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Major advances have been made in utilizing human-induced pluripotent stem cells (hiPSCs) for regenerative medicine. Nevertheless, the delivery and integration of hiPSCs into target tissues remain significant challenges, particularly in the context of retinal ganglion cell (RGC) restoration. In this study, we introduce a promising avenue for providing directional guidance to regenerated cells in the retina. First, we developed a technique for construction of gradient interfaces based on functionalized conductive polymers, which could be applied with various functionalized ehthylenedioxythiophene (EDOT) monomers. Using a tree-shaped channel encapsulated with a thin PDMS and a specially designed electrochemical chamber, gradient flow generation could be converted into a functionalized-PEDOT gradient film by cyclic voltammetry. The characteristics of the successfully fabricated gradient flow and surface were analyzed using fluorescent labels, time of flight secondary ion mass spectrometry (TOF-SIMS), and X-ray photoelectron spectroscopy (XPS). Remarkably, hiPSC-RGCs seeded on PEDOT exhibited improvements in neurite outgrowth, axon guidance and neuronal electrophysiology measurements. These results suggest that our novel gradient PEDOT may be used with hiPSC-based technologies as a potential biomedical engineering scaffold for functional restoration of RGCs in retinal degenerative diseases and optic neuropathies.

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CO2 is an abundant C1 resource but a green-house gas and chemically inert. Thus, its utilization has been a promising but challenging project. Herein, we report the unprecedented polymerization of CO2 and C6H4(SiMe2H)2 using B(C6F5)3 alone under mild conditions to give poly(silphenylene siloxane) accompanied by releasing CH4. The copolymerization can be extended to comonomers of phenylene silanes bearing functional groups. Moreover, it combines with Piers-Rubinsztajn reaction to establish a tandem polymerization system to achieve super thermal resistant poly(siloxane-co-silphenylene siloxane)s. Density functional theory reveals that B(C6F5)3 is activated by silanes to form free HB(C6F5)2, which is the true active species for CO2 reducing to borylformate, the rate controlling step of the polymerization procedure. The subsequent multiple reductions of borylformate to CH4 and the step-growth to poly(silphenylene siloxane)s can be fulfilled by both B(C6F5)3 and HB(C6F5)2, and the former shows a slightly higher activity. This work opens a new avenue of utilizing CO2 to fabricate polysiloxanes that is unable to access using current manners.

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The utilization of sulfur has been a global issue. Copolymerization of element sulfur (S8) with other monomers is a promising route to convert it to useful materials but is limited by the comonomers. Here, we report anionic hybrid copolymerization of S8 with acrylate and epoxide at room temperature, where S8 does not copolymerize with epoxide in the absence of acrylate. Yet, the proton transfer from the methyne in acrylate to the oxygen anion enables the ring-opening of the cyclic comonomer and hence the copolymerization. The cyclic comonomers can be expanded to lactone and cyclic carbonate. Specifically, the copolymer of S8 with bisphenl A diglycidyl ether and diacrylate displays mechanical properties comparable to those of most common plastics, namely, it has ultimate tensile strength as high as 60.8 MPa and Young's modulus up to 680 MPa. It also exhibits high UV resistance and good transparency. Particularly, it has excellent UV-induced self-healing, reprocessability and closed-loop recyclability due to the abundant dynamic S-S bonds and ester groups. This study provides an efficient strategy to turn element sulfur into closed-loop recyclable polymer with high mechanical and optical performances.

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Herein, poly(pentanediamine terephthalamide) (PA5T) homopolymer was synthesized via a salt-forming reaction+solid state polycondensation method using bio-based 1,5-pentanediamine and terephthalic acid as the primary raw materials. To address the issue of its narrower processing window, poly(hexamethylene terephthalamide)(PA6T), which also cannot be melt processed due to the processing window is negative, was introduced into its molecular chain to synthesize poly (pentanediamine/hexanediamine terephthaloyl) (PA5T-co-6T) copolymers. The structures were investigated by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance carbon spectroscopy (13C-NMR). Furthermore, the melting temperature, crystallization temperature, thermal stability, and crystal growth mode of the polymer were tested and analyzed using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and wide-angle x-ray diffraction (WAXD), respectively. The results demonstrate that the crystal growth mode gradually changes from three-dimensional spherical growth to two-dimensional disk-like or three-dimensional spherical growth with the increase of 6T chain segment content. Simultaneously, the crystallization temperature, melting temperature, and crystallization rate of the polymer all showed a trend of decreasing first and then increasing, which was due to the combined effects of the increase in the content of 6T chain segments on the molecular-chain structure and crystal structure of the polymer. Bio-based PA5T-co-6T has excellent heat resistance and a wider processing window than PA5T and PA6T, which possesses great application prospects in the fields of automotive, electronic appliances, and LED optics.

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Conventional wound dressings used in trauma treatment have a single function and insufficient adaptability to the wound environment, making it difficult to meet the complex demands of the healing process. Stimuli-responsive hydrogels can respond specifically to the particular environment of the wound area and realize on-demand responsive release by loading active substances, which can effectively promote wound healing. In this paper, BC/PAA-pH responsive hydrogels (BPPRHs) were prepared by graft copolymerization of acrylic acid (AA) to the end of the molecular chain of bacterial cellulose (BC) network structure. Antibacterial pH-responsive 'smart' dressings were prepared by loading curcumin (Cur) onto the hydrogels. Surface morphology, chemical groups, crystallinity, rheological, and mechanical properties of BPPRHs were analyzed by different characterization methods. The drug release behavior under different physiological conditions and bacteriostatic properties of BPPRH-Cur dressings were also investigated. The results of structural characterization and performance studies show that the hydrogel has a three-dimensional mesh structure and can respond to wound pH in a 'smart' drug release capacity. The drug release behavior of the BPPRH-Cur dressings under different environmental conditions conformed to the logistic and Weibull kinetic models. BPPRH-Cur displayed good antimicrobial activity against common pathogens of wound infections such as E. coli, S. aureus, and P. aeruginosa by destroying the cell membrane and lysing the bacterial cells. This study lays the foundation for the development of new pharmaceutical dressings with positive health, economic and social benefits.

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The direct acrylation of soybean oil was investigated by the activation of soybean oil's (SO's) internal fatty unsaturation with acidic catalysts. The effect of the catalyst and the reactant ratio with respect to the unsaturation and reaction time on the direct acrylation process were explored. ASO (acrylated soybean oil) with acrylation degrees (the number of acrylate molecules introduced in a triglyceride molecule) between 1.6 and 2.55 were obtained. The effect of the ASO acrylation degree on copolymerization processes was investigated. The resulting monomers were successfully copolymerized with meth(acrylate) monomers by the miniemulsion polymerization process, favoring the droplet nucleation mechanism and showing conversions higher than 97%. The acrylic-ASO copolymers presented lower Tg and higher hydrophobicity and oleophobicity than the acrylic copolymer.

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Organoborane reagents play a pivotal role as Lewis acids in acid-base pairs used in anionic polymerization and in other reactions; yet their high sensitivity to oxygen and moisture necessitates effective stabilization to prevent their oxidation and thus maintain their catalytic activity. In this study, we present novel encapsulation methods employing a cost-effective hexatriacontane (C36H74, C36) organogel to stabilize sensitive organoborane reagents, including triethyl borane (TEB) and a borinane-based ammonium salt (B3NBr). These organoboranes encapsulated in stable, self-standing organogel blocks enable their safe handling in open laboratory environments without the need for a glovebox. Upon heating such borane-containing organogel blocks organoboranes could be freed from the organogel and used to mediate both the homopolymerization of propylene oxide (PO) and the copolymerization of PO with CO2. Furthermore, efficient recovery of the C36 gelator from polymerization mixtures is achieved, with mass recovery ranging from 70% to 90%. This encapsulation method offers a practical and efficient solution for stabilizing, storing, and handling highly reactive organoborane reagents, thereby broadening their applicability and utilization in various chemical transformations.

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The preparation of polyolefins with high polar monomer contents (above 20 mol %) has long been a challenge. Half-titanocenes (Cp')[HC(Ar)N]2BOTiCl2 bearing bulky electron-donating N-heterocyclic boryloxy ligands have been designed and synthesized. The complexes (Cp*)[HC(Ar)N]2BOTiCl2 (2, Ar = 2,6-iPr2C6H3; 5, Ar = 2,4,6-Me3C6H2) supported by Cp* and the bulky boryloxy ligands have been shown to efficiently catalyze the copolymerization of ethylene with long chain α-olefins. In particular, precatalyst 5 enabled the controlled synthesis of poly(ethylene-co-9-decen-1-ol) with unprecedented high polar monomer contents up to 32.1 mol% while maintaining high catalytic activity. The structural analysis and DFT calculations disclosed that the bulky and strong electron-donating boryloxy ligands could effectively stabilize cationic active species. The mechanical studies on the hydroxyl-functionalized copolymers disclosed that they exhibited high strength and toughness because of the existence of hydrogen bonds in the polymer network.

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The molecular structure of the polymer PM6 is elaborately modified through random copolymerization by incorporating simple units of either difluoro-substituted thiophene (2FT) or dicyano-substituted thiophene (2CNT). The incorporation of the 2FT unit significantly enhanced the coplanarity of the random copolymers, leading to improved molecular crystallinity, whereas the introduction of the 2CNT unit featured the opposite effect. Thanks to the optimized morphology resembling a fiber-like interpenetrating network structure, the organic solar cells based on PM6-10%2FT:IT4F showed higher and more balanced charge mobilities, achieving a power conversion efficiency (PCE) of 12.65%, which is comparable to that of PM6-based devices. For comparison, the 2CN-series random copolymers-based devices exhibited lower PCEs of ˂12%. Interestingly, a superior PCE close to 19.0% is achieved in PM6:L8-BO:PM6-20%2CN based ternary device due to the significant improvement in open-circuit voltage. This work demonstrates that the crystallinity of donor polymers can be enhanced by introducing simple structural units to strengthen the coplanarity of the backbone, thereby achieving an optimized morphology that promotes favorable charge transport.

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Solid polymer electrolytes (SPEs) are pivotal in advancing the practical implementation of all-solid-state batteries. Poly(1,3-dioxane) (PDOL)-based electrolytes have attracted significant attention due to the pseudo-high conductivity achieved through sophisticated in situ polymerization methods; however, such PDOL-based electrolytes present challenges of crystallization over time and monomers residual during processing. In this study, integrating LiTFSI and LiDFOB as a universal copolymerization strategy for developing high-performance PDOL electrolytes with a wide range of epoxy crosslinkers is proposed. It is discovered that this approach leverages the protective effects of TFSI anions on the boron active center and catalyzes polymer chain growth via crosslinking. The homogenously crosslinked (benzene-centered) PDOL electrolyte exhibits remarkable thermo-mechanical stability (up to 100 °C), high ion migration number (tLi+ = 0.42), a wide electrochemical window (≈5.0 V vs Li+/Li), and high ionic conductivity (4.5×10-4 S cm-1). Notably, the crosslinked PDOL electrolyte is in the all-solid-state with minimal monomer/oligomer residual, exhibiting no crystallization during relaxation, delivering a robust performance in all-solid-state lithium metal batteries.

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Hydrogels are widely used as excellent drug carriers in the field of biomedicine. However, their application in medicine is limited by their poor mechanical properties and softness. To improve the mechanical properties of hydrogels, a novel triple-network amphiphilic hydrogel with three overlapping crosslinking methods using a one-pot free-radical polymerization was synthesized in this study. Temperature-sensitive and pH-sensitive monomers were incorporated into the hydrogel to confer stimulus responsiveness, making the hydrogel stimuli-responsive. The successful synthesis of the hydrogel was confirmed using techniques, such as proton nuclear magnetic resonance spectroscopy (1H NMR), Fourier-transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). In order to compare and analyze the properties of physically crosslinked hydrogels, physically-chemically double-crosslinked hydrogels, and physically-chemically clicked triple-crosslinked hydrogels, various tests were conducted on the gels' morphology, swelling behavior, thermal stability, mechanical properties, and drug loading capacity. The results indicate that the triple-crosslinked hydrogel maintains low swelling, high mechanical strength, and good thermal stability while not significantly compromising its drug delivery capability.

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The development of innovative synthetic strategies to create functional polycaprolactones is highly demanded for advanced material applications. In this contribution, we reported a facile synthetic strategy to prepare a class of CL-based monomers (R-TO) derived from epoxides. They readily polymerize via well-controlled ring-opening polymerization (ROP) to afford a series of polyesters P(R-TO) with high molecular weight (Mn up to 350 kDa). Sequential addition copolymerization of MTO and L-lactide (L-LA) allowed to access of a series of ABA triblock copolymers with composition-dependent mechanical properties. Notably, P(L-LA)100-b-P(MTO)500-b-P(L-LA)100 containing the amorphous P(MTO) segment as a soft midblock and crystalline P(L-LA) domain as hard end block behaved as an excellent thermoplastic elastomer (TPE) with high elongation at break (1438±204 %), tensile strength (23.5±1.7 MPa), and outstanding elastic recovery (>88 %).

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There is an urgent need for lithium-ion batteries with high energy density to meet the increasing demand for advanced devices and ecofriendly electric vehicles. Spinel LiNi0.5Mn1.5O4 (LNMO) is the most promising cathode material for achieving high energy density due to its high operating voltage (4.75 V vs Li/Li+) and impressive capacity of 147 mAh g-1. However, the binders conventionally used are prone to high potential and oxidation at the cathode side, resulting in a loss of the ability to bond active material and conductive agent integrity. This can lead to severe capacity fading and irreversible battery failure. This study demonstrates that incorporating acrylic anhydride and methyl methacrylate into conventional acrylonitrile through solution polymerization improves the binding energy and voltage resistance. The results indicate that the triblock poly(acrylonitrile-methyl methacrylate-acrylic anhydride) (PAMA) binder has a much higher peeling strength (0.506 N cm-1) compared to its polyvinylidene fluoride (PVDF) counterpart (0.3 N cm-1), making it a more feasible strategy. When assembled with LiNi0.5Mn1.5O4, the PAMA based electrode maintains a capacity retention of 70.7% after 800 cycles at 0.1 C, which is significantly higher than the 33.9% retention of the PVDFbased electrode. This is due to the large number of polar groups, including ─C≡N and ─C═O, on PAMA, which are conducive to adsorbing lithium polysulfide. The S@PAMA electrode is tested and maintained a capacity value of 628.7 mAh g-1 after long-term cycling, confirming its ability to effectively suppress the shuttle effect.

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Novel functionalized and/or grafted crosslinked chitosan adsorbents were synthesized and used to remove several toxic heavy metal ions such as nickel, lead, chromium, and cadmium ions from contaminated water. The chitosan biopolymer was functionalized by maleic anhydride (CS_MA) acting also as a crosslinking agent. Glutaraldehyde-crosslinked chitosan (CS_GA) grafted with poly(methyl methacrylate) (CS_MMA) was also synthesized. The synthesized adsorbents were characterized using a variety of analytical techniques such as SEM, TGA, and FTIR, which confirmed their chemical structures and morphology. The adsorption capacity of the adsorbents was analyzed under various conditions of contact time, adsorbent dose, initial concertation, temperature, and pH and evaluated against those of pure chitosan (CS) and the crosslinked chitosan(CS_GA). The ultimate removal conditions were 0.5 g/100 mL adsorbent dose, an initial metal ion concentration of 50 ppm, a temperature of 45 °C, and pH 9. CS_MMA had the highest removal percentages for all metal ions, ranging from 92% to 94%. The adsorption was demonstrated to fit a pseudo-first-order model that followed a Langmuir adsorption isotherm. The results highlight the capacity of the synthesized polymers to efficiently remove major toxic contaminants at low cost from contaminated water, present especially in low-income areas, without harming the environment.

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Transparent passive cooling materials can cool targets environmentally without interfering with light transmission or visual information reception. They play a prominent role in solar cells and flexible display cooling. However, achieving potent transparent cooling remains challenging, because light transmission is accompanied by thermal energy. Here we propose to realize effective passive cooling in transparent materials via a microscale phase separation hydrogel film. The poly(N-isopropylacrylamide-co-acrylamide) hydrogel presents light transmittance of >96% and infrared emissivity as high as 95%. The microphase-separated structure affords a higher enthalpy of evaporation. The film is highly adhesive. In field applications, it reduces temperatures by 9.14 °C compared to those with uncovered photovoltaic panels and 7.68 °C compared to those for bare flexible light-emitting diode screens. Simulations indicate that energy savings of 32.76-51.65 MJ m-2 year-1 can be achieved in typical tropical monsoon climates and temperate continental climates. We expect this work to contribute to energy-efficient materials and a carbon-neutral society.

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Combining natural polysaccharides with synthetic materials improves their functional properties which are essential for designing sustained-release drug delivery systems. In this context, the Aloe vera leaf mucilage/hydrogel (ALH) was reacted with acrylic acid (AA) to synthesize a copolymerized hydrogel, i.e., ALH-grafted-Polyacrylic acid (ALH-g-PAA) through free radical copolymerization. Concentrations of the crosslinker N,N'-methylene-bis-acrylamide (MBA), and the initiator potassium persulfate (KPS) were optimized to study their effects on ALH-g-PAA swelling. The FTIR and solid-state NMR (CP/MAS 13C NMR) spectra witnessed the formation of ALH-g-PAA. Scanning electron microscopy (SEM) analysis revealed superporous nature of ALH-g-PAA. The gel fraction (%) of ALH-g-PAA was directly related to the concentrations of AA and MBA whereas the sol fraction was inversely related to the concentrations of AA and MBA. The porosity (%) of ALH-g-PAA directly depends on the concentration of AA and MBA. The ALH-g-PAA swelled admirably at pH 7.4 and insignificantly at pH 1.2. The ALH-g-PAA offered on/off switching properties at pH 7.4/1.2. The metoprolol tartrate was loaded on different formulations of ALH-g-PAA. The ALH-g-PAA showed pH, time, and swelling-dependent release of metoprolol tartrate (MT) for 24 h following the first-order kinetic and Korsmeyer-Peppas model. Haemocompatibility studies ascertained the non-thrombogenic and non-hemolytic behavior of ALH-g-PAA.

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Film formation kinetics significantly impact molecular processability and power conversion efficiency (PCE) of organic solar cells. Here, two ternary random copolymerization polymers are reported, D18─N-p and D18─N-m, to modulate the aggregation ability of D18 by introducing trifluoromethyl-substituted pyridine unit at para- and meta-positions, respectively. The introduction of pyridine unit significantly reduces material aggregation ability and adjusts the interactions with acceptor L8-BO, thereby leading to largely changed film formation kinetics with earlier phase separation and longer film formation times, which enlarge fiber sizes in blend films and improve carrier generation and transport. As a result, D18─N-p with moderate aggregation ability delivers a high PCE of 18.82% with L8-BO, which is further improved to 19.45% via interface engineering. Despite the slightly inferior small area device performances, D18─N-m shows improved solubility, which inspires to adjust the ratio of meta-trifluoromethyl pyridine carefully and obtain a polymer donor D18─N-m-10 with good solubility in nonhalogenated solvent o-xylene. High PCEs of 13.07% and 12.43% in 1 cm2 device and 43 cm2 module fabricated with slot-die coating method are achieved based on D18─N-m-10:L8-BO blends. This work emphasizes film formation kinetics optimization in device fabrication via aggregation ability modulation of polymer donors for efficient devices.

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Triphenylphosphine functionalized carbon dots (TPP-CDs) showcase robust mitochondria targeting capacity owing to their positive electrical properties. However, TPP-CDs typically involve complicated synthesis steps and time-consuming postmodification procedures. Especially, the one-step target-oriented synthesis of TPP-CDs and the regulation of TPP linkage modes remain challenges. Herein, we propose a free-radical-initiated random copolymerization in combination with hydrothermal carbonation to regulate the TPP backbone linkage for target-oriented synthesis of triphenylphosphine copolymerization carbon dots (TPPcopoly-CDs). The linkage mechanism of random copolymerization reactions is directional, straightforward, and controllable. The TPP content and IC50 of hydroxyl radicals scavenging ability of TPPcopoly-CDs are 53 wt % and 0.52 mg/mL, respectively. TPP serves as a charge control agent to elevate the negatively charged CDs by 20 mV. TPPcopoly-CDs with negative charge can target mitochondria, and in the corresponding mechanism the TPP moiety plays a crucial role in targeting mitochondria. This discovery provides a new perspective on the controlled synthesis, TPP linkage modes, and mitochondrial targeting design of TPP-CDs.

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Using carbon disulfide (CS2) and carbonyl sulfide (COS) as sulfur-containing and one-carbon feedstocks to make value-added products is paramount for both pure and applied chemistry and environmental science. One of the practical strategies is to copolymerize these bulk chemicals with epoxides to produce sulfur-containing polymers. This approach contributes to improving the sustainability of polymer manufacturing, provides highly desired functional polymer materials, and has attracted much attention. However, these copolymerizations invariably exhibit the intensely complicated chemistry of O/S exchange reaction, leading to sulfur-containing polymers with diverse architectures. As the understanding of O/S exchange continues to deepen, recent efforts have guided significant advances in the synthesis of CS2- and COS-based polymers. This review examines the O/S exchange chemistry and summarizes the recent progress in this field to promote the further advance of synthesizing sulfur-containing polymers from CS2 and COS.

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A highly efficient low-cost adsorbent was prepared using raw and chemically modified cellulose isolated from sugarcane bagasse for decontamination of Cr(VI) from wastewater. First, cellulose pulp was isolated from sugarcane bagasse by subjecting it to acid hydrolysis, alkaline hydrolysis and bleaching with sodium chlorate (NaClO3). Then, the bleached cellulose pulp was chemically modified with acrylonitrile monomer in the presence Fenton's reagent (Fe+2/H2O2) to carry out grafting of acrylonitrile onto cellulose by atom transfer radical polymerization. The developed adsorbent (acrylonitrile grafted cellulose) was analyzed by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Both raw cellulose and acrylonitrile grafted cellulose were used for chromium removal from wastewater. The effects of metal ion concentration, pH, adsorbent dose and time were studied, and their values were optimized. The optimum conditions for the adsorption of Cr(VI) onto raw and chemically modified cellulose were: metal ion concentration: 50 ppm, adsorbent dose: 1 g, pH: 6, and time: 60 min. The maximum efficiencies of 73% and 94% and adsorption capacities of 125.95 mg/g and 267.93 mg/g were achieved for raw and acrylonitrile grafted cellulose, respectively. High removal efficiency was achieved, owing to high surface area of 79.92 m2/g and functional active binding cites on grafted cellulose. Isotherm and kinetics studies show that the experimental data were fully fitted by the Freundlich isotherm model and pseudo first-order model. The adsorbent (acrylonitrile grafted cellulose) was regenerated using three different types of regenerating reagents and reused thirty times, and there was negligible decrease (19%) in removal efficiency after using it for 30 times. Hence, it is anticipated that acrylonitrile could be utilized as potential candidate material for commercial scale Cr(VI) removal from wastewater.

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