An organocatalytic direct Mannich-cyclization cascade as [3+2] annulation: asymmetric synthesis of 2,3-substituted pyrrolidines

A new method for asymmetric synthesis of 2,3-substituted pyrrolidines from N-PMP aldimines and succinaldehyde via formal [3+2] cycloaddition is reported. This reaction involves proline catalyzed direct Mannich reaction and acid catalyzed reductive cyclization with high yields (up to 78%) and excellent enantioselectivities (up to >99%).     

Fluorogenic sensing of CH3CO2- and H2PO4- by ditopic receptor through conformational change

Cyclo-bis-(urea-3,6-dichlorocarbazole) (1) forms a 1 : 2 complex with CH(3)CO(2)(-) and H(2)PO(4)(-) through hydrogen bonding with the two urea moieties, resulting in fluorescence enhancement via a combined photoinduced electron transfer (PET) and energy transfer mechanism. The binding mechanism involves a conformational change of the two urea receptors to a trans orientation after binding of the first anion, which facilitates the second interaction.     

Photodamage and Photoprotection: An In vivo Approach Using Noninvasive Probes

Solar radiations trigger the physiological alteration in skin which progress toward photoaging. Sunscreens are known to be effective against the photodamaging effects of sunlight. The purpose of this study was to evaluate the extent to which aging signs caused by real‐life sunlight exposure could be avoided by comparing various parameters between sun‐exposed and sun‐protected skin using noninvasive probes. Female volunteers (n = 11) after getting their consent were provided with marketed sunscreen product to apply onto their skin for 6 months. Measurements were scheduled every 15 days from the baseline reading for 6 months. Cutometer, Mexameter and Corneometer were used for evaluation of facial skin parameters. Clinical evaluations showed the effects of sunlight exposure on different skin parameters by comparing sun‐protected and unprotected skin, where Gross elasticity (R2), Net elasticity (R5), Viscoelasticity (R6) and Biological elasticity (R7) showed insignificant results, while Hydration, Melanin and Erythema showed significant results. Sun‐exposed skin presented 0.72%, 0.66%, 0.77%, 1.39%, 1.99%, 2.01% and 3.15% changes in R2, R5, R6 and R7, melanin, erythema and hydration, respectively, which were potentially prevented by sunscreen application. Premature aging is inhibited by following photoprotective regimen on routine basis, emphasizing the potential benefit of sunscreen against early aging signs.     

Attachment of 4-methoxy benzyl units to a tripodal fluoroionophore shows reversal of output functionality with Cu(II) input

Syntheses of three tris-(2-aminoethyl)amine, tren based tripodal fluoroionophores (L₂, L₃, and L₅), are reported. These fluoroionophores are designed based on the fluorophore–spacer–receptor format (choice of fluorophore in all three cases is anthryl unit). In L₂, three anthracene moieties are attached to the three arms of tren via –CH₂-spacer whereas L₃ and L₅ have p-nitro benzyl and p-methoxy benzyl substitutions, respectively, on L₂, which are in close proximity to the photoinduced electron transfer (PET) center. All three fluoroionophores show appreciably lower fluorescence compared to anthracene due to effective PET process in these systems but the quantum yield varies depending upon the nature of substitution at the PET center. In the cases of L₂ and L₅ different amounts of fluorescence recovery are observed in the presence of different cation inputs whereas L₃ is almost inactive toward cation sensing. Detailed fluorescence emission studies on L₂ and L₅ in the presence of different cation inputs showed that L₅ having N4 donor sets bearing three p-methoxy benzyl units attached to the three nitrogen centers involving photoinduced electron transfer process is a viable candidate for enhancement of fluorescence with Cu(II) input. In the absence of p-methoxy benzyl units at the nitrogen centers' resulting system, L₂ shows quenching of fluorescence with the Cu(II) under same experimental conditions.     

Development of a fast and efficient CE enzyme assay for the characterization and inhibition studies of α‐glucosidase inhibitors

The inhibition of the α‐glucosidase enzyme plays an important role in the treatment of diabetes mellitus. We have established a highly sensitive, fast, and convenient CE method for the characterization of the enzyme and inhibition studies of α‐glucosidase inhibitors. The separation conditions were optimized; the pH value and concentration of the borate‐based separation buffer were optimized in order to achieve baseline separation of p‐nitrophenyl‐α‐d ‐glucopyranoside and p‐nitrophenolate. The optimized method using 25 mM tetraborate buffer, pH 9.5, was evaluated in terms of repeatability, LOD, LOQ, and linearity. The LOD and LOQ were 0.32 and 1.32 μM for p‐nitrophenyl‐α‐d ‐glucopyranoside and 0.83 and 3.42 μM for p‐nitrophenolate, respectively. The value of the Michaelis–Menten constant (K_m) determined for the enzyme is 0.61 mM, which is in good agreement with the reported data. The RSDs (n = 6) for the migration time was 0.67 and 1.83% for substrate and product, respectively. In the newly established CE method, the separation of the reaction analytes was completed in <4 min. The developed CE method is rapid and simple for measuring enzyme kinetics and for assaying inhibitors.     

Process optimisation for the biosynthesis of cellulase by Bacillus PC-BC6 and its mutant derivative Bacillus N3 using submerged fermentation

This study deals with optimisation of cultural conditions for enhanced production of cellulase by Bacillus PC-BC6 and its mutant derivative Bacillus N3. Influence of different variables including incubation time, temperature, inoculum size, pH, nitrogen sources and metal ions has been studied. The optimum conditions for cellulase production were incubation period of 72 h, inoculum size 4% incubation temperature 37°C, pH 7, 0.25% ammonium sulphate, 0.2% peptone as inorganic and organic nitrogen source in case of Bacillus PC-BC6. In case of mutant Bacillus N3, optimal conditions were incubation period of 48 h, incubation temperature 37°C, inoculum size 3%, pH 7, 0.2% ammonium chloride and 0.15% yeast extract. Presence of MnSO₄ and CaCl₂ enhances the enzyme production by Bacillus PC-BC6 and mutant Bacillus N3, respectively. This study was innovative and successful in producing cellulase economically by using cheap indigenous substrate Saccharum spontaneum.     

Binder-Free Fabrication of Prussian Blue Analogues Based Electrocatalyst for Enhanced Electrocatalytic Water Oxidation

Developing a cost-effective, efficient, and stable oxygen evolution reaction (OER) catalyst is of great importance for sustainable energy conversion and storage. In this study, we report a facile one-step fabrication of cationic surfactant-assisted Prussian blue analogues (PBAs) M_x[Fe(CN)₅CH₃C₆H₄NH₂]∙yC₁₉H₃₄NBr abbreviated as SF[Fe-Tol-M] (where SF = N-tridecyl-3-methylpyridinium bromide and M = Mn, Co and Ni) as efficient heterogeneous OER electrocatalysts. The electrocatalysts have been characterized by Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX) analysis, and X-ray photoelectron spectroscopy (XPS). In the presence of cationic surfactant (SF), PBAs-based electrodes showed enhanced redox current, high surface area and robust stability compared to the recently reported PBAs. SF[Fe-Tol-Co] hybrid catalyst shows superior electrochemical OER activity with a much lower over-potential (610 mV) to attain the current density of 10 mA cm⁻² with the Tafel slope value of 103 mV·dec⁻¹ than that for SF[Fe-Tol-Ni] and SF[Fe-Tol-Mn]. Moreover, the electrochemical impedance spectroscopy (EIS) unveiled that SF[Fe-Tol-Co] exhibits smaller charge transfer resistance, which results in a faster kinetics towards OER. Furthermore, SF[Fe-Tol-Co] offered excellent stability for continues oxygen production over extended reaction time. This work provides a surface assisted facile electrode fabrication approach for developing binder-free OER electrocatalysts for efficient water oxidation.     

A Haar wavelets based approximation for nonlinear inverse problems influenced by unknown heat source

In this discussion, a new numerical algorithm focused on the Haar wavelet is used to solve linear and nonlinear inverse problems with unknown heat source. The heat source is dependent on time and space variables. These types of inverse problems are ill-posed and are challenging to solve accurately. The linearization technique converted the nonlinear problem into simple nonhomogeneous partial differential equation. In this Haar wavelet collocation method (HWCM), the time part is discretized by using finite difference approximation, and space variables are handled by Haar series approximation. The main contribution of the proposed method is transforming this ill-posed problem into well-conditioned algebraic equation with the help of Haar functions, and hence, there is no need to implement any sort of regularization technique. The results of numerical method are efficient and stable for this ill-posed problems containing different noisy levels. We have utilized the proposed method on several numerical examples and have valuable efficiency and accuracy.     

Polypropylene/carbon nanotube magnetic composites obtained using carbon nanotubes from sawdust

Magnetic polypropylene (PP) nanocomposites with different loadings (from 0.5 to 20 wt %) of carbon nanotubes with iron (CNT‐Fe) were fabricated using the melt‐mixing method. The carbon nanotubes were synthesized by pyrolysis of sawdust from the furniture industry. The morphological characterization shows homogenous dispersion of the filler in the polymer matrix. The addition of only 0.5 wt % CNT‐Fe already results in ferromagnetic behavior in the diamagnetic polymer matrix. The thermal properties were investigated using thermogravimetric analysis and differential scanning calorimetry. The results show an increase in the maximum degradation, crystallization, and melting temperatures of the nanocomposites compared with neat PP. The nanocomposites showed improvement in terms of mechanical and oxygen permeability properties. A very significant result of the work is the high remnant magnetization and coercivity values of the nanocomposites at room temperature whereas most of the works on similar systems show magnetic properties only at very low temperatures.     

A gas-phase kinetic study on the thermal decomposition of 2-chloropropene

The gas-phase thermal decomposition of 2-chloropropene in the presence of a radical inhibitor was studied in the temperature range of 668.2–747.2 K and pressure between 11–76 Torr using the conventional static system. The dehydrochlorination to propyne and HCl was the only reaction channel and accounted for >98% of the reaction. The formation of propyne was found to be homogeneous and unimolecular and follows a first-order rate law. The observed rate coefficient is expressed by the following Arrhenius equation: $$ k_{total} = 10^{13.05 \pm 0.46} (s^{ - 1} )\exp ^{ - 242.6 \pm 6.2({{kJ} \mathord{\left/ {\vphantom {{kJ} {mol}}} \right. \kern-\nulldelimiterspace} {mol}})/RT} . $$ The hydrogen halide elimination is believed to proceed through a semipolar four-membered cyclic transition state. The presence of a methyl group on the α-carbon atom lowered the activation energy by 47 kJ mol^?1. The experimentally observed pressure dependence of the rate constant is compared with the theoretically predicted values that are obtained by RRKM calculations.