Green synthesis and biological evaluation of novel 5-fluorouracil derivatives as potent anticancer agents.

This study reports the formation of 5-FU co-crystals with four different pharmacologically safe co-formers; Urea, Thiourea, Acetanilide and Aspirin using methanol as a solvent. Two fabrication schemes were followed i.e., solid-state grinding protocol, in which API and co-formers were mixed through vigorous grinding while in the other method separate solutions of both the components were made and mixed together. The adopted approaches offer easy fabrication protocols, no temperature maintenance requirements, no need of expensive solvents, hardly available apparatus, isolation and purification of the desired products. In addition, there is no byproducts formation, In fact, a phenomenon embracing the requirements of green synthesis. Through FTIR analysis; for API the N-H absorption frequency was recorded at 3409.02 cm-1 and that of -C[bond, double bond]O was observed at 1647.77 cm-1. These characteristics peaks of 5-FU were significantly shifted and recorded at 3499.40 cm-1 and 1649.62 cm-1 for 5-FU-Ac (3B) and 3496.39 cm-1 and 1659.30 cm-1 for 5-FU-As (4B) co-crystals for N-H and -C[bond, double bond]O groups respectively. The structural differences between API and co-crystals were further confirmed through PXRD analysis. The characteristic peak of 5-FU at 2θ = 28.79918o was significantly shifted in the graphs of co-crystals not only in position but also with respect to intensity and FWHM values. In addition, new peaks were also recorded in all the spectra of co-formers confirming the structural differences between API and co-formers. In addition, percent growth inhibition was also observed by all the co-crystals through MTT assay against HCT 116 colorectal cell lines in vitro. At four different concentrations; 25, 50, 100 and 200 µg/mL, slightly different trends of the effectiveness of API and co-crystals were observed. However; among all the co-crystal forms, 5-FU-thiourea co-crystals obtained through solution method (2B) proved to be the most effective growth inhibitor at all the four above mentioned concentrations.

NiO/MnFe2O4 Nanocomposite Photoluminescence, Structural, Morphological, Magnetic, and Optical Properties: Photocatalytic Removal of Cresol Red under Visible Light Irradiation.

In this study, pure nickel oxide (NiO), manganese ferrite (MnFe2O4 or MFO), and binary nickel oxide/manganese ferrite (NiO/MFO1-4) nanocomposites (NCs) were synthesized using the Sol-Gel method. A comprehensive investigation into their photoluminescence, structural, morphological, magnetic, optical, and photocatalytic properties was conducted. Raman analysis, UV-Vis spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction techniques were used to characterize the materials. The synthesized samples exhibited superparamagnetic behavior, as revealed by our analysis of their magnetic properties. A lower recombination rate was shown by the photoluminescence analysis, which is helpful for raising photocatalytic activity. The photocatalytic activity was evaluated for the degradation of Cresol Red (CR) dye. 91.6% of CR dye was degraded by NiO/MFO-4 nanocomposite, and the NC dosage as well as solution pH affected the photocatalytic performance significantly. In four sequential photocatalytic cycles, the magnetically separable NCs were stable and recyclable. The enhanced photocatalytic activity and magnetic separability revealed the potential application of NiO/MFO-4 as an efficient photocatalyst for the removal of dyes from industrial wastewater under solar light irradiation.

Synthesis, Characterization, Theoretical and Experimental Anticancer Evaluation of Novel Cocrystals of 5-Fluorouracil and Schiff Bases against SW480 Colorectal Carcinoma.

The chemotherapeutic agent known as 5-fluorouracil (5-FU) is an artificial fluoropyrimidine antimetabolite that has been widely used for its antineoplastic properties. Cocrystals of 5-fluorouracil (5-FU) with five different Schiff bases (benzylidene-urea (BU), benzylidene-aniline (BA), salicylidene-aniline (SA), salicylidene-phenylhydrazine (SPH), and para-hydroxy benzylideneaniline (HBA)) are reported in this study. The newly synthesized cocrystals were analyzed by FTIR and PXRD. In this study, we investigated the antitumor efficacy of 5-FU derivatives in SW480 colon cancer cells via MTT assay at varying dose concentrations. Molecular docking was performed to predict the binding mechanism of TS with various 5-FU complexes. FTIR revealed the presence of respective functional groups in the prepared cocrystals. The frequencies (v) of N-H (3220.24 cm-1) and carbonyl groups (1662.38 cm-1) in the spectrum of 5-FU shifted considerably in all derivative cocrystal new interactions. There was a noticeable transformation in the PXRD peak of 5-FU at 2θ = 28.37° in all derivatives. The novelty of the present study lies in the fact that 5-FU-BA showed an anticancer potential IC50 (6.4731) far higher than that of 5-FU (12.116), almost comparable to that of the reference drug doxorubicin (3.3159), against SW480 cancel cell lines, followed by 5-Fu-HBA (10.2174). The inhibition rates of 5-FU-BA and 5-FU-HBA were highest among the derivatives (99.85% and 99.37%, respectively) in comparison with doxorubicin (97.103%). The results revealed that the synthesized 5-FU cocrystals have promising antitumor efficacy compared with previously reported 5-FU and 5-FU. The activities of the cocrystals were rationalized by a molecular modeling approach to envisage binding modes with the target cancer protein.

Green synthesis of coumarin derivatives using Brønsted acidic pyridinium based ionic liquid [MBSPy][HSO4] to control an opportunistic human and a devastating plant pathogenic fungus Macrophomina phaseolina.

An eco-friendly simple protocol has been devised for the preparation of coumarin derivatives using doubly Brønsted acidic task specific ionic liquid (TSIL) as a catalyst. Solvent-free conditions were employed for the reaction of different substituted phenols with ß-ketoester in TSIL to produce corresponding substituted coumarin derivatives in good to excellent yields at ambient conditions; at room temperature and with reduced reaction times. The ionic liquid catalyst can be recycled and reused up to five times. All the synthesized coumarins were evaluated for their antifungal activities against Macrophomina phaseolina, a plant as well as an opportunistic human pathogenic fungus affecting more than 500 plant species worldwide and with no registered commercial fungicide available against it, to date. Amongst all the coumarins tested, compounds 3f and 3i showed excellent antifungal activity comparable to reference fungicide mancozeb. The current methodology provides an easy and expedient way to access the coumarin core in search of potential fungicides for sustainable agriculture.

Depsitinuside: a new depside galactoside from an endophytic fungus isolated from Viburnum tinus.

Chromatographic purification of the extract of an endophytic fungal culture yielded depsitinuside (1), a new phenolic ester together with ergosterol (2) and (22E,24S)-24-methyl-5-α-cholesta-7,22-diene-3ß,5,6ß-triol (3). The structure of 1 was elucidated based on 1D, 2D NMR spectroscopy and high-resolution mass spectrometry, whereas the known compounds (2 and 3) were identified by (1)H NMR, mass spectrometry, and in comparison with the literature values. Compound 1 was evaluated for its enzyme inhibitory potential against acetylcholinesterase, butyrylcholinesterase and lipoxygenase, and was found inactive (10%-40% inhibition at a concentration of 2 mg/ml).

Enhancing catalytic potential of gold nanoparticles by linear and cross-linked polyurethane blending.

This work describes the synthesis of gold nanoparticles (AuNPs) and their subsequent stabilization using a water-borne polyurethane matrix of micro-particles (Au/PU) by a heating method. Composites were prepared both from linear and cross-linked polyurethane (LPU and CPU). Catalytic activities of synthesized composites exhibiting 226.4 nm size were evaluated for reduction of Congo red dye. More than 90% Congo red degradation was achieved in just 6 minutes with Au/LPU. Under similar conditions, 30% of dye was degraded with Au/CPU composite in 5 minutes. The effects of different variables such as concentration of dye, catalyst dose and concentration of reagents have been optimized. The degradation process followed first order kinetics. The most efficient composite (Au/LPU) was characterized using UV/Vis, FTIR, SEM, XRD and DLS techniques. The excellent catalytic activity can be attributed to the polyurethane matrix making the dye available to catalytic sites (AuNPs).

Sodium alginate blended membrane with polyurethane: Desalination performance and antimicrobial activity evaluation.

A series of polymeric membranes were synthesized by blending polyurethane with sodium alginate (0.2, 0.4, 0.6, 0.8 and 1.0%). The structural, morphological and thermal properties of the membranes were examined by FTIR, SEM, AFM and TGA, respectively. Performance evaluation (salt rejection and flux) was assessed through reverse osmosis technique (RO). The FTIR spectra of membranes confirmed extensive hydrogen bonding (3350 cm-1). The SEM and AFM analyses supported a progressively rising surface roughness of blended membranes. The hydrophilicity, crosslinking density and thermal stability of the membranes were improved with an increase in alginate content. The capability of salt (NaCl and MgCl2) rejection was improved with alginate up to 0.8%. In addition, the rejection of divalent ions was better than monovalent ions (94 ± 0.96% for NaCl and 98 ± 0.98% for MgCl2). The blended membranes ascertained an effective chlorine resistivity. The antibacterial activity was also promising, which enhanced with the alginate content in the membrane. The sodium alginate blended membrane with polyurethane proved to be an efficient approach to develop the blended membranes with tunable properties for water desalination.

Designing of biocompatible and biodegradable chitosan based crosslinked hydrogel for in vitro release of encapsulated povidone-iodine: A clinical translation.

Controlled drug delivery is a prime stratagem for minimizing both the frequency of therapeutic administration as well as systematic side effects with high drug content. One of the extensively studied approaches for controlling medicament delivery is the encapsulation of drug within polymer chains which sluggish the release on the basis of its crosslinked network. Recent advances in biomedical field have led to the fabrication of chitosan (CS) based biocompatible and biodegradable hydrogels for controlled delivery of encapsulated drug. In this study, CS-PVP based hydrogels are fabricated by varying the concentration of 3-glycidyloxypropyl trimethoxysilane (GPTMS) via solution casting technique. Swelling indices of prepared hydrogel samples were determined in different media including distilled water, different pH and electrolyte solutions. FTIR, TGA and WAXRD are conducted to evaluate the structural, thermal and crystalline properties of prepared hydrogels, respectively. Porosity (71%), hydrophilicity (55°) and mechanical properties (97.56 MPa of UTS and 85.23% E%) were investigated for the fabricated samples. Extensively in vitro biodegradation, antimicrobial performance and cytotoxicity were evaluated for these hydrogels. The drug release analysis was carried out to examine the release response of encapsulated iodopovidone at physiological conditions. These results tender a strategy for the design of structural hydrogel with different crosslinking mechanism like physical and covalent interactions. These insights obviate the demand for encapsulation and offer promising and translatable strategies for more effective release of drugs.

Linear and crosslinked Polyurethanes based catalysts for reduction of methylene blue.

The large amount of synthetic dyes in effluents is a serious concern to be addressed. The chemical reduction is one of the potential way to resolve this problem. In this study, linear and crosslinked polyurethanes i.e. LPUR & CLPUR were synthesized from toluene diisocyanate (TDI), polyethylene glycol (PEG;1000g/mole) and tetraethylenepentamine (TEPA). The structure and morphology of synthesized materials were examined by FTIR, SEM and BET. The CLPUR was found stable in aqueous system with 0.80g/cm3 density and 16.4998m2g-1 surface area. These materials were applied for the reduction of methylene blue in presence of NaBH4. Both, polymers catalyzed the process and showed 100% reduction in 16 and 28mins., respectively, while, the reduction rate was significantly low in absence of these materials, even after 120mins. Furthermore, negligible adsorption was observed with only 7% removal of dye. The best reduction rates were observed at low concentration of dye, increasing concentration of NaBH4 and with more dosage of polymeric catalyst. The kinetic study of process followed zero order kinetics. It was hence concluded that both synthesized polymers played a catalytic role in reduction process. However, stability in aqueous system and better efficiency in reduction process endorsed CLPUR as an optimal choice for further studies.

Co-concentration effect of silane with natural extract on biodegradable polymeric films for food packaging.

Novel biodegradable films were prepared by blending guar gum, chitosan and poly (vinyl alcohol) having mint (ME) and grapefruit peel (GE) extracts and crosslinked with nontoxic tetraethoxysilane (TEOS). The co-concentration effect of TEOS with natural extracts on the films was studied. FTIR analysis confirmed the presence of incorporated components and the developed interactions among the polymer chains. The surface morphology of the films by SEM showed the hydrophilic character due to porous network structure. The films having both ME and GE with maximum amount of crosslinker (100µL), showed maximum swelling (58g/g) and stability while the optical properties showed increased protection against UV light. This film sample showed compact network structure which enhanced the ultimate tensile strength (40.03MPa) and elongation at break (104.8%). ME/GE conferred the antioxidant properties determined by radical scavenging activity and total phenolic contents (TPC) as ME films have greater TPC compared to GE films. The soil burial test exhibited the degradation of films rapidly (6days) confirming their strong microbial activity in soil. The lower water vapour transmission rate and water vapour permeability showed better shelf life; hence, these biodegradable films are environmental friendly and have potential for food and other packaging.

By-product identification and phytotoxicity of biodegraded Direct Yellow 4 dye.

Citrus limon peroxidase mediated decolourization of Direct Yellow 4 (DY4) was investigated. The process variables (pH, temperature, incubation time, enzyme dose, H2O2 amount, dye concentration, co-metal ions and surfactants) were optimized for maximum degradation of dye. Maximum dye decolourization of 89.47% was achieved at pH 5.0, temperature 50 °C, enzyme dose 24 U/mL, H2O2 concentration 0.25 mM and DY4 concentration 18.75 mg/L and incubation time 10 min. The co-metal ions and surfactants did not affect the dye decolourization significantly. Response surface analysis revealed that predicted values were in agreement with experimentally determined responses. The degradation products were identified by UPLC/MS analysis and degradation pathway was proposed. Besides, phytotoxicity assay revealed a considerable detoxification in response of biodegradation of DY4 dye. C. limon showed promising efficiency for DY4 degradation and could possibly be used for the remediation of textile effluents.

Modification of cellulosic fiber with polyurethane acrylate copolymers. Part I: Physicochemical properties.

Polyurethane (PU) prepolymers were prepared by using two different diisocyanates i.e., toluene-2,4-diisocyanate (TDI) and or isophorone diisocyanate (IPDI), and poly (2-methyl-1,3-propylene glutarate), hydroxyl terminated group. PU prepolymer was reacted with 2-hydroxyethylacrylate (HEA) to form vinyl terminated PU prepolymer. Vinyl terminated PU prepolymers were further copolymerized with butyl acrylates (BuA) by emulsion process. The structure of proposed PUACs samples was confirmed by FT-IR, and their physicochemical properties were studied determining solid contents (%), emulsion stability and its appearance, tackiness and film appearance. Their acids and base chemical resistance was also studied and discussed. The synthesized PUACs samples were applied using dip-padding techniques on mill un-desized poly-cotton plain weave fabrics. The results emphasis that PUACs based on toluene-2,4-diisocyanate (TDI) have shown excellent performance against physical and chemical resistance as compared to isophorone diisocyanate (IPDI) based PUACs, however vice versa results were found in some studies.

Two new rotenoids from Boerhavia repens.

Two new rotenoids, boerharotenoids A (1) and B (2), and four known compounds, boeravinone (3), 5,7,3'-trihydroxycoumaronochromone (4), boeravinone F (5), and eupalitin-3-O-beta-D-galactopyranoside (6), have been isolated from Boerhavia repens and their structures established by spectroscopic (1D and 2D NMR) and mass spectrometric comparison with literature values.