date, several
edible micro/nano particles have been introduced and investigated as emulsifiers such
as cellulose microparticles (Wege, Kim, Paunov, Zhong, & Velev, 2008), chitin
nanocrystals (Tzoumaki, Moschakis, Kiosseoglou, & Biliaderis, 2011), granules of
modified starch (Yusoff & Murray, 2011), whey protein (J. Wu et al., 2015), soy
protein (Liu & Tang, 2013), pea protein (Liang & Tang, 2014), egg protein/arabic
gum (Wei & Huang, 2019), cyclodextrine (Xiao, Liu, Niu, & Kou, 2020), and starch
nanoparticles (Kargar, Fayazmanesh, Alavi, Spyropoulos, & Norton, 2012; Li, Sun, &
Yang, 2012). The application of edible particles as emulsifier has several advantages
over other solid stabilizers such as their excellent biocompatibility, biodegradability,
less harmful effects on human health (because of their digestible nature), possible
mass production without any environmental pollution, possible physical or chemical
modifications of the particles, control release ability, providing novel
texture and sensory properties to emulsion based products, and
providing template function in developing microcapsule type vehicles
for nutrient delivery (Berton-Carabin & Schroën, 2015; Tang, Quinlan, & Tam,
2015; Xiao, Li, & Huang, 2016). Obtaining a highly stabilized pickering emulsion of
nanoscale size is a big challenge for researchers. Interestingly, Xiao et al. stabilized a
robust pickering nanoemulsion using βcyclodextrin (CD), where a high loading
capacity of essential oil was achieved. In this system, β-CD/Tween-20 nanoparticles
were used for pickering nanoemulsion preparation, and the α-CD/polyethylene glycol
gels helped to sustain its stability (Xiao et al., 2020). Edible particles can also be
applied as a self-adhesive whereby it adheres to the surface of food or foodstuffs
thereby improving the external appearance of food (Henze, Fahie, Elenschleger,
Sabater, & Frank, 2016). 3.1.1. Preparation methods of edible particles Edible
particles can be mainly prepared using top-down strategies such as mechanical (ball,
wet, freezer milling and high pressure homogenizer) and chemical break down
methods. By mechanical methods, the size of particles and crystals are decreased by
applying turbulence and cavitation shear (Yusoff & Murray, 2011). By chemical
methods, submicron particles are obtained via acid treatment, mostly carried out for
cellulose and chitin. Sensitive amorphous parts in the cellulose are dissolved in strong
acids like sulphuric and hydrochloric acid without disrupting the crystalline region
(Tzoumaki et al., 2011). Another method for fabrication of edible particles is
precipitation method which is suitable for water insoluble materials. In this route,
materials are completely dissolved in a proper solvent, followed by dispersion of the
organic phase in an aqueous phase with ultimately removing the organic phase. Using
this method, micro/nano size particles are collected as precipitate after solvent
elimination. Materials concentration, ratio of solvent to water phase, method of
dispersion, and order of organic and aqueous solution addition are the main
parameters influencing the particle size (Xiao et al., 2014; Zou, Guo, Yin, Wang, &
Yang, 2015). Heat treatment is another fabrication method for particles production
especially for protein based materials. Protein molecules change their natural
polypeptide structure and aggregate to microparticles through interaction between
disulfide bonds and nonpolar molecules during heat treatment or by changing the
solvent properties (Ren, Tang, Zhang, & Guo, 2009; Xiao et al., 2016). The properties
of the aqueous media including pH, protein concentration, calcium content, ionic
strength, and condition of the process including temperature, shear rate, and time are
the factors affecting the microstructure and morphology of the obtained particles
(Dickinson, 2017). Microgel particles are distinct particles made of highly swollen
crosslinked polymers and can be applied as soft particle stabilizers. By increasing the
applied shear force, the dimensions of the particles decrease to submicron sizes
(Sağlam, Venema, van der Linden, & de Vries, 2014). However, to obtain microgel
particles of uniform size, it is required to avoid excessive heat induced growth of
precipitates when such shear forces are applied. Polysaccharides and protein based
materials are used for preparation of highly swollen microgels. Enzymes such as
transglutaminase, peroxidase or tyrosinase are often used as crosslinker (Farjami et
al., 2015; Olatunji, 2015; Xu, Teng, & Wang, 2016). This type of material can exhibit
stimuli responsive features, in which their structure possesses deformation and
rearrangement after applying foreign stimulus (Dickinson, 2016). Development of
protein/polysaccharide composite nanoparticles has been reported using complexation
method. The electrostatic interactions, hydrophobic interactions and hydrogen
bonding are responsible for the formation of protein/polysaccharides colloidal
nanoparticles. The biopolymer ratio and pH affect the morphology and size of
particles. The protein/polysaccharides particles have been utilized in the preparation
of surfactant-free food grade Pickering emulsions (Wei & Huang, 2019). Bacteria
biosynthesis and plant matter disintegration is the other fabrication route for
preparation of cellulose nanoparticles. 3.1.2. Encapsulation of active component into
edible particles Edible particles can also be applied to protect, isolate or control the
release of active molecules. Fig. 2-a illustrates the different types of particles
encapsulating active ingredient, which include multi and single-wall capsules, with
single or multi-cores, with the core encapsulated inside the particles or within the
wall, and with spherical or irregular shapes. Various methods are used for the
encapsulation of active component into particles, which mainly depend on the type of
core and shell materials, size of desired capsules, resistance to high temperature or
physical abrasions, etc. Among them, spray-drying and freeze-drying are the most
common ones, in which active components are incorporated into a protective matrix
that is inert to the encapsulated materials (Gharsallaoui, Roudaut, Chambin, Voilley,
& Saurel, 2007; Gouin, 2004). In spray drying technology, a fluid product is atomized
into dried powder by the aid of a hot gas stream (Gharsallaoui et al., 2007). The
microencapsulation process consists of feed preparation, followed by atomization of
feed to small droplets, rapid drying of liquid droplets in contact with a stream of hot
gas and powder collection (Castro-Rosas et al., 2017; Corrêa-Filho, MoldãoMartins,
& Alves, 2019; Shishir & Chen, 2017). Fig. 2-b schematically represents the spray-
drying process. In freeze drying technology, a product containing core and shell
component is frozen below −40 °C and dehydrated and transformed into a dry
material by sublimation under low pressure (Corrêa-Filho et al., 2019; Yamashita et
al., 2017). This technique is simple and suitable for the encapsulation of biological
agent sensitive to heat and oxygen (Ray, Raychaudhuri, & Chakraborty, 2016).
However, the high energy consumption and cost effective process are the
disadvantages of freeze drying technique. Moreover, the dried materials obtained
from freeze drying method have a porous structure exposing the encapsulated
materials to the medium; thereby provide less protection for the prolonged shelf life
of the encapsulated gradient (Gharsallaoui et al., 2007; Kaushik, Dowling, Barrow, &
Adhikari, 2015). Various techniques for preparation of nanoparticles containing active
components from edible polymers have been developed over the last three decades.
These methods mainly include nanoprecipitation or solvent displacement,
emulsification-solvent evaporation, emulsification-diffusion, double/multiple
emulsification, and electrospraying. Electrospraying is a relatively new technique
which showed some advantages over other methods, such as its simplicity, low cost,
reduced solvent usage and it is carried out in a single step. This technique could be
applied in agrifood sector and biomedical field for the preparation of controlled and/or
prolonged release systems for fertilizer, agrochemicals or drugs. Electrospraying
involves breaking the bulk liquid into very fine charged droplets by coulomb
repulsion. Droplets that exited