Fabrication of biopolymers and their use with metal zinc oxide nanoparticles: A Review

Jagram Meena1* , Jagjeevan Ram2

1Department of Chemistry, Gurukul Kangri Deemed to be University, Haridwar 249404 India

2Department of Physics, Ramjas College, Delhi University, Delhi 110007, India

Corresponding Author Email: jagram.meena@gkv.ac.in

DOI : http://dx.doi.org/10.5281/zenodo.8056710

Abstract

Zinc oxide nanoparticles have engaged most meditation due to their rare character, such as easy separation, surface-to-volume ratio, paramagnetic and high surface area. Natural biopolymers, namely, (Alginate, Chitosan, Dextran, Cellulose, Guar-Gum, Tamarind, and Pectin have posed as an incredible host for the synthesis of zinc oxide nanoparticles. Zinc oxide nanocomposites made of biopolymers have been created for a long time employing techniques including in-situ, ex-situ, co-precipitations, and green synthesis. Researchers are interested in fabricating biopolymer zinc oxide nanocomposites at the nanoscale for a variety of applications, including targeted drug delivery, sensor activity, catalysis activity, anticancer activity, antimicrobial activity, antifungal activity, antioxidant activity, and adsorption of inorganic/organic impurities. This review is designed to the report very firstly reported biopolymer zinc oxide nanocomposites (BZNCs) in last some areas and attractive approach in numerous applications.

Keywords

anti-catalyst activity etc., antimicrobial, antioxidant, Biopolymer, zinc oxide nanoparticles

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Introduction

Nanotechnology deals with materials having nanoscale in one dimension ranging between 1 to 100 nm. Nanotechnology, when integrated with other fields of study such as life sciences, physics, chemistry, medicine, engineering, cognitive sciences, and information technology, has grown in relevance due to its wide range of applications [1]. It entails changing or creating materials of that size to make them more robust, lightweight, quick, and lasting. Numerous fields, including engineering, biology, chemistry, medicine, modelling, and the bioprocessing sector, have benefited from the use of nanotechnology. These uses depend on a few elements, such as increased surface area, physical characteristics, and nanoscale size, which provide chances for control and result in a wide range of functions. Recent discoveries in biological agents have been made possible by new developments in nanotechnology, particularly the capacity to make designed nanoparticles of any shape and size [2]. Zinc oxide nanoparticles are one of the important metal oxides materials that have been extensively employed in materials research due to their distinctive physical, chemical, and biological properties, such as their biocompatibility, environmental friendliness, low cost, and non-toxic nature [3]. Many different synthesis techniques, such as the sol-gel process, the hydrothermal process, the wet chemical procedure, etc., have been reported worldwide. ZnO NPs can have a variety of orientations, morphologies, sizes, and forms by altering a number of factors, including the type of solvent used, reaction temperature, etc. Here is a quick description of some significant kinds of ZnO NP production techniques. Biopolymers are abundant, low-cost, and naturally ecologically benign polymers. Because they are particularly sustainable, renewable, and non-toxic, opportunities are widely employed in agriculture, industries, medicine, and the environment [12].

This has also been shown in the biopolymers studied in the field of metal-polymer nanocomposites, such as chitosan, starch, alginate, tamarind gum, and pectin. Dextran, Mannan, PAA, PVA-A, Guar gum, cellulose, gelatin, etc.) [4,13-25].

                                         Fig.1 Biopolymers structure

Natural biopolymers are added to zinc oxide nanocomposites, expanding their scope of use for things like biomedical adsorption. Diffusion of drugs in the environment, and microbial activity antioxidant performance anti-cancer and catalytic properties [46-50]. The creation of biopolymer-based magnetic metal nanoparticles and nanocomposites, as well as their uses, are the main topics of the current article. The review will also provide readers with information on current techniques used for the synthesis of BMNPs and their biomedical applications.

 Fig.2 biopolymers zinc oxide physical, chemical and biological activity

2.1 Green synthesis of biopolymer and Zinc oxide nanocomposite (BZNCs)

The green synthesis method is an environmentally friendly, energy-efficient, and cost-effective approach to nanoparticle synthesis. ZnO NPs are synthesized from this method using plants, bacteria, fungi, algae, and viruses. Different ZnO NP orientations, morphologies, sizes, and shapes can be obtained by varying a set of parameters such as solvent type. As novel materials with distinct properties, ZnO-based nanocomposites have piqued the interest of researchers.

                      Fig.3 Zinc oxide nanoparticles various biopolymers reduced

The biosynthesis of nanocomposites using environmentally friendly techniques has been the focus of intensive research over the last decade. Green sources function as both reducing agents and stabilizers in the formation of nanoparticles with controlled size and shape. This biopolymer/ZnO composite safeguards the most recent research on essential synthetic techniques and application-driven discussions about biopolymer/ZnO hybrids over the previous decades. The synthetic approach can be divided into two parts: ZnO surface fictionalization and the preparation of biopolymer/ZnO nanocomposites. Polyethylene, chitosan, starch, alginate, tamarind gum, and pectin are examples of biopolymers. Cellulose, gelatine, guar gum, dextran, mannan, PAA, PVA-A, pectin, polyethylene (LLDPE), poly (lactic acid) (PLA), chitosan, tamarind, cellulose, alginate poly (3-hydroxybutyrate-co-3-hydroxy valerate) (PHBV), poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate) (PHB), semolina flour and bovine skin gelatin type-B (BSG) Different processing methods have been used to combine biopolymer with ZnO NPs of various particle shapes and sizes. A number of synthesis methods for ZnO NPs have been published worldwide, including the sol-gel process [20], the hydrothermal process [21], the wet chemical method, and the chemical vapour deposition (CVD) method [22]. Methods of co-precipitation [23], micro emulsion [24], microwave-assisted synthesis [25], green synthesis [26], etc.

The incorporation of natural biopolymers into zinc oxide nanocomposites expands their applications on a large scale, such as biomedical, adsorption. Environmental drug distribution, antimicrobial activity antioxidant activity anti-cancer activity and catalytic activity [46-50].

                      Fig.4 Biopolymer/Zinc oxide nanocomposites various method

2.2 Data from the literature on the synthesis of different biopolymer/ZnO nanocomposite (BZNCs)

Different metal/metallic oxide nanoparticles (Fe, Cu, Au, Ag, Zn, V, Ti, Cr, Ni, Co, etc.) have been created using various biopolymers-based metallic nanocomposites (Table 1). Co-precipitations, green synthesis, in-situ precipitations, ex-situ precipitations, hydrothermal technique, and others are some of the main approaches for biopolymer-based metallic nanoparticle creation. Biopolymers are significant in the preparation of metal/metallic oxide nanoparticles because they act as a capping and reducing agent. Biopolymer is a cation that can form nanocomposites and nanoparticles by forming complexes with anions. ZnO nanoparticles were combined into nanostructured coatings made from chitosan and alginate [5] another survey to reduce mango quality loss, a coating approach is used in this study. As a filler, mango was coated with traditional carrageenan and ZnO nanoparticles of carrageenan [6]. Therefore in study, a new nanocomposite coating was developed as a potential strategy for preserving the qualitative characteristics of the samples. Chitosan and zinc oxide nanoparticles (Zno) were used to prevent microbial growth on fresh-cut papaya. [7] A combination of two obstacles was considered for the storage life of fresh strawberries: sodium alginate (SA) as an edible covering and nano-ZnO.[8] In other studies, nano-ZnO was combined with carboxymethyl cellulose (CMC) covering and synthesized on pomegranate arils. In this contribution, PLA-based nanocomposite films with multifunctional end-use capabilities were synthesized using the In-corporation method with ZnO nanoparticles (NPs) [untreated: ZnO (UT) and 3-methacryloxypropyltrimethoxysilane treated: ZnO (ST). in a polymer matrix by solvent casting Other studies found that melting PLA with 0.5–3 percent ZnO rod-like nanoparticles produced novel PLA-ZnO nanocomposite films [12].

Table 1 Data from the literature on the synthesis of several biopolymer/ZnO nanocomposite (BZNCs)

Biopolymermetal                            TechniqueReferences
Alginate and chitosan           ZnOIn-situ[5]
CarrageenanZnOGreen synthesis[6]
ChitosanZnOCo- precipitation[7]
Sodium alginateZnOIn-situ[8]
Carboxymethyl celluloseZnOIn –situ[9]
3-methacryloxypropyl trimethoxysilane treatedZinc OxideGreen synthesis[11]
PLAYZnOGreen synthesis[12]
Poly (3-hydroxybutyrateZinc OxideGreen synthesis[13]
poly (3-hydroxybutyrate-co-3-hydroxy valerateZnOGreen synthesis[14]
PBATZnOGreen synthesis[15]
clove essential oilZnOHydrothermal method[16]
Polylactic acidZnOEx-situ[17]
linear low-density polyethyleneZinc OxidePrecipitation[18]
PLA film incorporatedZinc OxideCo-precipitation[19]
modified cellulosic                                                                                         Zinc OxideIn-situ[20]
PolyanilineZinc OxideIn-situ[21]
poly (lactic acid) or polylactide (PLA) ZnO      Green synthesis[22]

Poly (3-hydroxybutyrate) (PHB)-based bio nanocomposites with various concentration of ZnO nanoparticles were synthesized by casting.  Biodegradable nanocomposites were generated by solution casting ZnO nanoparticles into the bacterial polyester poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) [14]. The structure of poly (butylene adipate terephthalate) (PBAT) was studied in relation to zinc oxide (ZnO) loadings. [16] We made bovine skin gelatin (BSG) composite films with 2% zinc oxide nanorods (ZnO NRs) and 25 and 50 percent clove essential oil (CEO) (w/w of protein) [16]. Despite no prior treatment of ZnO particles, such as silanization, to reduce their incompatibility with the polymer, the biocomposite films had a high dispersion of ZnO particles in the PLA matrix [18]. A novel nano packaging film was created by incorporating ZnO nanoparticles into a polymer. Matrix of PLA (lactic acid) PLA films with zinc and zinc oxide nanoparticles (ZnO NPs) are recognized as multifunctional materials because of their unique properties [20]. Nanocomposites comprising polyaniline and zinc oxide nanoparticles with polycarbonate as the supporting matrix was created by direct mixing [21-22].

3. Application of Biopolymer Zinc oxide nanocomposites

According to a literature review, the majority of the (BZNCs) containing zinc oxide NPs were initially developed for a variety of applications involving the selective adsorption of target pollutants in the presence of other ions. Because they can combine the properties of nanoparticles and biopolymers, biopolymer zinc oxide nanocomposites (BZNCs) offer a wide range of applications. Supported anticatalysts, antibacterial, antifungal, antioxidant, antifouling activity sensors and biosensors, biomedical devices, electro-conductive pastes and glues, special coatings, paints and varnishes, magnetic fluids, and antifriction biopolymeric coatings are examples of such a wide range of applications in various fields. The following is a list of several applications of (BZNCs) that have been created as of now. From the perspective of applications, encapsulating zinc oxide nanoparticles in a biopolymer host material is obliged; however, it is also necessary to determine whether the host material’s functionality influences the overall sorption behaviour of the zinc oxide nanoparticles (BZNCs). In theory, microbial infections cause the majority of clinical disorders in the world, posing serious health risks to humans.

                                      Fig.5 application of Biopolymer/Zinc oxide nanocomposites

3.1 Food packaging applications for biopolymer zinc oxide nanocomposite materials

In recent years, wide kinds of (BZNCs) have been synthesized and proven to exhibit powerful antibacterial properties (Table 5). A variety of methods have been used to assess the antibacterial activity of (BZNCs). The most popular technique for evaluating the antibacterial activity of PMNPs against a variety of bacteria and fungi is the agar well diffusion method since it is easy, rapid, and logical. Antibacterial properties of AgNPs stabilized by different polysaccharides on Gram-positive and Gram-negative bacteria are outstanding. P. aeruginosa, L. fermentum, coil According to the findings, [23]. When compared to Gram-negative (V. parahaemolyticus. and P. Vulgaris) bacteria, the CS/Ag/ZnO nanocomposite showed antibacterial efficacy against Gram-positive (B. licheniformis and B. cereus) bacteria at 8 g mL1. [23] . The complexes were more effective against bacteria than against fungi, with MIC values of 0.000313 percent (CS@Zn) for both E. Coli and Corynebacter. [24] Antibacterial activity of PHBV/ZnO films was shown against human pathogen bacteria, with Escherichia coli showing a larger effect than Staphylococcus aureus. In both nonpolar and polar simulants, the overall migration values of the nanocomposites declined with increasing nanoparticle concentration and fell below the current benchmark for food packaging materials [14]. Finally, the inhibition zone analysis reveals that chitosan-capped ZnO nanorods have a better antibacterial effect against E. coli than uncapped ZnO nanomaterial and chitosan [25].  The in vitro test revealed that gelatin can considerably increase ZnO biocompatibility while maintaining its antibacterial capabilities against E. coli and S. aureus [26].

One of the most important semiconductors at the nanoscale is ZnO, which also possesses a wide range of morphological structures, a high redox potential, outstanding physicochemical stability, high electron mobility, nontoxicity, and n-type carrier defects [18-20]. It can be used to create electronic components like transistors, LEDs, UV photodetectors, and light-emitting diodes (LEDs). [28] It is a desirable choice for mechanical actuators and piezoelectric transducers due to its piezoelectric properties [29–30]. [169] Biopolymer thermal behavior has also been enhanced by ZnO nanoparticles. [34-35]. Besides, it is also frequently employed in catalysis, energy storage, and biological domains. The antibacterial activity of this Chitosan/Ag/ZnO nanocomposite against B. 409 licheniformis, B. cereus, V. parahaemolyticus, and P. Vulgaris was outstanding. The biofilm growth of bacteria and Candida albicans was efficiently suppressed by the C/Ag/ZnO nanocomposite 410. The 411 CS/Ag/ZnO nanocomposite has no harmful effects on murine macrophages, indicating that it might be employed safely for medicinal reasons [52].

The antitumor activity of chitosan-assembled zinc oxide nanoparticles (CZNP) against cervical cancer cells was successfully tested [57].

3.2 Antimicrobial/antifungal anti-catalyst/Drug delivery/anticancer action, of biopolymer and zinc oxide are some of the applications of (BZNCs).

Table 2 Antimicrobial/antifungal anti-catalyst/Drug delivery/anticancer action, metal removal/organic compound removal of biopolymer and zinc oxide are some of the applications of (BZNCs).

Biopolymer/Zinc oxideAntimicrobial strains[Ref.]
Chitosan Ag/ZnOE. coil, P. aeruginosa, L. fermentum[23]
chitosan–Zn complexAntibacterial activity[24]
Alginate and chitosan add ZnOAntimicrobial activity[5]
. Poly (3-hydroxybutyrate)/ZnO bio nanocompositesAntibacterial activity[13]
ZnO-reinforced poly (3-hydroxybutyrate-co-3-hydroxyvalerate) bio nanocompositesAntimicrobial activity[14]
 chitosan capped ZnO nanorods Antimicrobial activity[25]
Zinc oxide /gelatinAntibacterial activity[26]
Crosslinked carboxymethyl starch/cellulose ZnO/ZnPhoto degradation of dyes]27]
Chitosan/ corn starch/ sodium alginate ZnOPhotocatalytic reaction[28]
carrageenan and ZnO nFood packing’s[6]
carboxymethyl cellulose-chitosan-ZnO NPs nanocompositeFood packings[27]
Gelatin-Zinc Oxide Nanocomposite Application in Spinach Packaging. [28]
ZnO/graphene-oxide nanocomposite wn photocatalytic p[29]
Poly(styrene-co-acrylonitrile)/ZnO Hybrid Nanoparticles   an Efficient Ligand Exchange Strategy  [30]
Facile synthesis of chitosan/ZnO bio-nano compositeDrug delivery [41]
ZnO-polystyrene nanocomposite forUV-shielding applications[42]
Chitosan-based zinc oxide nanoparticleAnticancer activity[43]

3.3 Some of the applications of biopolymer include metal removal, organic compound removal, by Biopolymer and zinc oxide (BZNCs).

Chemical precipitation, adsorption, oxidation-reduction, evaporation, ionic exchange, electrochemical treatment, and membrane separation techniques are the most modern methods for effectively removing heavy metals from wastewaters. The effectiveness and mechanism of cationic heavy metal absorption by ZnO and CuO have not been thoroughly studied. [51]. The adsorptions batch method is being used to remove organic and inorganic pollutants from wastewater treatment utilizing biopolymer and zinc oxide nanocomposites. Then, using the solution casting procedure, such nanoparticle solutions are employed to create films. Different types of metal oxides were disseminated within biopolymer, porous host materials to create (BZNCs) with better durability, mechanical strength, and adsorption properties. Table 2 lists several examples of (BZNCs) that have been developed and used to adsorb various target species from contaminated water and wastewater. In this paper, we investigate the functionalization of graphene oxide with zinc oxide nanoparticles (ZnO) to improve aluminium (Al) and copper (Cu) removal capability in acidic environments. [31,51,52]. The material was used as an adsorbent for the removal of Congo red from aqueous solutions.  [32] The adsorbent guar gum–nano and zinc oxide (GG/ZnO) nanocomposite was employed to improve the removal of Cr (VI) from aqueous solution.[33]  Another literature review found that nanomaterials like graphene oxide (GO) might be used to remove complicated pollutants. In this publication (ZnO), preliminary findings from the use of GO functionalized with zinc oxide nanoparticles to remove Mn (II) ions from acidic waters are presented. [34] Nano-engineered ZnO NR-rGO nanocomposites demonstrate effective water remediation in terms of organic dye degradation and heavy metal ion removal.. The synthesis of ZnO NR-rGO nanocomposite via a simple template-free hydrothermal approach is described here to boost visible photocatalytic efficiency [35] . According to the findings of this study, adding ZnCl2 to a chitosan–polyaniline hybrid increases reactive dye adsorption and photocatalytic degradation [36]. The goal of this study was to make a ZnO@Chitosan core/organically shell nanocomposite (ZO-CS) that may be used to remove Pb(II), Cd(II), and Cu(II) ions from polluted water [37]. This study presents the development of a Zeolite/Zinc Oxide Nanocomposite. Using a co-precipitation technique, (Zeolite/ZnO NCs) were produced. The adsorption of Lead Pb (II) and Arsenic As (V) from aqueous solution was then investigated on the produced Nanocomposite. Nano-ZnO/Chitosan composite beads (nano-ZnO/CT-CB) were used to remove Reactive Black 5 (RB-5) from an aqueous solution in this investigation. Using a microwave-assisted combustion process, ZnO nanoparticles were created. [39] Another work, “Polyaniline/ZnO nanocomposite: a novel adsorbent for the removal of Cr (VI) from aqueous solution,” used sodium tripolyphosphate as the cross-linker to create physically cross-linked chitosan hydrogel beads, and during this process, ZnO nanoparticles were produced in situ. [43] .” The goal of the study was to see if these nanocomposite beads could be used to deliver drugs. [41] Using a solution casting technique, flexible and self-supporting ZnO-polystyrene (PS) nanocomposite thin films (about 360 m) were made. These films were incredibly transparent in the visible range and had good UV-absorbing properties. [42]  . The Synthesis of nickel nanorods and their conversion in to nanoparticles and it’s have various application may be use like as the cancer therapy, medical, environment, pharmaceutical activity [53].

      Table 3, Metal removal/organic compound removal of biopolymer and zinc oxide are some of the applications of (BZNCs).

guar gum–nano zinc oxideChromium[33]
Graphene Oxide–ZnO NanocompositesAluminum and Copper Ions from Acid Mine Drainage Wastewater[31]
Graphene Oxide–ZnO NanocompositesRemoval of Mn(II) from Acidic Wastewaters [34]
Multifunctional ZnO nanorod-reduced graphene oxide hybrids nanocompositesMetal removal[35]
s chitosan–polyaniline/ZnO hybrid compositeorange 16 dye[36]
ZnO@Chitosan   Cu(II), Pb(II) and Cd(II[37]    
 Zeolite/Zinc Oxide Nanocomposite Lead Pb (II) and Arsenic As (V) [38]
ZnO/ChitosanCongo Red[32]
ZnO/Chitosan composite beadsRemoval of RB5 [39]
Polyaniline/ZnO nanocomposites is a novelAdsorbent for the Removal of Cr(VI) from Aqueous Solution[40]
Synthesis of nickel nanorodsconversion in to nanoparticles[53]

Conclusion

The ability of bioactive molecules found in a variety of different biopolymers to reduce and stabilise was what made it possible to create ZnO NPs utilizing a green synthesis technique. The possibilities of enhancing the quality of ZnO NPs and modifying the reaction conditions to improve the production of ZnO NPs on a wide scale are attainable with the gained comprehensive information on the formation mechanism of ZnO NPs. The efficiency of ZnO NPs synthesized from different biopolymers in agriculture, including fertility efficiency, an increase in the rate of germination, adventitious roots, fruits size, and sugar and protein content of crops, is significantly influenced by the biomolecule content of the extract used in the process.Adsorptions, antioxidants, antifungal activity, anti-cancer activity, antimicrobial activity, biosensor activity, biomedical, drug delivery, gene therapy, catalytic activity, food packaging preservation, electrochemical activity, bioimaging, and property are among the many applications for which biopolymers stabilised metal/metallic oxide nanoparticles have emerged as a competent bio biopolymeric biocomposite. Biopolymers are in charge of the form and size of metal/metallic oxide nanoparticles in addition to capping, decreasing, and stabilizing them. The impact of biopolymers on the shape and size of nanoparticles has received less attention thus far. The size and shape of metal/metallic oxide nanoparticles are determined by biopolymers, according to research. The size of Zinc oxide nanoparticles can be affected by differences in molecular weight. It’s critical to remember that biopolymers are in charge of reaction shape and size, as well as reaction temperature, technique variety, reaction time and sonication time. This review will be useful to scientists who are working on improving the stability of Fe/Zn oxide nanoparticles stabilised by biopolymers and their application.   

Acknowledgment

The research facilities were provided by Sri Venkateswara College, Delhi University, Delhi, India, and Gurukul Kangri Deemed to be University, Hardwar, India.

Conflict of interest: The authors don’t have any conflicts of interest

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