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Shiv Nadar University

(SoNS) School of Natural Sciences

Polybenzoxazines obtained especially from green synthons are facing challenges of the requirement of high ring-opening polymerization (ROP) temperature of the monomer, thus affecting their exploration at the industrial front. This demands effective structural changes in the monomer itself, to mediate catalyst-free polymerization at a low energy via one-step synthesis protocol. In this regard, monomers based on disulfide-linked bisbenzoxazine were successfully synthesized using cystamine (biobased) and cardanol (agro-waste)/phenol. Reduction of the disulfide bridge in the monomer using dithiothreitol under mild conditions in situ transformed the oxazine ring in the monomer, via neighboring group participation of the -SH group in a transient intermediate monomer, into a thiazolidine structure, which is otherwise difficult to synthesize. Structural transformation of ring-opening followed by the ring-closing intramolecular reaction led to an interconversion of O-CH2-N containing a six-membered oxazine ring to S-CH2-N containing a five-membered thiazolidine ring and a phenolic-OH. The structure of the monomer with the oxazine ring and its congener with the thiazolidine ring was characterized by spectroscopic methods and X-ray analysis. Kinetics of structural transformation at a molecular level is studied in detail, and it was found that the reaction proceeded via a transient 2-aminoethanethiol-linked benzoxazine intermediate, as supported by nuclear magnetic resonance spectroscopy and density functional theory studies. The thiazolidine-ring-containing monomer promotes ROP at a substantially low temperature than the reported mono-/bisoxazine monomers due to the dual mode of facilitation of the ROP reaction, both by phenolic-OH and by ring strain. Surprisingly, both the monomer structures led to the formation of a similar polymer structure, as supported by thermogravimetric analysis and Fourier transform infrared study. The current work highlights the benefits of inherent functionalities in naturally sourced feedstocks as biosynthons for the new latest generation of benzoxazine monomers. © 2021 American Chemical Society.

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Chemistry

Biomacromolecules

Self-Polymerization Promoting Monomers: In Situ Transformation of Disulfide-Linked Benzoxazines into the Thiazolidine Structure

Excellent cyclic stability and fast charge/discharge capacity demonstrated by supercapacitors foster research interest into new electrode materials with 100\% cycle life and high specific capacitance. We report an improvement in the electrochemical performance of MoS2/multiwalled carbon nanotubes (MWCNT) nanohybrid and intensively explored its performance in symmetric and asymmetric supercapacitor (ASC) assembly. The symmetric assembly of MoS2/MWCNT exhibits capacitance of around 274.63 F g-1 at 2 A g-1 with higher specific energy/power outputs (20.70 Wh kg-1/1.49 kW kg-1) as compared to the supercapacitor based on pristine MoS2 (5.82 Wh kg-1/1.07 kW kg-1). On the other hand, a unique all-carbon-based ASC assembled with MoS2/MWCNT and VSe2/MWCNT composite with K2SO4 as electrolyte delivers the highest energy density of 32.18 Wh kg-1 at a power density of 1.121 kW kg-1 with exceptional cycling stability and excellent retention of about 98.43\% even after 5000 cycles. These outstanding results demonstrate the excellent electrochemical properties of both symmetric and asymmetric systems with high energy density and performance, which further enable them to be a potential candidate for supercapacitor applications. © 2021 IOP Publishing Ltd.

Physics

Nanotechnology

Energy storage performance of 2D MoS2 and carbon nanotube heterojunctions in symmetric and asymmetric configuration

Herein we report a series of telescoping methodologies for one pot synthesis of biologically relevant γ-carboline derivatives 6 and spiro[pyrrolidinone-3,3′]indole 7. Initially the three consecutive steps of cyclopropanation, phthalimide deprotection, and Boc-deprotection have been congregated in a single reaction vessel to afford a ∼1:1 mixture of 6 and 7. Next, careful optimization of the reaction sequence and the conditions generated an orthogonal approach to access compounds 6 and 7 exclusively. Air oxidation of the γ-carbolinones 6 afforded aromatic γ-carbolines 8. © 2021 American Chemical Society.

Journal of Organic Chemistry

Orthogonal Syntheses of γ-Carbolinone and Spiro[pyrrolidinone-3,3′]indole Derivatives in One Pot through Reaction Telescoping

To improve the production rate of MoS2 nanosheets as an excellent supercapacitor (SC) material and enhance the performance of the MoS2-based solid-state SC, a liquid phase exfoliation method is used to prepare MoS2 nanosheets on a large scale. Then, the MnO2 nanowire sample is synthesized by a one-step hydrothermal method to make a composite with the as-synthesized MoS2 nanosheets to achieve a better performance of the solid-state SC. The interaction between the MoS2 nanosheets and MnO2 nanowires produces a synergistic effect, resulting in a decent energy storage performance. For practical applications, all-solid-state SC devices are fabricated with different molar ratios of MoS2 nanosheets and MnO2 nanowires. From the experimental results, it can be seen that the synthesized nanocomposite with a 1:4 M ratio of MoS2 nanosheets and MnO2 nanowires exhibits a high Brunauer-Emmett-Teller surface area (118 m2/g), optimum pore size distribution, a specific capacitance value of 212 F/g at 0.8 A/g, an energy density of 29.5 W h/kg, and a power density of 1316 W/kg. Besides, cyclic charging-discharging and retention tests manifest significant cycling stability with 84.1% capacitive retention after completing 5000 rapid charge-discharge cycles. It is believed that this unique, symmetric, lightweight, solid-state SC device may help accomplish a scalable approach toward powering forthcoming portable energy storage applications. ©

ACS Omega

High-Performance MnO2Nanowire/MoS2Nanosheet Composite for a Symmetrical Solid-State Supercapacitor

Disposable devices for sensing biomarkers like Na+ ion in sweat was developed using UV-Ozone irradiated laser-induced graphene (LIG) based electrodes. Solid-state ion-selective electrodes (ISEs) sensitive to Na+ ions were fabricated by a two-step drop-coating process of polyvinyl chloride solution containing plasticizer, ionophore and ion-exchanger on LIG electrode. Hydrophobic to hydrophilic transition induced by UV-Ozone treatment reduced the contact angle, resulting in better permeation of the ion-selective membrane into the ozonized LIG film. Raman spectroscopy and IR absorption studies indicate physisorption of ozone on LIG. Performance of ozonized LIG (O-LIG) electrodes was much better than pristine LIG and screen-printed carbon electrodes. Sensitivity of 60.2 ± 0.9 mV/ decade to Na+ ions and a lower limit of detection of 1 × 10−6 M was achieved using O-LIG based ISEs. Response time of the devices were around 1 min. © 2021 Elsevier Ltd

Fulltext

Electrochimica Acta

Potentiometric ion-selective sensors based on UV-ozone irradiated laser-induced graphene electrode

The stereoselectivity and stereospecificity of the triflate-mediated intramolecular Schmidt reaction of substituted 3-(1-azidocyclohexyl)propanol derivatives leading to octahydro-1H-pyrrolo[1,2-a]azepine, the structural skeleton of several important families of alkaloids such as the Stemona alkaloids, has been examined. The reaction involves an initial intramolecular SN2 reaction between the azide moiety and the triflate affording an intermediate spirocyclic aminodiazonoium salt that undergoes the expected 1,2-shift/N2-elimination followed by hydride-mediated iminium salt reduction. Remarkably, chiral alcohols are converted to the azabicyclic derivative with no or limited racemization. The initial asymmetric alcohol center controls the diastereoselectivity of the whole process, leading to the formation of one out of the four possible diastereoisomers of disubstituted octahydro-1H-pyrrolo[1,2-a]azepine. The origin of the stereoselectivity is rationalized based on theoretical calculations. The concise synthesis of (−)-(cis)-3-propylindolizidine and (−)-(cis)-3-butyllehmizidine, two alkaloids found in the venom of workers of the ant Myrmicaria melanogaster, is reported.

Angewandte Chemie - International Edition

Stereoselective and Stereospecific Triflate-Mediated Intramolecular Schmidt Reaction: Ready Access to Alkaloid Skeletons**

Violacein is a naturally found pigment that is used by some gram negative bacteria to defend themselves from various gram positive bacteria. As a result, this molecule has caught attention for its potential biomedical applications and has already shown promising outcomes as an antiviral, an antibacterial, and an anti-tumor agent. Understanding the interaction of this molecule with a cellular membrane is an essential step to extend its use in the pharmaceutical paradigm. Here, the interaction of violacein with a lipid monolayer formed at the air–water interface is found to depend on electrostatic nature of lipids. In presence of violacein, the two dimensional (2D) pressure–area isotherms of lipids have exhibited changes in their phase transition pressure and in-plane elasticity. To gain insights into the out-of-plane structural organization of lipids in a membrane, X-ray reflectivity (XRR) study on a solid supported lipid monolayer on a hydrophilic substrate has been performed. It has revealed that the increase in membrane thickness is more pronounced in the zwitterionic and positively charged lipids compared to the negatively charged one. Further, the lipid molecules are observed to decrease their tilt angle made with the normal of lipid membrane along with an alteration in their in-plane ordering. This has been quantified by grazing incidence X-ray diffraction (GIXD) experiments on the multilayer membrane formed in an environment with controlled humidity. The structural reorganization of lipid molecules in presence of violacein can be utilized to provide a detailed mechanism of the interaction of this molecule with cellular membrane. © 2021 Elsevier B.V.

Life Sciences

Biochimica et Biophysica Acta - Biomembranes

Discerning perturbed assembly of lipids in a model membrane in presence of violacein

Hydrocarbon pollutants are recalcitrant to degradation and their accumulation in the environment is toxic to all life forms. Bacteria encode numerous catalytic enzymes and are naturally capable of metabolizing hydrocarbons. Scientists harness biodiversity in aquatic ecosystems to isolate bacteria with biodegradation and bioremediation potential. Such isolates from the environment provide a rich set of metabolic pathways and enzymes, which can be further utilized to scale up the degradation process at an industrial scale. In this article, we outline the general process of isolation, propagation, and identification of bacterial species from aquatic habitats and screen their ability to utilize hydrocarbons as the sole carbon source in vitro using simple techniques. The present protocol describes the isolation of various bacterial species and their subsequent identification using the 16S rRNA analysis. The protocol also presents steps for characterizing the hydrocarbon degrading potential of bacterial isolates. This protocol will be useful for researchers trying to isolate bacterial species from environmental habitats for their biotechnological applications. © 2021 JoVE Journal of Visualized Experiments.

Journal of Visualized Experiments

Isolation, Propagation, and Identification of Bacterial Species with Hydrocarbon Metabolizing Properties from Aquatic Habitats

Cancer therapies have undergone a tremendous progress over the past decade. Precision medicine provides a more tailored approach, making the combination of existing therapies more precise. Different types of cancers are characterized by unique biomarkers that are targeted using various genomic approaches by clinicians and companies worldwide to achieve efficient treatment with minimal side effects. Precision medicine has two broad approaches namely stratified and personalized medicine. The driver mutations could vary within a subtype while the same driver mutations could be found across different subtypes. Precision medicine has recently gained a lot of importance for breast cancer therapy. Various kinds of mutations like hotspot mutations, gene alterations, gene amplification mutations are targeted to design a more specific therapy. Apart from these known gene mutations there are various unknown mutations. Thus, tumor heterogeneity can pose a challenge to precision medicine. For breast cancer, one of the most successful models developed in case of precision medicine is the anti-HER2 therapies as HER2 was considered to have the worst prognosis being highly malignant. But now due to the advent of HER2 receptor targeted therapies, it has a good prognosis. Moreover, precision medicine helps in identifying if the drug molecules being used for the treatment of one kind of cancer can be beneficial in the treatment of another kind of cancer as well, considering the signaling pathways and machinery is similar in most of the cancers. This reduces the time for new drug development and is economically more feasible. Precision medicine will prove to be very advantageous in case of brain metastasis. © 2021, The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.

Molecular and Cellular Biochemistry

Current updates on precision therapy for breast cancer associated brain metastasis: Emphasis on combination therapy

Withania somnifera, commonly known as Ashwagandha, is a medicinal plant used for thousands of years for various remedies. Extracts of Ashwagandha contain more than 200 metabolites, with withanone (win) being one of the major ones responsible for many of its medicinal properties. Recently, several cases of liver toxicity resulting from commercially available Ashwagandha products have been reported. The first report of Ashwagandha-related liver damage was from Japan, which was quickly resolved after drug-withdrawal. Later, similar cases of liver toxicity due to Ashwagandha consumption were reported from the USA and Iceland. Towards understanding the liver toxicity of Ashwagandha extracts, we studied win, a representative withanolide having toxicophores or structural alerts that are commonly associated with adverse drug reactions. We found that win can form non-labile adducts with the nucleosides dG, dA, and dC. Using various biochemical assays, we showed that win forms adducts in DNA and interfere with its biological property. Win also forms adducts with amines and this process is reversible. Based on the data presented here we concluded that win is detoxified by GSH but under limiting GSH levels it can cause DNA damage. The work presented here provides a potential mechanism for the reported Ashwagandha-mediated liver damage. © 2021 The Author(s)