Oxidative Esterification of Benzaldehyde and Deactivated Aromatic Aldehydes with N-Bromosuccinimide-pyridine

Whereas the oxidative esterification of benzaldehyde to methyl benzoate with N-bromosuccinimide (NBS)-pyridine requires dark conditions and 5 equivalents each of NBS and K₂CO₃ and gave only moderate yield (52%) of the product (McDonald et al. J. Org. Chem. 1989, 54, 1213), simple change of base to pyridine gave the desired product in 83% gas chromatographic yield with only 1 equivalent each of NBS and pyridine. Moreover, the reaction could be conducted without exclusion of light. Aromatic aldehydes bearing electron-withdrawing substituents at meta/para position yielded the corresponding methyl esters in still better yields.

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Galactose-Grafted 2D Nanosheets from the Self-Assembly of Amphiphilic Janus Dendrimers for the Capture and Agglutination of Escherichia coli

High aspect ratio, sugar-decorated 2D nanosheets are ideal candidates for the capture and agglutination of bacteria. Herein, the design and synthesis of two carbohydrate-based Janus amphiphiles that spontaneously self-assemble into high aspect ratio 2D sheets are reported. The unique structural features of the sheets include the extremely high aspect ratio and dense display of galactose on the surface. These structural characteristics allow the sheet to act as a supramolecular 2D platform for the capture and agglutination of E. coli through specific multivalent noncovalent interactions, which significantly reduces the mobility of the bacteria and leads to the inhibition of their proliferation. Our results suggest that the design strategy demonstrated here can be applied as a general approach for the crafting of biomolecule-decorated 2D nanosheets, which can perform as 2D platforms for their interaction with specific targets.     

Integrating CuO−Fe2O3 Nanocomposites and Supramolecular Assemblies of Phenazine for Visible‐Light Photoredox Catalysis

A photoredox catalytic ensemble consisting of CuO‐Fe₂O₃ nanocomposites and oligomeric derivative of phenazine has been developed. The prepared system acts as an efficient photoredox catalyst for C?N bond formation reaction via SET mechanism under ‘green’ conditions (aerial environment, mixed aqueous media, recyclable), requiring less equivalents of base and amine substrate. The present study demonstrates the significant role of supramolecular assemblies as photooxidants and reductants upon irradiation and their important contribution towards the activation of the metallic centre through energy transfer and electron transfer pathways. The potential of oligomer 4 : CuO‐Fe₂O₃ has also been explored for C?C bond formation reactions via the Sonogashira protocol.     

Photocatalytic degradation of azo dyes using Zn-doped and undoped TiO2 nanoparticles

Undoped and Zn-doped TiO₂ nanoparticles were synthesized by the sol gel method. The dopant (Zn) was taken at 0.1, 0.2, 0.5, 0.7, and 1.0 mol%. The initial precursors were titanium tetraisopropoxide and zinc acetate. The samples were characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and UV–vis diffuse reflectance. The photocatalytic activity of the prepared nanoparticles was studied by observing their role in degradation of two azo dyes, i.e., Eriochrome Black T and Methyl Red under UV–visible light. The results revealed that Zn-doped TiO₂ nanoparticles exhibited better degradation as compared to undoped TiO₂ nanoparticles. In this study, 0.7 mol% Zn-doped TiO₂ showed highest photocatalytic activity. Doping of Zn allowed better separation of electron–hole pairs which results in increased oxidation and reduction reactions.     

Hybrid inorganic–organic poly(carborane‐siloxane‐arylacetylene) structural isomers with in‐chain aromatics: Synthesis and properties

Structural isomers of thermo‐oxidatively stable poly(carborane‐siloxane‐arylacetylene) (PCSAA), namely, m‐PCSAA and p‐PCSAA, were synthesized by the reaction of the dimagnesium salts of m‐diethynylbenzene or p‐diethynylbenzene with 1,7‐bis(chlorotetramethyldisiloxyl)‐m‐carborane. The developed polymers have exceptional thermo‐oxidative properties similar to their diacetylene counterpart poly(carborane‐siloxane‐acetylene), PCSA. Thermal treatment of either of the PCSAAs results in a fully crosslinked thermoset by 500 °C resulting from the cycloaddition reactions involving the acetylene and aryl functionalities and subsequent formation of bridging disilylmethylene entities as discerned from Fourier transform infrared, ¹³C and ²⁹Si solid‐state NMR, and XPS studies. X‐ray diffraction analysis revealed that the thermosets obtained from p‐PCSAA possess enhanced crystallinity when compared to that obtained from m‐PCSAA possibly due to more efficient packing interactions of the p‐diethynylbenzene groups during thermoset formation. The presence of the aryl groups in the backbone of the PCSAAs' chains appeared to have enhanced the storage and bulk moduli of their thermosets when compared to the thermoset of PCSA. Dielectric studies of m‐PCSAA and p‐PCSAA revealed segmental relaxation peaks, α, above their glass transition temperatures with p‐PCSAA exhibiting a broader peak with a slower relaxation rate than m‐PCSAA. © 2013 Wiley Periodicals, Inc.^? J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2638–2650     

MASS SPECTROMETRIC FRAGMENTATION OF UNSYMMETRICALLY SUBSTITUTED METHYLPHOSPHONATE DIESTERS

Abstract

A series of structurally related unsymmetrically substituted methylphosphonate diesters have been synthesised and subjected to electron impact (El) mass spectral studies. These studies though aimed at total identification of the compounds, resulted in certain interesting observations and hence are being reported. In order to confirm the observations under electron impact and to support the mechanism of fragmentation we have also performed MSNS experiments in both daughter ion and parent ion modes.     

Study of the Release Mechanism of Terminalia chebula Extract from Nanoporous Silica Gel

Sol/gel-derived silica gel was prepared at room temperature from tetraethyl orthosilicate precursor. The extracts of Terminalia chebula (Haritoki) were entrapped into the porous silica gel. Fourier transform infrared analysis revealed the proper adsorption of herbal values in the nanopores of the silica gel. Porosity was estimated by transmission electron microscope studies. The release kinetics of the extract in both 0.1 N HCl, pH 1.2, and Phosphate-buffer saline (PBS), pH 7.2, were determined using UV–Vis spectroscopy. Different dissolution models were applied to release data in order to evaluate the release mechanisms and kinetics. Biphasic release patterns were found in every formulation for both the buffer systems. The kinetics followed a zero-order equation for first 4 h and a Higuchi expression in a subsequent timeline in the case of 0.1 N HCl. In the case of PBS, the formulations showed best linearity with a first-order equation followed by Higuchi’s model. The sustained release of the extract predominantly followed diffusion and super case II transport mechanism. The release value was always above the minimum inhibitory concentration.