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.

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.

Tailoring of spherical nanocellulose via esterification with methionine followed by protonation to generate two different adsorbents for mercuric ions and Congo red.

Herein, we report two different adsorbents from spherical nanocellulose (SNC) in successive steps, for the adsorption of Hg2+ ions and Congo red (CR). Cellulose extracted from pine needles was subsequently converted to SNC through mixed acidic hydrolysis. As-obtained SNC was esterified with methionine at C6 of the anhydroglucose unit of SNC to SNC-methionine ester (SNC-ME). The amino group of methionine residue in SNC-ME was protonated to SNC-PME with positive surface charge. The SNC-ME and SNC-PME were evaluated as Hg2+ ions and CR adsorbents, respectively. The SNC, SNC-ME, SNC-PME, Hg2+-loaded SNC-ME, and CR-loaded SNC-PME were characterized by FTIR, XRD, XPS, Zeta potential, BET, FESEM, EDS, and surface charge analysis. SNC-ME showed Hg2+ ions removal efficiency of 94.8 ±â€¯1.9 % in 40 min, while SNC-PME showed CR removal efficiency of 96.1 ±â€¯3.8 % in 90 min. The adsorption data of both the adsorbents fitted best into pseudo-second order kinetic and Langmuir isotherm. The maximum adsorption capacity of SNC-ME for Hg2+ ions was 211.5 ±â€¯3.1 mg/g and that of SNC-PME for CR was 281.1 ±â€¯7.1 mg/g. The astounding recyclability of the adsorbents for ten repeat cycles with significant cumulative adsorption capacity of 760.9 ±â€¯12.8 mg/g for Hg2+ ions and 758.8 ±â€¯12.7 mg/g for CR endorses their spectacular potentiality for wastewater treatment.

Fabricating whole pine needles biomass with phenylhydrazine-4-sulphonic acid for effective removal of cationic dyes and heavy metal ions from wastewater.

We applied a holistic, sustainable, and green approach to develop an effective multipurpose adsorbent from whole pine needles (PNs), a forest waste lignocellulosic biomass. The PNs were oxidized and modified with phenylhydrazine-4-sulphonic acid (ɸHSO3H) to OPN-ɸHSO3H. The latter was characterized and tested as an adsorbent for cationic dyes, malachite green (MG), methylene blue (MB), crystal violet (CV), and metal ions (Hg2⁺ and Pb2⁺). The adsorption followed different kinetic models: Elovich for MG and MB, pseudo-second-order for CV, and pseudo-first-order for Hg2⁺ and Pb2⁺. Langmuir isotherm indicated maximum adsorption capacities of 303.4 ± 8.91 mgg-1 (MG), 331.4 ± 17.50 mgg-1 (MB), 376.6 ± 22.47 mgg-1 (CV), 210.8 ± 28.86 mgg-1 (Hg2⁺), and 172.9 ± 20.93 mgg-1 (Pb2⁺) within 30 min. Maximum removal efficiencies were 99.0% (MG), 98.0% (MB), 96.04% (CV), 95.5% (Hg2⁺), and 89.8% (Pb2⁺). The adsorbent demonstrated significant regeneration and reusability over ten cycles, proving highly efficient for both cationic dyes and metal ions, with wide potential for practical applications where more than one adsorbate is present.

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.

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.

Tuning anti-microbial activity of poly(4-vinyl 2-hydroxyethyl pyridinium) chloride by anion exchange reactions.

A series of new bioactive polymers with pendant choline analogous group was prepared by anion exchange reaction direct at the quaternary nitrogen of the polycation. Poly(4-vinyl 2-hydroxyethyl pyridinium) chloride was prepared in situ by simultaneous polymerization and quaternization of 4-vinyl pyridine with 2-chloroethanol that also acts as catalyst. The counter anion (Cl(-)) of the polycation was exchanged by anion exchange reaction with Br(-), (-)OH, (-)SH, NO(3) (-), BF(4) (-) or CF(3)COO(-). Evidence of anion exchange was obtained by the characterization of the resultant polymers. The nature of the counter anion has profound effect on their properties including strong anion-dependent anti-microbial activity against bacteria and fungus. Polymer containing (-)OH was observed to be the most potent anti-microbial agent with the lowest minimum inhibitory concentration against both the classes of microbes studied.

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.

A study in the adsorption of Fe(2+) and NO(3)(-) on pine needles based hydrogels.

Novel supports for use as cation and anion adsorbents were prepared from lignocellulosics using pine needles and their carboxymethylated forms by network/hydrogel formation with acrylamide and N,N-methylene bisacrylamide. The hydrogels thus prepared were further functionalized by partial alkaline hydrolysis with 0.5 N NaOH and were characterized by FTIR, SEM and nitrogen analysis. Adsorption of Fe(2+) on these hydrogels was carried as a function of time, temperature, pH and ionic strength. The hydrogel having the maximum adsorption capacity was loaded with Fe(2+) at the conditions those afforded maximum uptake and was used as novel anionic adsorbent for NO(3)(-). The water uptake capacities and biodegradability of the hydrogels before and after the ion loading was studied to evaluate the possible end-uses of these hydrogels as alternate materials in the removal of ionic species from water.

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.

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.

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.

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.

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.