Transient states in [2 + 2] photodimerization of cinnamic acid: correlation of solid-state NMR and X-ray analysis

13C-CPMAS and other solid-state NMR methods have been applied to monitor the solid-state reactions of trans-cinnamic acid derivatives, which are the pioneer and model compounds in the field of topochemistry previously studied by X-ray diffraction, AFM, and vibrational spectroscopy. Single-crystal X-ray analyses of photoirradiated alpha-trans-cinnamic acid where the monomers are arranged in a head-to-tail manner have revealed the formation of a centrosymmetric alpha-truxillic acid photodimer. For a centrosymmetric dimer, however, two cyclobutane carbon signals and one carbonyl carbon signal were expected apart from other aromatic carbon signals. Instead, four cyclobutane and two carbonyl carbon signals were observed suggesting the formation of a non-centrosymmetric photodimer. Removing hydrogen bonds from the system by esterfication of alpha-truxillic acid yield a centrosymmetric photodimer. Careful analysis of the obtained products via solid-state NMR clearly showed that the observed peak splittings in the 13C-CPMAS spectra did not originate from packing effects but rather result from asymmetric hydrogen bonds distorting the local symmetry. Further evidence of this rather dynamic hydrogen-bonding stems from high-temperature X-ray data revealing that only the joint approach of both X-ray analysis and solid-state NMR at similar temperatures allows for the successful characterization of dynamic processes occurring in topochemical reactions, thus, providing detailed insight into the reaction mechanism of organic solid-state transformations.     

Rapid preparative isolation of erythrocentaurin from Enicostemma littorale by medium‐pressure liquid chromatography,its estimation by high‐pressure thin‐layer chromatography,and its α‐amylase inhibitory activity

Erythrocentaurin is a relatively simple natural product present among the members of Gentianaceae. A preparative method for the isolation of erythrocentaurin from the ethyl acetate fraction of Enicostemma littorale using medium‐pressure liquid chromatography has been reported. The method consisted of a simple step gradient from 10 to 20% ethyl acetate in n‐hexane. Using a 70 × 460 mm Si60 column, this method is capable of processing 20 g of material in <3 h (purity ≈ 97%). The recovery of erythrocentaurin was 87.77%. Estimation of erythrocentaurin in extracts and fractions based on high‐pressure thin‐layer chromatography was carried out on silica gel 60 F₂₅₄ plates with toluene/ethyl acetate/formic acid (80:18:2 v/v/v) as the mobile phase. The densitometric analysis was performed at 230 nm. A well‐separated compact band of erythrocentaurin appeared at R_f 0.54 ± 0.04. The analytical method showed good linearity in the concentration range of 200–1500 ng/band with a correlation coefficient of 0.99417. The limits of detection and quantification were found to be ≈60 and ≈180 ng/band, respectively. Erythrocentaurin exhibited a concentration‐dependent α‐amylase inhibition (IC₅₀ 1.67 ± 0.28 mg/mL). The outcome of the study should be considered for pharmacokinetic and biotransformation studies involving E. littorale.     

An HPTLC Method for the Simultaneous Analysis of Compactin and Citrinin in Penicillium citrinum Fermentation Broth

JPC – Journal of Planar Chromatography – Modern TLC - A simple and precise high-performance thin-layer chromatographic (HPTLC) method has been established for simultaneous analysis of...     

Existence and uniqueness of solutions for multi-point boundary value problems for fractional differential equations

In this work, we investigate existence and uniqueness of solutions for a class of nonlinear multi-point boundary value problems for fractional differential equations. Our analysis relies on the Schauder fixed point theorem and the Banach contraction principle.     

Origin of Electric Field Dependence of the Charge Mobility and Spatial Energy Correlations in C60-Based Field Effect Transistors

We report on the influence of the lateral electric field on the charge mobility in organic field-effect transistors (OFET) based on C₆₀ films with multigrain morphology. The experimental data were quantitatively described using a recent analytical model by accounting for the strong local electric fields in a multigrain transistor channel and for the energy correlation effects. To rationalize the presence of a correlated disorder in a non-polar C₆₀ material, we show that randomly oriented permanent dipoles in organic gate dielectric layers can generate a significant dipolar disorder in an adjacent nonpolar semiconductor layer.     

Green Synthesized ZnO Nanoparticles as Biodiesel Blends and Their Effect on the Performance and Emission of Greenhouse Gases

Pollution and global warming are a few of the many reasons for environmental problems, due to industrial wastes and greenhouse gases, hence there are efforts to bring down such emissions to reduce pollution and combat global warming. In the present study, zinc oxide nanoparticles are green synthesized using cow dung as fuel, through combustion. Synthesized material was characterized by FTIR, XRD, UV, and FESEM. The as-prepared ZnO-GS NPs were employed as a transesterification catalyst for the preparation of biodiesel from discarded cooking oil. The biodiesel obtained is termed D-COME (discarded cooking oil methyl ester), which is blended with 20% commercial diesel (B20). Additionally, this blend, i.e., B20, is further blended with varying amounts of as-prepared ZnO-GS NPs, in order to ascertain its effects on the quality of emissions of various greenhouse gases such as hydrocarbons, CO_x, NO_x. Moreover, the brake thermal efficiency (BTHE) and brake specific fuel consumption (BSFC) were studied for their blends. The blend (B20) with 30 mg of ZnO-GS, i.e., B20-30, displays the best performance and reduced emissions. Comparative studies revealed that the ZnO-GS NPs are as efficient as the ZnO-C NPs, indicating that the green synthetic approach employed does not affect the efficiency of the ZnO NPs.     

A numerical method for solving boundary value problems for fractional differential equations

A numerical scheme, based on the Haar wavelet operational matrices of integration for solving linear two-point and multi-point boundary value problems for fractional differential equations is presented. The operational matrices are utilized to reduce the fractional differential equation to system of algebraic equations. Numerical examples are provided to demonstrate the accuracy and efficiency and simplicity of the method.     

Straightforward Synthesis of Mn3O4/ZnO/Eu2O3-Based Ternary Heterostructure Nano-Photocatalyst and Its Application for the Photodegradation of Methyl Orange and Methylene Blue Dyes

Zinc oxide-ternary heterostructure Mn₃O₄/ZnO/Eu₂O₃ nanocomposites were successfully prepared via waste curd as fuel by a facile one-pot combustion procedure. The fabricated heterostructures were characterized utilizing XRD, UV–Visible, FT-IR, FE-SEM, HRTEM and EDX analysis. The photocatalytic degradation efficacy of the synthesized ternary nanocomposite was evaluated utilizing model organic pollutants of methylene blue (MB) and methyl orange (MO) in water as examples of cationic dyes and anionic dyes, respectively, under natural solar irradiation. The effect of various experimental factors, viz. the effect of a light source, catalyst dosage, irradiation time, pH of dye solution and dye concentration on the photodegradation activity, was systematically studied. The ternary Mn₃O₄/ZnO/Eu₂O₃ photocatalyst exhibited excellent MB and MO degradation activity of 98% and 96%, respectively, at 150 min under natural sunlight irradiation. Experiments further conclude that the fabricated nanocomposite exhibits pH-dependent photocatalytic efficacy, and for best results, concentrations of dye and catalysts have to be maintained in a specific range. The prepared photocatalysts are exemplary and could be employed for wastewater handling and several ecological applications.     

Morphology dependent dispersion of third-order optical nonlinear susceptibility in TiO2

Nanostructured TiO₂ in different shapes such as nanosheet, nanowire, and nanoflower, as well as nanosphere have been prepared and characterized. Nonlinear optical (NLO) properties were measured at 532 nm using open and closed aperture Z-scan technique with respect to the shape. NLO behaviour of the nanostructured TiO₂ is found to be shape dependent in suspensions at the investigated wavelengths and is accounted in terms of effective surface-to-volume ratio of the structures. The values of different optical constants viz, β,n ₂,χ ⁽³⁾ for different morphological structures were evaluated and compared. The optical limiting thresholds of the samples were also investigated and it is found to decrease with increase in the net light matter interaction area of the sample.