Stereoselective synthesis of highly O-functionalized enantiopure 2,3,4-trisubstituted tetrahydrofurans by tandem debenzylative cyclization of glycal derived 2,3-epoxy alcohols

A new and highly efficient methodology for the construction of synthetically important highly O-functionalized enantiopure 2,3,4-trisubstituted tetrahydrofurans with three contiguous stereocenters is reported.     

Alkylation of phenol: a mechanistic view

The current work utilizes the ab initio density functional theory (DFT) to develop a molecular level of the mechanistic understanding on the phenol alkylation in the presence of a cation-exchange resin catalyst, Amberlyst-15. The catalyst is modeled with the benzene sulfonic acid, and the effect of this acid on olefins such as isopropene (i-Pr) and tributene (t-Bu) in a phenol solution mimics the experimental condition. A neutral-pathway mechanism is established to account for early-stage high concentration of the phenolic ether observed in experiments. The mechanism involves an exothermic reaction between olefin and the benzene sulfonic acid to form ester followed by three reaction pathways leading to direct O-alkylation, o-C-alkylation, and p-C-alkylation. Our calculations conclude that O-alkylation to form the phenolic ether is the most energetically favorable in the neutral condition. An ionic rearrangement mechanism describes intramolecular migrations of the alkyl group from the phenolic ether to form C-alkylphenols, while the positively charged protonation significantly lowers transition barriers for these migrations. The ionic rearrangement mechanism accounts for high yields of o-C-alkylphenol and p-C-alkylphenol. Competition between the H atom and the alkyl R group at the substitutive site of the protonated ortho configuration is found to be the determining factor to the ortho/para ratio of C-alkylation products.     

Sol–gel derived nanocrystalline multiferroic BiFeO3 and R (R=Er and Tm) doped therein: Magnetic phase transitions and enhancement of magnetic properties

Nanocrystalline BiFeO₃ and rare earth ion doped BiFeO₃ (Bi_0.9R_0.1FeO₃, R=Er and Tm) were prepared by sol–gel method. Rietveld analysis of the X-ray diffractograms of the samples revealed that small amount of impurity phase of Bi₂Fe₄O₉ was formed together with the desired phase. In the thermal variation of magnetic mass susceptibility (χ_m) of the samples, one sharp transition below T_M (T_M∼100 K, 50 K and 30 K for BiFeO₃, Bi_0.9Er_0.1FeO₃ and Bi_0.9Tm_0.1FeO₃, respectively) was observed, which clearly hint the change of the domination of the ferromagnetic exchange interaction over the usual antiferromagnetic exchange interaction. Also, static magnetization (M) and susceptibility of each doped sample have been drastically enhanced compared to that of BiFeO₃. The values of χ_m and M measured at different temperatures confirmed that the magnetic behavior of the doped systems has been dominated by the paramagnetic/ferromagnetic clusters below ∼T_M. Another phase transition were observed in the χ_m vs. T curve of the samples at relatively higher temperature T_B (∼260 K for BiFeO₃, ∼220 K for Bi_0.9Er_0.1FeO₃ and ∼180 K for Bi_0.9Tm_0.1FeO₃), which may be attributed to the charge ordering transition. Ferroelectric hysteresis loops of the samples observed at 100 Hz confirmed the presence of ferroelectric ordering of the samples. Measured values of dielectric constants at 1 kHz of each sample in presence and absence of magnetic field confirmed a substantial magnetoelectric coupling of all the samples.     

1,2,3-Triazolyl-tetrahydropyrimidine Conjugates as Potential Sterol Carrier Protein-2 Inhibitors: Larvicidal Activity against the Malaria Vector Anopheles arabiensis and In Silico Molecular Docking Study

Alteration of insect growth regulators by the action of inhibitors is becoming an attractive strategy to combat disease-transmitting insects. In the present study, we investigated the larvicidal effect of 1,2,3-triazolyl-pyrimidinone derivatives against the larvae of the mosquito Anopheles arabiensis, a vector of malaria. All compounds demonstrated insecticidal activity against mosquito larvae in a dose-dependent fashion. A preliminary study of the structure–activity relationship indicated that the electron-withdrawing substituent in the para position of the 4-phenyl-pyrimidinone moiety enhanced the molecules’ potency. A docking study of these derivatives revealed favorable binding affinity for the sterol carrier protein-2 receptor, a protein present in the intestine of the mosquito larvae. Being effective insecticides against the malaria-transmitting Anopheles arabiensis, 1,2,3-triazole-based pyrimidinones represent a starting point to develop novel inhibitors of insect growth regulators.     

Harnessing Deep Neural Networks to Analyze Multi-Channel Anion Sensing Characteristics of a Ru(II)-Pyrazolyl-Bis(Benzimidazole) Complex

In this work, the anion-responsive conduct of a Ru(II)-bipyridine complex incorporating pyrazolyl-bis (benzimidazole) ligand is thoroughly investigated in acetonitrile and water via absorption and emission spectroscopy as well as by square-wave voltammetry (SWV). Substantial alteration of the photo-redox behavior of the complex is observed in the presence of the selected anions. The free form of the complex exhibits emission indicating the “on-state”, while inclusion of anions leads to quenching of emission and represents the “off-state”. The restoration of the initial state of the complex is feasible in the presence of acid and the process is reversible and can be recycled. In essence, the complex functions as anion- and acid-responsive molecular switches. Additionally, we applied herein neural network based deep learning methodologies, viz. Artificial Neural Networks (ANNs) and Adaptive Neuro-Fuzzy Inference System (ANFIS)} for thorough analysis and fully understand the multi-channel anion sensing behavior of the complex.