Simple,Copper(I)-Catalyzed Oxidation of Benzylic/Allylic Alcohols to Carbonyl Compounds: Synthesis of Functionalized Cinnamates in One Pot

An environmentally benign [Cu(I)]-catalyzed oxidation of activated (benzylic/allylic) alcohols to the corresponding carbonyl compounds is presented. Interestingly, the reaction was also compatible with benzylic alcohols containing ortho-bromo substituents on the aromatic ring without competing with the expected intermolecular Buchwald coupling. Significantly, the catalytic system enables the synthesis of cinnamate-esters in a sequential domino one-pot fashion via oxidation followed by Wittig–Horner protocol.     

Total synthesis of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide γ-butyrolactones

The first total synthesis of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide was achieved in a convergent pathway. The salient features of our synthesis include Ohira–Bestmann reaction, regioselective alkyne addition to terminal epoxide, TEMPO/BAIB mediated oxidative lactonization, and partial hydrogenation.     

An efficient synthesis of 3-(N-piperidinemethyl)-2,2,5,5-tetramethyl-1-oxy-3-pyrroline,a promising radioprotector for cancer radiotherapy

Nitroxides can ameliorate the toxic effects of radiation during cancer therapy. Nitroxides are paramagnetic and can be used in magnetic resonance imaging (MRI) and electron paramagnetic resonance imaging (EPRI) to monitor in vivo oxidative stress status. Compound 5 (3-(N-piperidinemethyl)-2,2,5,5-tetramethyl-1-oxy-3-pyrroline) was found to be the most effective nitroxide radioprotector. An efficient synthesis for this promising radioprotector was developed.     

Total synthesis of two γ-butyrolactone containing compounds (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide

The first total synthesis of (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide was accomplished using Jacobsen hydrolytic kinetic resolution, Ohira–Bestmann reaction, regioselective alkyne addition to terminal carbon atom of epoxide, intramolecular TEMPO/BAIB mediated oxidative lactonization and partial hydrogenation as the key steps.     

Ion beam irradiation of ZnS dispersed in PMMA and its photocatalytic application

ZnS nanoparticles implanted with 45 keV O⁵⁺ ion beam exhibited 83.6 % degradation of methyl blue in 2 h. This idea was utilized to fabricate nanocomposite system of ZnS and PMMA where ZnS nanoparticles were immobilized in PMMA film and irradiated with 45 keV O⁵⁺ ion beam at particle fluence of 2.5 × 10¹⁵, 1 × 10¹⁶ and 4 × 10¹⁶ particles/cm². These irradiated batches of ZnS nanoparticle immobilized in PMMA batches revealed formation of porous structure characterized by scanning electron microscopy and these batches exhibited 54 % photocatalytic degradation of methyl blue in 80 min which was higher as compared to the pristine ZnS nanoparticles.     

Thermal performance of stable SiO2 nanofluids and regression correlations to estimate their thermophysical properties

The present work investigates the best mix ratio of Glycerol in Water as a medium to prepare a stable nanofluid. Increasing the proportion of glycerol enhances the aqueous mix's dynamic viscosity and improves the prepared nanofluid's stability. The thermal conductivity and viscosity of the Glycerol and Water mixtures determination were undertaken at various Glycerol ratios. The best percentage of glycerol in the mixture is found to have the least amount of thermal conductivity loss and the optimum viscosity gain. Silica (SiO₂) nanofluid of 0.25%, 0.5%, 1%, and 1.5% weight concentrations was prepared with this optimal mixture of Glycerol and Water. The stability of these SiO₂ nanofluids is evaluated by determining the zeta potential at different time intervals. The nanofluids prepared were observed to be stable for one month. The thermal conductivity and viscosity of the nanofluids are measured between the temperature limits of 30°–70°C. A peak increment of 32.1%and 46.3% in thermal conductivity and viscosity is observed. Furthermore, when the percentage enhancement ratio (PER) and Mouromtseff ratio of these nanofluids is examined, it is observed that they have more excellent thermal performance at higher temperatures. Regression correlations are developed to estimate the thermal conductivity and viscosity of the prepared nanofluids with a maximum deviation of 9%.     

A simple and cost-effective synthesis of sulfated β-cyclodextrin and its application as chiral mobile phase additive in the separation of cloperastine enantiomers

Journal of Inclusion Phenomena and Macrocyclic Chemistry - A simple and cost-effective method for the synthesis of sulfated β-cyclodextrin, one of the most widely used chiral mobile phase...     

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.

     

Order-Unity 13C Nuclear Polarization of [1-13C]Pyruvate in Seconds and the Interplay of Water and SABRE Enhancement

Signal Amplification By Reversible Exchange in SHield Enabled Alignment Transfer (SABRE-SHEATH) is investigated to achieve rapid hyperpolarization of ¹³C₁ spins of [1-¹³C]pyruvate, using parahydrogen as the source of nuclear spin order. Pyruvate exchange with an iridium polarization transfer complex can be modulated via a sensitive interplay between temperature and co-ligation of DMSO and H₂O. Order-unity ¹³C (>50 %) polarization of catalyst-bound [1-¹³C]pyruvate is achieved in less than 30 s by restricting the chemical exchange of [1-¹³C]pyruvate at lower temperatures. On the catalyst bound pyruvate, 39 % polarization is measured using a 1.4 T NMR spectrometer, and extrapolated to >50 % at the end of build-up in situ. The highest measured polarization of a 30-mM pyruvate sample, including free and bound pyruvate is 13 % when using 20 mM DMSO and 0.5 M water in CD₃OD. Efficient ¹³C polarization is also enabled by favorable relaxation dynamics in sub-microtesla magnetic fields, as indicated by fast polarization buildup rates compared to the T₁ spin-relaxation rates (e. g., ∼0.2 s⁻¹ versus ∼0.1 s⁻¹, respectively, for a 6 mM catalyst-[1-¹³C]pyruvate sample). Finally, the catalyst-bound hyperpolarized [1-¹³C]pyruvate can be released rapidly by cycling the temperature and/or by optimizing the amount of water, paving the way to future biomedical applications of hyperpolarized [1-¹³C]pyruvate produced via comparatively fast and simple SABRE-SHEATH-based approaches.     

Spectral editing in solid-state MAS NMR of quadrupolar nuclei using selective satellite inversion

A sensitivity enhancement method based on selective adiabatic inversion of a satellite transition has been employed in a (pi/2)CT-(pi)ST1-(pi/2)CT spectral editing sequence to both enhance and resolve multisite NMR spectra of quadrupolar nuclei. In addition to a total enhancement of 2.5 times for spin 3/2 nuclei, enhancements up to 2.0 times is reported for the edited sites in a mixture of rubidium salts.