Page of 54 RSC Advances View Article Online DOI: 10.1039/C6RA16795K Chemical modification of starch and its application as an adsorbent material Muhammad Saleem, Rizwan Ullah Khan, Raja Summe Ullah, Qing Chen, Jialiang Wu State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P.R China Abstract Starch is a biopolymer of the plant origin which is cheap abundant and has many applications in food and non-food industries However, in the native form, its applications are limited due to shortcomings, such as loss of viscosity and thickening power upon cooking and storage, retrogradation characteristics and absence of certain groups responsible for a particular function, etc So, in order to reduce its limitations and improve its applications, modification of starch is necessary It can be modified by several ways like chemical modification, physical modification and genetic modification but the most important one is the chemical modification In this review, we selected the published data related to the chemical modification like grafting, cross-linking, esterification, etherification and dual modification of starch and application of modified starch for the adsorption of organic dyes and heavy metals from water Keywords: Starch, chemical modification, heavy metals, dyes, adsorption ∗ Introduction Correspondence to Prof Li Wang, E-mail: opl_wl@dial.zju.edu.cn and Haojie Yu, E-mail: hjyu@zju.edu.cn Tel: +86-571-8795-3200; Fax: +86-571-8795-1612 RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 Muhammad Haroon, Li Wang∗, Haojie Yu*, Nasir M Abbasi, Zain-ul-Abdin, RSC Advances Page of 54 View Article Online DOI: 10.1039/C6RA16795K A naturally occurring biopolymer, starch is a cheap, biodegradable, renewable and abundantly available polysaccharide molecule, which is obtained from plants.1 Starch granules are made of mainly two kinds of alpha-glucan, amylose and amylopectin, comparatively linear α-glucan which has % α(1-6) and 99 % α(1-4) linkages while amylopectin has extremely branched structure having about % α(1-6) and 95 % α(14) linkages Small amount of proteins and lipids are also present in starch 2, Naturally occurring starch has limited industrial applications due to insolubility in water at room temperature, easy retrogradation and instability of its pastes and gels The functionality of starch can be modified by a several ways like chemical modification, genetic modification and physical modification.1 In this review, we have focused on the chemical modification of starch The most important use of the chemically modified starch is its use as an adsorbent for the removal of dyes and heavy metals The major contaminating sources of heavy metals are metallurgy, electroplating industries, industrial sewage and household sewage.4 These metals cause renal tubular damage, cancer, hyperkeratosis, anxiety and depression, irritation and damage to the nervous system in human beings5 and cardiovascular, hematologic, reproductive, metabolic and endocrine disturbances, necrosis, restricted growth, skin lesions, and hypocalcaemia in fish.6 Similarly in our modern industrial society, many industries use dyes to color their products.7 These dyes in an effluent, even in a small amount can have harmful effects, not only on the environment, but also on living organisms In addition, some dyes and their degradation products are carcinogenic and toxic These dyes are important sources of water pollution and their treatment becomes a major problem for environmental managers.8 RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 which are about 98-99 % of the total net weight of the starch Amylose is a Page of 54 RSC Advances View Article Online DOI: 10.1039/C6RA16795K Usually, heavy metals and dyes are removed from wastewater by flotation, chemical precipitation, electrochemical deposition, ion exchange and adsorption However, the processes other than adsorption have certain limitations like waste of chemicals, best techniques used for the removal of heavy metals and other wastes from wastewater The process for removing waste on sorbents requires three main steps In first step, the adsorbate particles migrate from solution to the surface of sorbent In second step these particles get adsorbed on the surface and in third step further movement of these particles within the sorbent particles occurs.9 Activated carbon is considered as a good adsorbent because of its large surface area and outstanding adsorption property, but its use is limited due to its high cost, non-selective adsorption and regeneration problems.10-12 Mostly, the synthetic polymers used for the removal of heavy metals are non-biodegradable and non-renewable and may act as secondary pollutants So, these synthetic polymers are not environmental friendly adsorbents Starch, a plant biopolymer is considered to be the excellent substitute comparing with activated carbon and other synthetic polymer adsorbents because it is biodegradable and environmentally safe However, native starch can’t be used directly as an adsorbent due to its no adsorption ability for heavy metals and most of the dyes In order to make starch as good adsorbent for heavy metals and dyes, there is a need to modify native starch by the introduction of active groups like xanthate, carboxylate, acrylate, amine phosphate and many other groups, which have chelating ability.13 Dithiocarbamate starch (DTCS),14 porous starch citrate (PSC), porous starch xanthate (PSX)15 and etherified corn starch containing maleic acid and itaconic acid16 have been used for the adsorption of heavy metals from water These modified starches are supposed to form chelation and ionic interactions with heavy metals causing the RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 sludge production, poor settlement and non-selectiveness So, adsorption is one of the RSC Advances Page of 54 View Article Online DOI: 10.1039/C6RA16795K removal of these metals A novel amphoteric starch having quaternary ammonium and phosphate groups has been effectively utilized for cationic and anionic contaminants treatment.17 Similarly, magnetic nanocomposite hydrogel (m-CVP) beads, prepared (CMS-g-PVI), poly(vinyl alcohol) (PVA) and Fe3O4 with glutaraldehyde (GA) in boric acid, have been utilized for the removal of congo red (CR) and crystal violet (CV) dyes and some transition metal ions like Cu+2, Pb+2 and Cd+2.18 Cross-linked amphoteric starch having quaternary ammonium and carboxymethyl groups has been used for the removal of acid and basic dyes Acid dyes were removed by ammonium group, while basic dyes were removed by carboxymethyl group.19 The purpose of the modification of starch is to enhance the useful properties (like adsorption) of starch and to reduce its unwanted properties.20 Although, some review papers have been published which describe the modification and applications of starch,1, 21 but some aspects of chemical modification and applications of the modified starch are still not described in detail In this review, we have focused our discussion on the chemical modification of starch and its application as an adsorbent material for the removal of different chemical dyes and heavy metals from wastewater Chemical modification The introduction of new functionality in the starch is called chemical modification of starch The new functionality may be carboxyl, acetyl, hydroxypropyl, amine, amide or any other functional group which gives specific properties to the starch The presence of a large number of hydroxyl groups on starch provides more reactive sites for the chemical modification of starch Studies related to the chemical modification of starch have been started in early 1940s There are various methods of chemical RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 by cross-linking the mixture of carboxymethyl starch-graft-polyvinyl imidazole Page of 54 RSC Advances View Article Online DOI: 10.1039/C6RA16795K modification of starch, but some important methods are grafting, cross-linking, etherification, esterification and dual modification.21 2.1 Grafting further polymerized on this chain The time of grafting is variable and it may takes minutes, hours and sometime days to complete.22 Like other biopolymer, starch is also graftified for various applications in different fields like drug delivery, tissue engineering and wastewater treatment Generally three approaches grafting onto, grafting from and grafting through are used for synthesis of graft co-polymers Grafting onto approach is related to the reaction between functional groups of two different polymers Grafting from approach is referred to the grafting in which a polymer with specific functional group triggers the polymerization of vinyl monomers Grafting through approach involves copolymerization of macromonomers.23 Among these approaches, grafting from approach is the most frequently used technique, because of its high grafting yield, which is due to easy access of the reactive groups to the chain ends of the growing polymers.24 The different types of grafting are shown in the flowing sheet diagram (Fig 1).22, 25 Basically grafting follows three reaction paths, free-radical path, ionic path and living polymerization path RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 In this process, monomers are covalently bonded to the main polymer chain and then RSC Advances Page of 54 View Article Online Fig Flow sheet diagram of grafting.21, 24 2.1.1 Free-radical grafting Free-radical grafting (FRG) is the most important and most commonly used method of grafting.21 It is the easiest and economical method for modification of biopolymers for different applications like wastewater treatment, tissue engineering, drug delivery and food additives On the basis of initiators required to start FRG, it is further divided into following three types 2.1.1.1 Grafting induced by chemical initiators In this type of grafting, usually, vinyl monomers are grafted onto biopolymers initiated by chemical initiators The different chemical initiators used are ceric ammonium nitrate (CAN), cerium sulphate (Ce2(SO4)), ceric ammonium sulfate (CAS), Fenton’s reagent (Fe+2 + H2O2), Co (II) potassium monopersulfate, Co (III) acetylacetonate complex salts, azobisisobutyronitrile (AIBN), potassium persulfate (KPS) ammonium persulfate (APS) and benzoyl peroxide (BPO).22, 26 Among redox initiators, CAN is the most commonly used initiator because it results in the product with high grafting efficiency and low amount of homopolymer formation The general synthetic rout of grafting of vinyl monomer on starch is given in Scheme Nair et al prepared cassava starch-graft-polymethacrylamide (St-g-PMAM) using CAN as a free RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 DOI: 10.1039/C6RA16795K Page of 54 RSC Advances View Article Online DOI: 10.1039/C6RA16795K radical initiator The maximum grafting percentage (79.9 %) was obtained, when 0.878 g/L CAN was used for grafting 20 g of methacrylamide (MAM) on 10 g of starch and the reaction was carried out for h at 55 ˚C.27 Lele grafted potato starch starch grafted with acrylonitrile using two initiators system ((Ce(SO4)2 and CAN) showed three times higher grafting percentage than using single initiator (CAN).29 Mishra et al prepared starch-graft-polyacrylamide (St-g-PAM) by using microwave radiations combined with CAN as radical initiators This method resulted in qualitative product with better grafting yield than the methods in which only chemical initiators were used.30 RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 with acrylic acid (AA) using CAN as an initiator.28 Apopei et al found that potato RSC Advances Page of 54 View Article Online Scheme General synthetic route for the grafting of vinyl monomer on starch induced by Ce+4.31 This grafted polymer acted as superabsorbent for the removal of heavy metals.32 The comparative mechanism of grafting of acrylamide on starch by CAN with and without microwave assistance is given in Scheme Witono et al carried out grafting of cassava starch with AA using Fe+2/H2O2 redox system as a radical initiator Grafting efficiency was found to depend on concentration of starch, temperature and starch to RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 DOI: 10.1039/C6RA16795K Page of 54 RSC Advances View Article Online DOI: 10.1039/C6RA16795K monomer ratio.33 Grafting of acrylic acid on starch using Fenton’s reagent is given in Scheme Grafting of acrylamide on starch by CAN: (a) with microwave irradiation and (b) without microwave irradiation.34 Scheme Grafting of starch with acrylic acid using Fenton’s reagent: (a) grafted product and (b) homopolymer (a side product).33 Mohammed et al synthesized a superabsorbent grafted polymer of potato starch by grafting acryloylated starch with AA in the presence of same radical initiating system (Fe+2+H2O2) The product synthesized by this method had lower homopolymer concentration and higher adhesive and film forming properties than the copolymer formed by direct grafting of AA on starch.35 Synthesis of acryloylated starch-graftpoly (acrylic acid) is shown in Scheme Guo et al used KMnO4, HIO4, and H2SO4 for grafting AM on starch With this system, grafting yield and grafting efficiency were increased and the homopolymer content was decreased in comparison with KMnO4 alone.36 Djordjevic et al found that when AA was grafted onto the hydrolyzed potato starch in the presence of three different type of initiators i.e AIBN, RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 Scheme RSC Advances Page 10 of 54 View Article Online DOI: 10.1039/C6RA16795K KPS and BPO, KSP resulted into the higher grafting yield than the other two.37 Scheme Synthesis of acryloylated starch-graft-poly acrylic acid (ASt-g-PAA).35 They also grafted AM on potato starch using the same three initiators and found that the maximum grafting yield, grafting percentage and graft efficiency was obtained with BPO.38 Scheme Grafting of acrylic acid on hydrolyzed starch.37 Hydrogel based on grafting of L-aspartic acid on wheat starch was synthesized by Vakili et al using two types of initiators, CAN and AIBN The maximum value of grafting percentage for CAN and AIBN was 59.94 % and 80.25 %, respectively So AIBN was found as better initiator than CAN in this case.39 Grafting of L-aspartic acid on starch is given in Scheme 10 RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 Grafting of acrylic acid on hydrolyzed starch is given Scheme RSC Advances Page 40 of 54 View Article Online Fig Effect of adsorbate medium pH on the percent dye removal (Adopted with permission from reference 154) Güçlü et al removed a basic dye, safranine T from aqueous solution by St-g-AA The adsorption process was found to increase with rise in pH and followed Freundlich isotherm.155 Al et al used St-g-PAA/Na-montmorillonite for the adsorption of this dye and found that adsorption process followed the same Freundlich isotherm.156 Klimaviciute et al removed different anionic dyes like acid yellow 36, acid blue 78, acid orange 7, acid orange 52, acid blue 25 and acid red 151 from water using crosslinked starch with quaternary ammonium group and non-cross-linked starch with quaternary ammonium group For both type of starches, the adsorption model was fitted with Langmuir model and the mechanism of adsorption was ionic interaction between positively charged ammonium groups of starch and negatively charged anionic dyes When adsorption efficiency of both types of starches were compared, it was found that non-cross-linked starch showed less adsorption than cross-linked starch because of solubility problem.157 The structure of the dyes discussed above are given in Scheme 19 and the brief summary of the adsorption of dyes by different starch derivatives along with their maximum adsorption efficiencies for particular dye is given in Table 40 RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 DOI: 10.1039/C6RA16795K Page 41 of 54 RSC Advances View Article Online DOI: 10.1039/C6RA16795K Adsorption efficiency (mg/g) light 227.27 S/No Type of starch derivatives Dyes adsorbed Reference(s) Cross-linked amphoteric starch Acid yellow 2G Acid red G 19, 149 Dithiocarbamate-modified starch Cross-linked amino starch 217.39 Methyl green 133.33 Methyl violet 333.33 Basic green 104.75 Acid orange 281.30 Acid orange 10 196.32 Acid red 18 149.41 Acid black 219.30 Acid green 25 245.42 Acid orange 883.15 Acid orange 10 561.84 Acid green 25 831.70 Acid red 18 949.03 Amido black 650.39 10B 111.10 Starch/humic acid composite Methylene blue Hydroxyethyl starch-graft- Malachite green poly(N,N-dimethyl acrylamide)-co-acrylic acid Cross-linked starch-gDirect red 81 poly(N,N-diethylaminoethyl methacrylate) Starch-graft-polyacrylic acid Safranine T Starch-graft-polyacrylic acid/Na-montmorillonite composite Cationic starch with quaternary ammonium group 145 147, 148 151 − 153 112 154 204 155 Safranine T 2237 156 Acid yellow 36 − 157 Acid blue 78 Acid orange Acid orange 52 Acid blue 25 Acid red 151 − − − − − 41 RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 Table Adsorption of dyes with different starch derivatives RSC Advances Page 42 of 54 View Article Online Scheme 19 Structure of dyes (a) acid red G, (b) acid light yellow 2G, (c) methyl violet, (d) safranine T, (e) methyl green, (f) methylene blue, (g) acid orange 10, (h) acid orange 7, (i) acid orange 52, (j) acid green 25, (k) congo red, (l) acid black 1, (m) acid red 18, (n) acid blue 78, (o) acid blue 25, (p) reactive blue, (q) acid yellow 36 and (r) malachite green19, 20, 145-157 Conclusion Starch is a natural biodegradable biopolymer of the plant origin which is modified by various methods to improve its useful properties and eradicate its negative impacts, which limit its use Among various techniques used for the modification of starch, chemical modification is the most important and advance technique which mainly includes grafting, cross-linking, esterification, etherification and dual modification 42 RSC Advances Accepted Manuscript Published on 12 August 2016 Downloaded by Northern Illinois University on 12/08/2016 21:55:24 DOI: 10.1039/C6RA16795K Page 43 of 54 RSC Advances View Article Online DOI: 10.1039/C6RA16795K The modified starch has many applications, but the most important one is its use as an adsorbent material for the removal of heavy metals and organic dyes from wastewater as their presence in water is not only harmful for aquatic life but also effect human So, modified starch is considered as prominent adsorbent for the removal of these materials from wastewater However, there are still a lot of possibilities to improve its adsorption ability for heavy metals and organic dyes We can use enzymolysed starch and porous starch instead of normal starch to improve its adsorption efficiency The solubility problems in certain modified starch must be traced and minimized for better reusability Starch may also be modified for adsorption of CO2, SO2 and 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