Towards scalable and degradable bioplastic films from Moringa oleifera gum/poly(vinyl alcohol) as packaging material.

The use of plant gum-based biodegradable bioplastic films as a packaging material is limited due to their poor physicochemical properties. However, combining plant gum with synthetic degradable polymer and some additives can improve these properties. Keeping in view, the present study aimed to synthesize a series of bioplastic films using Moringa oleifera gum, polyvinyl alcohol, glycerol, and citric acid via thermal treatment followed by a solution casting method. The films were characterized using analytical techniques such as FTIR, XRD, SEM, AFM, TGA, and DSC. The study examined properties such as water sensitivity, gas barrier attributes, tensile strength, the shelf life of food, and biodegradability. The films containing higher citric acid amounts showed appreciable %elongation without compromising tensile strength, good oxygen barrier properties, and biodegradation rates (>95%). Varying the amounts of glycerol and citric acid in the films broadened their physicochemical properties ranging from hydrophilicity to hydrophobicity and rigidity to flexibility. As all the films were synthesized using economical and environmentally safe materials, and showed better physicochemical and barrier properties, this study suggests that these bioplastic films can prove to be a potential alternative for various packaging applications.

A two-in-one thiosemicarbazide and whole pine needle-based adsorbent for rapid and efficient adsorption of methylene blue dye and mercuric ions.

Herein, we report the synthesis of an oxidized pine needle-thiosemicarbazone Schiff base (OPN-TSC) from whole pine needles (WPN) as a dual-purpose adsorbent to remove a cationic dye, methylene blue (MB), and Hg2+ ions in separate processes. The adsorbent was synthesized by periodate oxidation of WPN followed by a reaction with thiosemicarbazide. The syntheses of OPN and OPN-TSC were confirmed by FTIR, XRD, FESEM, EDS, BET, and surface charge analysis. The emergence of new peaks at 1729 cm-1 (-CHO stretching) and 1639 cm-1 (-COO- stretching) in the FTIR spectrum of OPN confirmed the oxidation of WPN to OPN. FTIR spectrum of OPN-TSC has a peak at 1604 cm-1 (C = N stretching), confirming the functionalization of OPN to OPN-TSC. XRD studies revealed an increase in the crystallinity of OPN and a decrease in the crystallinity of OPN-TSC because of the attachment of thiosemicarbazide to OPN. The values of %removal for MB and Hg2+ ions by OPN-TSC were found to be 87.36% and 98.2% with maximum adsorption capacity of 279.3 mg/g and 196 mg/g for MB and Hg2+ ions, respectively. The adsorption of MB followed pseudo-second-order kinetics with correlation coefficient (R2 of 0.99383) and Freundlich isotherm (R2 = 0.97239), whereas Hg2+ ion removal demonstrated the Elovich (R2 = 0.97076) and Langmuir isotherm (R2 = 0.95110). OPN-TSC is regenerable with significant recyclability up to 10 cycles for both the adsorbates. The studies established OPN-TSC as a low-cost, sustainable, biodegradable, environmentally benign, and promising adsorbent for the removal of hazardous cationic dyes and toxic metal ions from wastewater and industrial effluents, especially the textile effluents.

KMnO4-oxidized whole pine needle based adsorbent for selective and efficient removal of cationic dyes.

In the present study, we report the chemical modification of the dried and fallen pine needles (PNs) via a simple protocol using KMnO4 oxidation. The oxidized PNs (OPNs) were evaluated as adsorbents using some cationic and anionic dyes. The successful synthesis of OPNs adsorbent was characterized by various techniques to ascertain its structural attributes. The adsorbent showed selectivity for the cationic dyes with 96.11% removal (Pr) for malachite green (MG) and 89.68% Pr for methylene blue (MB) in 120 min. Kinetic models namely, pseudo-first order, pseudo-second order, and Elovich were applied to have insight into adsorption. Additionally, three adsorption isotherms, i.e., Langmuir, Freundlich, and Temkin were also applied. The dye adsorption followed a pseudo-second-order kinetic model with R2 > 0.99912 for MG and R2 > 0.9998 for MB. The adsorbent followed the Langmuir model with a maximum adsorption capacity (qm) of 223.2 mg/g and 156.9 mg/g for MG and MB, respectively. Furthermore, the OPNs showed remarkable regeneration and recyclability up to nine adsorption-desorption cycles with appreciable adsorption for both the dyes. The use of OPNs as an adsorbent for the removal of dyes from wastewater, therefore, provides an ecologically benign, low-cost, and sustainable solution.

We have carried out the chemical modification of the dried and fallen pine needles (PNs) via a simple protocol using KMnO₄ oxidation. The oxidized PNs (OPNs) were evaluated as adsorbents using some cationic and anionic dyes and the adsorbent showed selectivity for the cationic dyes. As far as the authors are aware, no such report has been documented in the literature wherein an adsorbent based on oxidized PNs with a simple protocol has been used for dye removal.

Functionalized Moringa oleifera Gum as pH-Responsive Nanogel for Doxorubicin Delivery: Synthesis, Kinetic Modelling and In Vitro Cytotoxicity Study

Environment-responsive-cum-site-specific delivery of therapeutic drugs into tumor cells is a foremost challenge for chemotherapy. In the present work, Moringa oleifera gum-based pH-responsive nanogel (MOGN) was functionalized as a doxorubicin (DOX) carrier. It was synthesized via free radical polymerization through the γ-irradiation method using acrylamide and N,N'-MBA followed by hydrolysis, sonication, and ultracentrifugation. The swelling behavior of MOGN as a function of pH was assessed using a gravimetric method that revealed its superabsorbent nature (365.0 g/g). Furthermore, MOGN showed a very high loading efficiency (98.35 %L) of DOX by MOGN. In vitro release studies revealed that DOX release from DOX-loaded MOGN was 91.92% at pH 5.5 and 12.18% at 7.4 pH, thus favorable to the tumor environment. The drug release from nanogel followed Korsmeyer-Peppas model at pH 5.5 and 6.8 and the Higuchi model at pH 7.4. Later, the efficient DOX release at the tumor site was also investigated by cytotoxicity study using Rhabdomyosarcoma cells. Thus, the synthesized nanogel having high drug loading capacity and excellent pH-triggered disintegration and DOX release performance in a simulated tumor environment could be a promising candidate drug delivery system for the targeted and controlled release of anticancer drugs.

Functionalization of nanocellulose to quaternized nanocellulose tri-iodide and its evaluation as an antimicrobial agent.

The reported research involves formation of quaternized nanocellulose triiodide for use as an agent for controlled release of iodine. Nanocellulose was extracted from bagasse and the extracted cellulose nanofibers (CNFs) were quaternized with 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (CHPTAC) in NaOH/urea solution. This was followed by exchange of Cl- with I3- by reaction with KI/I2. Nanofibers having I3- anions were characterized by SEM, TEM, XRD, XRF and FTIR spectroscopy. The iodine content was estimated to be 33.42% and the fibers showed no leaching of molecular I2 in detectable amounts. The fibers showed a maximum activity of 94.73% and 99.86% against E. coli and S. aureus, respectively. These are capable of sustaining 100% antimicrobial activity over a period of six months. These fibers can thus find potential applications as a disinfectant agent in biomedical and water purification processes.

Improving activity and stabilization of urease by crosslinking to nanoaggregate forms for herbicide degradation.

Bioremediation is the most effective green protocol for degradation of environmental contaminants. Present study involves carrier free urease immobilization with synthesis of its new crosslinked aggregates using two different crosslinkers, divinyl benzene (DVB) and tripropyleneglycol dimethacrylate (TPGDA) via free radical mechanism. Resulting crosslinked ureases were further converted to nanoform (CLUNAs) using solvent evaporation technique. The activity of free and the crosslinked ureases was studied as a function of operational parameters viz. temperature (20-80), pH (2-11) and substrate concentration (5-20 mM) using urea as substrate at contact time of 10 min. Storability study of the pristine urease and CLUNAs was carried out for 40 days, and the CLUNAs were reused in 10 repeat cycles to assess their reusability. Isoproturone degradation was studied under the above-cited range of pH and temperature and results were recorded after 24 h.

New Nanoaggregates of Crosslinked Laccase for Reactive Red Bioremediation.

Environmental concerns have led to an increased interest in developing green technologies for bioremediation of wastewater pollutants. In view of this, laccases have emerged as attractive green catalysts due to their applicability in oxidizing broad range of substrates. In the present work laccase was extracted from Coriolus versicolor (MTCC 138) and stabilized by formation of new crosslinked laccase nanoaggregates (CLNAs) using two different crosslinkers-N,N-methylenebisacrylamide (N, N-MBAAm) and ethyleneglycol dimethacrylate (EGDMA). Evaluation of laccase activity profile of the free as well as the well characterized CLNAs was carried out, and these were used in reactive red (RR) bioremediation. The CLNAs showed enriched catalytic activity at different temperatures and pH than the free laccase, good reusability when studied up to six cycles, and thermal and storage stability. CLNAs exhibited good bioremediation ability, which was enhanced in the presence of 1-hydroxybenzo triazole (HBT), a laccase mediator.

Enhanced catalytic activity of new acryloyl crosslinked cellulose dialdehyde-nitrilase Schiff base and its reduced form for nitrile hydrolysis.

Immobilization of enzymes to improve their catalytic properties is an attractive protocol which makes them suitable candidates to meet various industrial demands. Present study describes the synthesis of new acryloyl crosslinked cellulose dialdehyde (ACCD) for nitrilase immobilization. Nitrilase was immobilized onto ACCD via Schiff base formation i.e. imine linkages (-CH=N-). Effect of different operational parameters viz. temperature, pH and substrate concentration on the free and the immobilized nitrilases were evaluated by hydrolysis of mandelonitrile. Immobilization resulted into enhanced catalytic activity of nitrilase under different operating conditions of temperature and pH. The optimum temperature and pH for immobilized forms of nitrilase was obtained to be 55 °C and 8.0 which was higher than its free form (40 °C, 6.0). Immobilized nitrilase also exhibited good thermal and storage stability over the free form and is reusable up to sixteen repeat cycles with an appreciable retention activity.

New glucose oxidase-immobilized stimuli-responsive dextran nanoparticles for insulin delivery.

Designing strategies for the use of biopolymer-based nanoparticles as drug delivery carriers is a considerable challenge in pharmaceutical science. Present study reports synthesis of a novel glucose responsive and in-vitro pH triggered insulin delivery system comprised of glucose oxidase immobilized on acryloyl crosslinked dextran dialdehyde (ACDD) nanoparticles. Scanning electron microscopy, transmission electron microscopy and particle size analysis data revealed that these carriers possess nanosize which is an important parameter for drug delivery applications. In-vitro insulin release studies were performed under artificial gastric fluid (AGF, pH 1.2) and artificial intestinal fluid conditions (AIF, pH 7.4) at physiological temperature (37 °C). Insulin release profile showed controlled release of about 70% under AIF conditions for 24 h. Insulin release mechanism studied using different kinetic models revealed that Korsmeyer-Peppas model appropriately explained the mechanism as 'non-Fickian' diffusion release of insulin. These glucose responsive stimuli sensitive nanocarriers exhibited controlled release of about 90% under AIF conditions in the presence of glucose. These findings revealed that these nanoparticles are promising and reliable delivery systems to overcome problems related with subcutaneous insulin therapy.

Synthesis of a PEGylated Dopamine Ester with Enhanced Antibacterial and Antifungal Activity.

Drug-polymer conjugation is a simple and efficient approach to synthesizing new, effective, and potent antimicrobial agents to counter the problem of microbial resistance. In the present study, a PEGylated dopamine ester (PDE) was synthesized using the PEGylation process and synthesis of PDE was confirmed by Fourier-transform infrared spectroscopy, elemental analysis (CHNS-O), and atomic force microscopy techniques. Later, the antimicrobial activity of PDE was assessed against four strains of bacteria (Bacillus subtilis, Staphylococcus aureus, Pseudomonas aeruginosa, and Proteus vulgaris; Gram (-)) and two fungi (Aspergillus niger and Aspergillus fumigatus) by the agar well diffusion method. The minimum inhibitory concentration (MIC) of PDE was also determined by the broth dilution method against bacteria. PDE showed significant zones of inhibition ranged from 21 to 27 mm for bacteria and 16 to 20 mm for fungi under study, which were much higher than those for dopamine hydrochloride. MIC values of PDE showed its potential antimicrobial property.

l-Cysteine functionalized bagasse cellulose nanofibers for mercury(II) ions adsorption.

Presence of mercury ions in water, even in trace amounts, is a serious environmental hazard. Hence, there is imperative need to develop innovative and environmentally-friendly materials for their removal from wastewaters. In the present study, cellulose nanofibers (CNFs) extracted from bagasse was esterified with l-cysteine to yield thiol and amine functionalized green material (Cys-CNFs) for removal of Hg2+ ions. The Cys-CNFs were well characterized by SEM, TEM, FTIR, EDS and XRD and evaluated for selective removal of Hg2+ ions from the simulated wastewater. It was observed that Cys-CNFs adsorb Hg2+ ions even at a very low concentration of 1.0mg/L and it exhibited a maximum adsorption capacity of 116.822mgg-1. Kinetic analysis of the data revealed that pseudo-second order kinetics and Langmuir isotherm were followed for adsorption of Hg2+ ions.

Fractionation and physicochemical characterization of lignin from waste jute bags: Effect of process parameters on yield and thermal degradation.

In this work lignin was extracted from waste jute bags using soda cooking method and effect of varying alkali concentration and pH on yield, purity, structure and thermal degradation of lignin were studied. The Lignin yield, chemical composition and purity were assessed using TAPPI method and UV-vis spectroscopy. Yield and purity of lignin ranged from 27 to 58% and 50-94%, respectively for all the samples and was maximum for 8% alkali concentration and at pH 2 giving higher thermal stability. Chemical structure, thermal stability and elementary analysis of lignin were studied using FTIR, HNMR, thermo gravimetric analysis (TGA) and Elemental analyzer. FTIR and HNMR results showed that core structure of lignin starts breaking beyond 10% alkali concentration. S/G ratio shows the dominance of Syringyl unit over guaiacyl unit.

Extraction and functionalization of bagasse cellulose nanofibres to Schiff-base based antimicrobial membranes.

The work reported in this paper involves synthesis of a nanocellulose/chitosan composite and its further modification to antimicrobial films. Bagasse, an easily available biowaste, was used as source to extract nanocellulose fibres (CNFs) by subjecting it to mechanical and chemical treatments including alkaline steam explosion and high shear homogenization. The CNFs were subjected to periodate oxidation to obtain nanocellulose dialdehyde (CDA). The aldehyde groups of CDA were reacted with amino groups of chitosan to form Schiff-base. The resulting CDA/chitosan composite fibres were characterized at various steps. The fibres were then cast into films using cellulose acetate as a binder. The films have good physical strength. The composite films show excellent antimicrobial properties when tested against Staphylococcus aureus and Escherichia coli. Such antimicrobial films have potential applications in the formation of antimicrobial packaging material.

Bio-waste derived dialdehyde cellulose ethers as supports for α-chymotrypsin immobilization.

Enzyme immobilization is an important technique to enhance stability, storability and reusability of enzymes. In the present work, pine needles, a forest bio-waste, were used as a feedstock of cellulose to synthesize new materials as supports for immobilization of α-chymotrypsin (CT) enzyme. The extracted cellulose from pine needles was etherified with different alkyl bromides (RBr) and etherified products were further modified to dialdehyde via oxidation with NaIO4 to get the desired products, dialdehyde cellulose ethers (ROcellCHO). CT was then covalently immobilized onto as-synthesized dialdehyde cellulose ethers via Schiff-base formation, i.e., imine linkage. The synthesized products and enzyme immobilization were confirmed by different characterization techniques and the activity assay of the free and the immobilized CT was carried out using standard protocol with variation of different parameters such as temperature, pH and substrate concentration. The storage stability and reusability of the immobilized CT were also investigated. CT activity was also studied in simulated physiological conditions in the artificial gastric fluid and artificial intestinal fluid. Artificial neural network (ANN) model was employed to correlate the relationship with% relative activity and time, temperature and pH affecting enzyme activity. A good correlation of experimental data was predicted by ANN model.

Nitrogen-Doped Mesoporous Carbon: A Top-Down Strategy to Promote Sulfur Immobilization for Lithium-Sulfur Batteries.

The loss of active sulfur material is a challenge in the application of lithium-sulfur (Li-S) batteries. To immobilize sulfur, a nitrogen-doped mesoporous carbon (PMC) was synthesized with polyaniline (PANi) as the carbon source, which was used for development of Li-S batteries. The nitrogen content and pore system of the PMCs were modulated by varying the pyrolysis temperature to impart good electrochemical properties to the Li-S cells. As a result, the optimal capacity reversibility was obtained with the PMC synthesized at 700 °C that consisted of 12.8 % nitrogen. The enhanced cycle performance of Li-S cells was also validated at high sulfur contents up to 70 % and high C-rates up to 2 C. Furthermore, such sulfur/PMC cathodes could alleviate volume expansion during the discharge process. The results suggest that our synthesized nitrogen-doped PMCs prepared by this top-down strategy are promising materials to immobilize active sulfur in Li-S batteries.

Functionalized Polyacrylonitrile Nanofibrous Membranes for Covalent Immobilization of Glucose Oxidase.

Nanofibrous membrane (NFM) with uniform morphology and large surface area was prepared from 10% solution of polyacrylonitrile (PAN) in N,N-dimethylformamide by electrospinning technique. NFM was chemically modified for use as a support for the immobilization of glucose oxidase. Chemical modification of NFM was carried out by two different methods. In the first method, the cyano groups of PAN were modified to amino groups by a two-step process, while in the second method the carboxylic groups were generated first and then further reacted with hexamethylene diamine to create a reactive spacer arm for the immobilization of enzyme. Scanning electron microscopy studies showed that the surface morphology of NFM was not changed by chemical modification and its mechanical strength was improved. The immobilized glucose oxidase (GOx) retained 54 and 60% of its original activity up to 25 cycles with the PAN NFMs modified by the first and the second method, respectively. The GOx-immobilized NFM from the second method showed promising performance with higher enzyme immobilization, activity retention, and favorable kinetic parameters.

Gallic acid-based alkyl esters synthesis in a water-free system by celite-bound lipase of Bacillus licheniformis SCD11501.

Gallic acid (3, 4, 5- trihydroxybenzoic acid) is an important antioxidant, anti-inflammatory, and radical scavenging agent. In the present study, a purified thermo-tolerant extra-cellular lipase of Bacillus licheniformis SCD11501 was successfully immobilized by adsorption on Celite 545 gel matrix followed by treatment with a cross-linking agent, glutaraldehyde. The celite-bound lipase treated with glutaraldehyde showed 94.8% binding/retention of enzyme activity (36 U/g; specific activity 16.8 U/g matrix; relative increase in enzyme activity 64.7%) while untreated matrix resulted in 88.1% binding/retention (28.0 U/g matrix; specific activity 8.5 U/g matrix) of lipase. The celite-bound lipase was successfully used to synthesis methyl gallate (58.2%), ethyl gallate (66.9%), n-propyl gallate (72.1%), and n-butyl gallate (63.8%) at 55(o) C in 10 h under shaking (150 g) in a water-free system by sequentially optimizing various reaction parameters. The low conversion of more polar alcohols such as methanol and ethanol into their respective gallate esters might be due to the ability of these alcohols to severely remove water from the protein hydration shell, leading to enzyme inactivation. Molecular sieves added to the reaction mixture resulted in enhanced yield of the alkyl ester(s). The characterization of synthesised esters was done through fourier transform infrared (FTIR) spectroscopy and (1) H NMR spectrum analysis.

Functionalization of tetracycline and evaluation of its antibacterial activity including against resistant bacteria.

Ever growing resistance of pathogenic bacteria against the existing antibiotics has forced researchers to look for new methods and techniques to design effective antimicrobial agents. In the present study a new tetracycline-based antimicrobial polymer (AMP) was synthesized from tetracycline and methacrylic acid (MAAc) using lipase as catalyst. The AMP, thus obtained, was transformed into nanoparticles via an emulsion method. The AMP and its nano-form were characterized by FTIR, NMR, XRD, SEM and EDAX. The antibacterial activity of the AMP was studied against both resistant (-) [P. aeruginosa] and susceptible (+) [S. aureus] bacteria. The synthesized AMP, including its nanoform, was observed to be more potent and efficient antimicrobial agent than the precursor tetracycline.

Star-shaped polymers of bio-inspired algae core and poly(acrylamide) and poly(acrylic acid) as arms in dissolution of silica/silicate.

Silica, in natural waters (due to weathering of rocks) decreases system performance in water processing industry due to scaling. In view of that, the present work involves the synthesis of novel green star shaped additives of algae core (a bio-inspired material as diatom maintains silicic acid equilibrium in sea water) as silica polymerization inhibitors. Star shaped materials with bio-inspired core and poly(acrylamide) [poly(AAm)] and poly(acrylic acid) [poly(AAc)] arms were synthesized by economical green approach. The proficiency was evaluated in 'mini lab' scale for the synthesized APAAm (Algae-g-poly(AAm)) and APAAc (Algae-g-poly(AAc)) dendrimers (star shaped) in colloidal silica mitigation/inhibition at 35 °C and 55 °C. Synthesized dendrimers were equally proficient in silica inhibition at 12 h and maintains ≥450 ppm soluble silica. However, APAAm dendrimers of generation 0 confirmed better results (≈300 ppm) in contrast to APAAc dendrimers in silica inhibition at 55 °C. Additionally, dendrimers also worked as a nucleator for heterogeneous polymerization to inhibit silica homo-polymerization. APAAm dendrimer test set showed no silica deposit for more than 10 days of inhibition. EDX characterization results support nucleator mechanism with Si content of 6.97%-10.98% by weight in silica deposits (SiO2-APAAm dendrimer composites).

A new guar gum-based adsorbent for the removal of Hg(II) from its aqueous solutions.

Modification of biopolymers by oxidation is an easy process to develop effective adsorbents for the removal of toxic metal ions from their aqueous solutions. In the present study, guar gum (GG) was crosslinked with epichlorohydrin and then oxidized to the polydialdehyde form (GG-clPDA). The latter was converted to a Schiff-base, GG-clCHN(CH2)6NCHGG, by reaction with hexamethylenediamine. Different forms of the modified GG were characterized by SEM, FTIR and XRD and investigated as adsorbents for the removal of Hg(II) ions from their aqueous solutions. The adsorption process was carried out through the variation of time, temperature, pH and initial concentration of Hg(II) ions. GG-clCHN(CH2)6NCHGG was observed to be an efficient adsorbent with a maximum adsorption capacity of 41.13 mg/g. It is reusable up to five cycles at the optimum conditions obtained for the maximum ions uptake. The kinetic data generated fit the Freundlich isotherm and pseudo-second order kinetics.