Bimlesh Lochab

Naturally occurring phenolic sources: monomers and polymers

Exploration of sustainable alternatives to chemicals derived from petro-based industries is the current challenge for maintaining the balance between the needs of a changing world while preserving nature. The major source for sustainable chemicals is either the natural existing plant sources or waste generated from agro-based industries. The utility of such resources will supplement new processed materials with different sets of properties and environmental friendliness due to their biodegradability and low toxicity during preparation, usage and disposal. Amongst other polymers used on a day-to-day basis, phenolic resins account for vast usage. Replacement of petro-based monomers such as phenol and its derivatives either partly or completely utilized for the synthesis of such resins is ongoing. Extraction of natural phenolic components from cashew nut shell liquid, lignin, tannin, palm oil, coconut shell tar or from agricultural and industrial waste, and their utilization as synthons for the preparation of bio-based polymers and properties obtained are reviewed in this paper. This review article is designed to acknowledge efforts of researchers towards the “3C” motto – not only trying to create but also adapting the principles to conserve and care for a sustainable environment. This review paper describes how extraction, separation and recovery of desired phenolic compounds have occurred recently; how substituted phenol compounds, unmodified and modified, act as monomers for polymerization; and how the presence of sustainable phenolic material affects the properties of polymers. There are about 600 references cited and still there is a lot to uncover in this research area.

Azido Polymers—Energetic Binders for Solid Rocket Propellants

2. PREPARATION OF AZIDO POLYMERS. . . . . . . . . . . . . . . . . . . . . . . 508 2.1. Polymerization of Glycidyl Azide (GA) . . . . . . . . . . . . . . . . . . . . . . 508 2.1.1. Derivatization of polyepichlorohydrin (PECH). . . . . . . . . . . 508 2.2. Direct Conversion of Epichlorohydrin to Glycidyl Azide Polymer (GAP).. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513 2.3. Simultaneous Degradation and Azidation of PECH and Its Copolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514 2.4. Block Copolymers of GAP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515 2.5. Polymerization of Azidomethyl Oxetanes . . . . . . . . . . . . . . . . . . . . . 515 2.6. Poly(allyl azide) (PAA). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519

Sustainable Sulfur-rich Copolymer/Graphene Composite as Lithium-Sulfur Battery Cathode with Excellent Electrochemical Performance

A sulfur-rich copolymer, poly(S-r-C-a) has been synthesized via a sustainable route, showing the utility of two major industrial wastes- elemental sulfur (petroleum waste) and cardanol (agro waste), to explore its potential as cathode material for Li-S batteries. The sulfur-rich copolymer exhibited a reduction in the active material dissolution into the electrolyte and a low self-discharge rate behavior during the rest time compared to an elemental sulfur cathode, indicating the chemical confinement of sulfur units. The presence of organosulfur moieties in copolymer suppress the irreversible deposition of end-discharge products on electrode surfaces and thus improve the electrochemical performances of Li-S batteries. This sulfur copolymer offered a reversible capacity of 892 mA h g−1 at 2nd cycle and maintained the capacity of 528 mA h g−1 after 50 cycles at 200 mA g−1. Reduced graphene oxide (rGO) prepared via a sustainable route was used as a conductive filler to extract the better electrochemical performances from this sulfur copolymer. Such sustainable origin batteries prepared via economically viable showed an improved specific capacity of ~975 mA h g−1 after 100 cycles at 200 mA g−1 current rate with capacity fading of 0.15% per cycle and maintained a stable performance over 500 cycles at 2000 mA g−1.

Cardanol benzoxazines – interplay of oxazine functionality (mono to tetra) and properties

Cardanol, a sustainable origin phenol, was utilized as a reactive diluent to mediate solventless Mannich-type condensation reaction with para-formaldehyde and primary aromatic amines to form a homologous series of benzoxazine (Bz) monomers namely C-a, C-ddm, C-trisapm and C-tetraapm which differ in their degree of oxazine functionality as mono-, di-, tri- and tetra-oxazine respectively. A strong correlation is reflected between the number of oxazine rings in the monomer and the polymerization behavior, thermo-mechanical transitions, and properties of the polybenzoxazine synthesized. The monomer structure was confirmed by FTIR, 1H-, 13C-NMR spectroscopy and mass spectrometry. The curing, rheological, thermo-mechanical and thermal properties were determined using DSC, FTIR, rheometer, DMTA, LSS and TGA studies. The curing characteristic due to ROP of Bz monomers was supported both by DSC and FTIR studies. The presence of neighboring oxazine group in monomers (C-a to C-tetraapm) strongly attenuates the curing temperature (Ti = 225–140 °C), enhances Tg, thermal stability, and mechanical properties. Interestingly, DFT calculations also supported the lowest curing temperature for highest oxazine functionality monomer (C-tetraapm). The interplay between the degree of oxazine functionality in the monomer; extent of H-bonding and crosslink density values in sustainable origin synthesized polybenzoxazines is suggested. The thermoset showed an increasing trend (PC-a < PC-ddm < PC-trisapm < PC-tetraapm) in Tg (58–109 °C), thermal stability (355–391 °C), char yield (13–37%), LOI (23–31) and storage modulus (3.6–66.5 MPa) values. The monomers are liquid to semi-viscous paste at room temperature and showed potential for solventless processing in adhesive applications.

Blends of benzoxazine monomers

This article describes synthesis, characterization and properties of blends of benzoxazine (Bz) monomers, i.e., m-alkylphenyl-3,4-dihydro-2H-benzoxazine (Bz-C), 6,6′-(propane-2,2-diyl)bis(3-phenyl-3,4-dihydro-2H-benzoxazine (Bz-A) and 3-phenyl-3,4-dihydro-2H-benzoxazine-p-carboxylic acid (Bz-pA). Binary blends of Bz-C with Bz-pA, and Bz-A with Bz-pA were prepared by first synthesizing Bz-C or Bz-A followed by the addition of all the ingredients of Bz-pA. In a similar manner, ternary blends of Bz-C, Bz-A and Bz-pA were prepared by first synthesizing Bz-C and subsequent addition of all the ingredients of Bz-A and Bz-pA in one pot. The Bz monomer blends were characterized by 1H-NMR, FTIR spectroscopy, and differential scanning calorimetry. The temperature of onset of curing (To), due to ring-opening polymerization of Bz was found to decrease significantly by incorporation of carboxyl groups (Bz-pA) showing thereby the catalytic effect of acid functionality. Bz polymers showed good thermal stability and incorporation of Bz-pA in blends resulted in a highly cross-linked network. The interlaminar shear strength of glass fabric reinforced composites and the lap shear strength of metal–metal joints using these resin blends was also investigated.

Thermal behaviour of poly(allyl azide)

The paper describes the synthesis of low molecular mass poly(allyl chloride) (PAC) (Mn= 856-3834 g mol-1) using Lewis acid (ALCL3, FeCL3, TiCL4) and al powder. Branching in PAC was indicated on the basis of elemental analysis and 1H-NMR spectroscopy. azidation of pac could be carried out at 100°C by using NaN3 and DMSO as solvent. Curing of poly(allyl azide) (PAA) by cyclic dipolar addition reaction with EGDMA (ethylene glycol dimethacrylate, 5-45 phr) was investigated by differential scanning calorimetry and structure of cured polymer was confirmed by FTIR. A two-step mass loss was exhibited by uncured and cured PAA in nitrogen atmosphere. A mass loss of 20-28% (155-274°C) and 50-61% (330-550°C) was observed.

Graphene Oxide-Coated Surface: Inhibition of Bacterial Biofilm Formation due to Specific Surface–Interface Interactions

Graphene oxide (GO) is a promising and remarkable nanomaterial that exhibits antimicrobial activity due to its specific surface–interface interactions. In the present work, for the first time, we have reported the antibacterial activity of GO-coated surfaces prepared by two different methods (Hummers’ and improved, i.e., GOH and GOI) against bacterial biofilm formation. The bacterial toxicity of the deposited GO-coated surfaces was investigated for both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) models of bacteria. The mechanism of inhibition is different on the coated surface than that in suspension, as determined by measurement of the percentage inhibition of biofilm formation, Ellman’s assay, and colony forming unit (CFU) studies. The difference in the nature, degree of oxidative functionalities, and size of the synthesized GO nanoparticles mitigates biofilm formation. To better understand the antimicrobial mechanism of GO when coated on surfaces, we were able to demonstrate that beside reactive oxygen species-mediated oxidative stress, the physical properties of the GO-coated substrate effectively inactivate bacterial cell proliferation, which forms biofilms. Light and atomic force microscopy (AFM) images display a higher inhibition in the proliferation of planktonic cells in Gram-negative bacteria as compared to that in Gram-positive bacteria. The existence of a smooth surface with fewer porous domains in GOI inhibits biofilm formation, as demonstrated by optical microscopy and AFM images. The oxidative stress was found to be lower in the coated surface as compared to that in the suspensions as the latter enables exposure of both a large fraction of the active edges and functionalities of the GO sheets. In suspension, GOH is selective against S. aureus whereas GOI showed inhibition toward E. coli. This study provides new insights to better understand the bactericidal activity of GO-coated surfaces and contributes to the design of graphene-based antimicrobial surface coatings, which will be valuable in biomedical applications.

Stable Dispersions of Covalently Tethered Polymer Improved Graphene Oxide Nanoconjugates as an Effective Vector for siRNA Delivery

Conjugates of poly(amidoamine) (PAMAM) with modified graphene oxide (GO) are attractive nonviral vectors for gene-based cancer therapeutics. GO protects siRNA from enzymatic cleavage and showed reasonable transfection efficiency along with simultaneous benefits of low cost and large scale production. PAMAM is highly effective in siRNA delivery but suffers from high toxicity with poor in vivo efficacy. Co-reaction of GO and PAMAM led to aggregation and more importantly, have detrimental effect on stability of dispersion at physiological pH preventing their exploration at clinical level. In the current work, we have designed, synthesized, characterized and explored a new type of hybrid vector (GPD), using GO synthesized via improved method which was covalently tethered with poly(ethylene glycol) (PEG) and PAMAM. The existence of covalent linkage, relative structural changes and properties of GPD is well supported by Fourier transform infrared (FTIR), UV-visible (UV-vis), Raman, X-ray photoelectron (XPS), elemental analysis, powder X-ray diffraction (XRD), thermogravimetry analysis (TGA), dynamic light scattering (DLS), and zeta potential. Scanning electron microscopy (SEM), and transmission electron microscopy (TEM) of GPD showed longitudinally aligned columnar self-assembled ∼10 nm thick polymeric nanoarchitectures onto the GO surface accounting to an average size reduction to ∼20 nm. GPD revealed an outstanding stability in both phosphate buffer saline (PBS) and serum containing cell medium. The binding efficiency of EPAC1 siRNA to GPD was supported by gel retardation assay, DLS, zeta potential and photoluminescence (PL) studies. A lower cytotoxicity with enhanced cellular uptake and homogeneous intracellular distribution of GPD/siRNA complex is confirmed by imaging studies. GPD exhibited a higher transfection efficiency with remarkable inhibition of cell migration and lower invasion than PAMAM and Lipofectamine 2000 suggesting its role in prevention of breast cancer progression and metastasis. A significant reduction in the expression of the specific protein against which siRNA was delivered is revealed by Western blot assay. Furthermore, a pH-triggered release of siRNA from the GPD/siRNA complex was studied to provide a mechanistic insight toward unloading of siRNA from the vector. Current strategy is a way forward for designing effective therapeutic vectors for gene-based antitumor therapy.

Sustainable one-step strategy towards low temperature curable superparamagnetic composite based on smartly designed iron nanoparticles and cardanol benzoxazine

Despite recent advances in polybenzoxazines (PBzs), especially of sustainable origin, the lowering of the curing temperature still remains a challenge in addressing their exploration in low-temperature processing applications. Innovative iron-based catalysts which are naturally abundant, cost-effective, and with larger surface area could demonstrate a practical, economic and facile approach for the development of iron NPs–polybenzoxazine composites. Here we propose an approach to develop a composite based on smartly-capped iron nanoparticles (NPs) and agro-waste phenolic-sourced cardanol benzoxazine monomer as a one-step solution with the benefits of lowering the curing temperature and providing superparamagnetism. NPs are smartly designed with a variation in the nature of the functionality in the capping agent and are characterized by thermogravimetry analysis (TGA), Fourier transform infrared (FTIR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The NPs showed a spherical shape of ∼10 nm in size with appreciable magnetic characteristics. Both iron ions and available functionalities in the capping agent endow benefits in lowering the curing temperature of cardanol benzoxazine (64 °C), and enhancing its maximum thermal stability (34 °C), as determined by differential scanning calorimetry (DSC) and TGA, respectively. In addition, the nature of the chemical linkages in the polybenzoxazine network and the initial growth in the molecular weight of the polymer were found to be influenced by iron NPs, as supported by FTIR, nuclear magnetic resonance (1H-NMR), UV-visible (UV-vis) spectroscopy, and gel permeation chromatography (GPC). The capping-agent-facilitated NPs distribution in the polybenzoxazine matrix was determined by atomic force microscopy (AFM). Polymer nanocomposites even with a 5 wt% loading of NPs showed good magnetic saturation and superparamagnetic behavior. The present work demonstrated a one-step solution with the incorporation of NPs in a benzoxazine monomer accounting for modification in the properties of polybenzoxazine composites with the benefits of magnetism.

Benzoxazine derivatives of phytophenols show anti-plasmodial activity via sodium homeostasis disruption

Development of new class of anti-malarial drugs is an essential requirement for the elimination of malaria. Bioactive components present in medicinal plants and their chemically modified derivatives could be a way forward towards the discovery of effective anti-malarial drugs. Herein, we describe a new class of compounds, 1,3-benzoxazine derivatives of pharmacologically active phytophenols eugenol (compound 3) and isoeugenol (compound 4) synthesised on the principles of green chemistry, as anti-malarials. Compound 4, showed highest anti-malarial activity with no cytotoxicity towards mammalian cells. Compound 4 induced alterations in the intracellular Na+ levels and mitochondrial depolarisation in intraerythrocytic Plasmodium falciparum leading to cell death. Knowing P-type cation ATPase PfATP4 is a regulator for sodium homeostasis, binding of compound 3, compound 4 and eugenol to PfATP4 was analysed by molecular docking studies. Compounds showed binding to the catalytic pocket of PfATP4, however compound 4 showed stronger binding due to the presence of propylene functionality, which corroborates its higher anti-malarial activity. Furthermore, anti-malarial half maximal effective concentration of compound 4 was reduced to 490 nM from 17.54 µM with nanomaterial graphene oxide. Altogether, this study presents anti-plasmodial potential of benzoxazine derivatives of phytophenols and establishes disruption of parasite sodium homeostasis as their mechanism of action.