Horseradish Peroxidase Catalyzed Synthesis of Polycardanol Microcapsules

Polymers synthesized from naturally derived monomers are valuable since they decrease the reliance on petroleum based feed stocks. Cashew nut shell oil (CNSL) is a side-product from processing of edible Cashew nuts of Annacardium occidentale. One of the major components of CNSL is cardanol, which is a phenol derivative having an unsaturated pentadecyl substituent in the ‘meta’ position with varying amount of unsaturation (no double bonds to three double bonds). The substituent in the meta position can also be hydrogenated to yield completely saturated hydrogenated cardanol. Cardanol can be utilized to stabilize the dispersions of oil in water and vice versa since it displays amphiphilic behavior owing to the phenolic head and the C15 aliphatic tail. Here we report the horseradish peroxidase (HRP) catalyzed polymerization of cardanol at oil water interface to obtain polycardanol microcapsules. A synthetic analogue of hydrogenated cardanol, 3-pentadecylphenol (3PDP), was also oxidatively polymerized at the oil-water interface to obtain Poly(3-pentadecylphenol) microcapsules.     

Synthesis and structural studies of some copper-benzoate complexes

The reaction of CuCl₂·2H₂O with 3,5-diisopropylpyrazole (Pz^iPr2H) in the presence of sodium parafluorobenzoate (Na-p-FBz) resulted in the formation of an oxo-chloro-bridged tetranuclear complex [Cu₄(Pz^iPr2H)₄(μ-O)(μ-Cl)₆] 1, whereas the reaction of Cu(NO₃)₂·3H₂O with Pz^iPr2H in the presence of different benzoates gave [Cu(Pz^iPr2H)₂(μ-OCH₃)]₂(NO₃)₂ 2, [Cu(Pz^iPr2H)₃(NO₃)(p-ClBz)]·CH₃CN 3, [Cu(p-CH₃Bz)₂(Pz^iPr2H)]₂·2CH₃CN 4, [Cu(p-OCH₃Bz)₂(CH₃CN)]₂·4CH₃CN 5 and [Cu(p-CNBz)(CH₃CN)]₂ 6. Single-crystal X-ray diffraction studies confirmed these formulations. DNA binding studies for these complexes were performed by means of UV-visible absorption titration and viscosity measurements. Gel electrophoresis studies showed that hydroxyl radicals are involved in DNA cleavage in the presence of the complexes.     

Organocatalytic asymmetric Friedel–Crafts reaction of 1-naphthols with isatins: an enantioselective synthesis of 3-aryl-3-hydroxy-2-oxindoles

An organocatalytic enantioselective Friedel–Crafts reaction of 1-naphthols with isatins has been developed employing bifunctional thiourea–tertiary amine organocatalysts. A variety of isatin derivatives react well with 1-naphthols in the presence of Cinchona derived thiourea 1a to provide biologically important chiral 3-aryl-3-hydroxy-2-oxindoles (3a–zg) in good yield (70–84%) and moderate to good enantioselectivity (37–83%).     

Development of Polar Organic Mode Chromatographic Method by Polysaccharide-Based Immobilized Chiral Selector and Validation for the Determination of the Enantiopurity of Novel Mineralocorticoid Receptor Antagonist Atropisomer–Esaxerenone

Esaxerenone is a new nonsteroidal mineralocorticoid receptor antagonist utilized to treat high blood pressure. Chemically, esaxerenone is a pyrrole derivative consisting of hindered rotation, which results in stereoisomers named atropisomers. Currently, no methods exist for the separation and quantification of these atropisomers. A new and accurate chiral liquid chromatographic technique was developed and validated to estimate the enantiomeric purity of esaxerenone. Polar organic chiral separation was carried out on an immobilized amylose-based chiral stationary phase (Chiralpak IG) with methanol:acetonitrile:diethylamine (9:1:0.1, v/v/v) mixture as a mobile phase. The total runtime was 15 min, and the resolution (R_s) between the atropisomers was more than 3.0. The detection and quantification thresholds for the R-atropisomer were found to be 0.03 and 0.1 µg mL^?1, respectively, for a test concentration of esaxerenone (1000 µg mL^?1). Over the range from the limit of quantification to 0.3 percent, the method's linearity for the R-atropisomer was excellent (R²?>?0.999). The R-atropisomer recovery varied from 95 to 102%, confirming the method’s good accuracy. For a 48-h research period, the chemical was shown to be stable.

     

Effect of Cold Atmospheric Plasma Jet and Gamma Radiation Treatments on Gingivobuccal Squamous Cell Carcinoma and Breast Adenocarcinoma Cells

Surgery, chemotherapy and radiotherapy, the conventional treatment modalities of cancer though successful are limited by presence of residual tumor cells, toxic side-effects and treatment resistance, thus raising the need for investigating other novel approaches. Here, we have used a cold atmospheric plasma (CAP) jet and assessed the in vitro efficacy in gingivobuccal squamous cell carcinoma (GB-SCC) – ITOC-03, breast adenocarcinoma—MCF7 and HEK293 cells. Cells lines were subjected to varying doses of ionizing radiation (0, 2, 4, 6, 8 Gy) and CAP jet treatment (0, 60, 180, 240, 300 s). CAP jet treatment showed time dependent increase in H₂O₂ and NO₂^? concentration. Cell viability assay showed potent effect of CAP jet on all three cell lines in comparison to radiation treatment, while helium gas treatment showed minimal inhibitory effect. Irradiated, CAP jet and helium gas treated cells showed loss of nucleic acid features, 788 cm^?1 and 1340 cm^?1 in Raman spectra, indicating DNA damage. Principal Component Analysis (PCA) showed distinct classification of CAP-treated and control cells, while Principal Component – Linear Discriminant Analysis (PC-LDA) based classification of Raman spectra showed ITOC-03 and HEK293 cells to be sensitive to CAP jet and radiation treatment in comparison to MCF7 cells. Collectively, cell viability assay and Raman spectroscopy have shown potent effect of CAP jet in GB-SCC and breast adenocarcinoma cells.

     

Shock Processing of Amino Acids Leading to Complex Structures—Implications to the Origin of Life

The building blocks of life, amino acids, are believed to have been synthesized in the extreme conditions that prevail in space, starting from simple molecules containing hydrogen, carbon, oxygen and nitrogen. However, the fate and role of amino acids when they are subjected to similar processes largely remain unexplored. Here we report, for the first time, that shock processed amino acids tend to form complex agglomerate structures. Such structures are formed on timescales of about 2 ms due to impact induced shock heating and subsequent cooling. This discovery suggests that the building blocks of life could have self-assembled not just on Earth but on other planetary bodies as a result of impact events. Our study also provides further experimental evidence for the ‘threads’ observed in meteorites being due to assemblages of (bio)molecules arising from impact-induced shocks.     

Full potential calculation of electronic properties of rutile RO2 (R=Si, Ge, Sn and Pb) compounds via modified Becke Johnson potential

The electronic properties of RO₂ (R=Si, Ge, Sn and Pb; a group IVA element) compounds in rutile structure have been calculated using WIEN2k implementation of full potential linearized augmented plane wave (FPLAPW) method. The exchange and correlation (XC) effects are taken into account by an orbital independent modified Becke Johnson (MBJ) potential as coupled with Local Density Approximation (LDA) for all the compounds except for PbO₂ where only Generalized Gradient Approximation (GGA) is considered for the same. We predict a direct band gap in all these compounds with continuous decrease as the atomic size of IVA element increases such that there is an appearance of semimetallic band structure for the last compound, PbO₂. The largest band gap (7.66 eV) has been found for SiO₂, which governs its insulating nature. We observe that MBJLDA results for band gaps of these compounds are far better than those obtained using GGA and Engel-Vosko's GGA (EV-GGA). A very good agreement is observed between MBJLDA band gaps with corresponding experimental values as compared to other calculations. The electronic band structures are also analyzed in terms of contributions from various electrons.     

A concise synthetic strategy to functionalized chromenones via [5+1] heteroannulation and facile C-N/C-S/C-O bond formation with various nucleophiles

A highly efficient strategy to 2,3-substituted chromen-4H-ones has been developed. The methodology involves unexpected intramolecular heteroannulation of readily accessible substituted 2-hydroxy-ω-nitroacetophenone with carbon disulfide in the presence K₂CO₃ followed by methylation with methyl iodide. These chromenones were further reacted with various nucleophiles such as amines, thiols, and alkoxide resulting in the facile C-N, C-S, and C-O bond formation. The scope and generality have been discussed.     

Local-global principles for representations of quadratic forms

We prove a local-global principle for the problem of representations of quadratic forms by quadratic forms over ℤ, in codimension ≥5. The proof uses the ergodic theory of p-adic groups, together with a fairly general observation on the structure of orbits of an arithmetic group acting on integral points of a variety.     

The service system M/M R /∞ with impatient customers

An infinite server queue is considered where customers have a choice of individual service or batch service. Transient results have been obtained for the first two moments of the system size distribution. Waiting time distribution is important in system evaluation and steady state results are obtained.