Synthesis of Benzoxazoles Catalyzed by MCM-41, a Green and Reusable Catalyst

Benzoxazoles can be rapidly and efficiently synthesized from acyl chloride with 2-aminophenols in one simple step, which provided a practical and efficient method for high-throughput synthesis of this important class of heterocyclic compounds.     

Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle

Spherical assemblies of the type [Pd_nL_2n]²ⁿ⁺ can be obtained from Pd^II salts and curved N-donor ligands, L. It is well established that the bent angle, α, of the ligand is a decisive factor in the self-assembly process, with larger angles leading to complexes with a higher nuclearity, n. Herein, we report heteroleptic coordination cages of the type [Pd_nL_nL′_n]²ⁿ⁺, for which a similar correlation between the ligand bent angle and the nuclearity is observed. Tetranuclear cages were obtained by combining [Pd(CH₃CN)₄](BF₄)₂ with 1,3-di(pyridin-3-yl)benzene and ligands featuring a bent angle of α=120°. The use of a dipyridyl ligand with α=149° led to the formation of a hexanuclear complex with a trigonal prismatic geometry; for linear ligands, octanuclear assemblies of the type [Pd₈L₈L′₈]¹⁶⁺ were obtained. The predictable formation of heteroleptic Pd^II cages from 1,3-di(pyridin-3-yl)benzene and different dipyridyl ligands is evidence that there are entire classes of heteroleptic cage structures that are privileged from a thermodynamic point of view.     

Radiochromic Hydrogen-Bonded Organic Frameworks for X-ray Detection

Porous materials have been investigated as efficient photochromic platforms for detecting hazardous radiation, while the utilization of hydrogen bonded organic frameworks (HOFs) in this field has remained intact. Herein, two HOFs were synthesized through self-assembly of tetratopic viologen ligand and formic acid (PFC-25, PFC-26), as a new class of “all-organic” radiochromic smart material, opening a gate for HOFs in this field. PFC-26 is active upon both X-ray and UV irradiation, while PFC-25 is only active upon X-ray irradiation. The same building block yet different radiochromic behaviors of PFC-25 and PFC-26 allow us to gain a deep mechanistic understanding of the factors that control the detection specificity. Theoretical and experimental studies reveal that the degree of π-conjugation of viologen ligand is highly related to the threshold energy of triggering a charge transfer, therefore being a vital factor for the particularity of radiochromic materials. Thanks to its convenient processibility, nanoparticle size, and UV silence, PFC-25 can be further fabricated into a portable naked-eye sensor for X-ray detection, which shows obvious color change with the merits of high transmittance contrast, good sensitivity (reproducible dose threshold of 3.5 Gy), and excellent stability. The work exhibits the promising practical potentials of HOF materials in photochromic technology.     

Application of Net Analyte Signal Standard Addition Method (NASSAM) for Simultaneous Determination of Lead and Tin by Differential Pulse Polarography

Differential pulse polarography was used for simultaneous determination of Sn²⁺ and Pb²⁺. But there is a problem for simultaneous determination and it is high overlapped DPPs of mentioned cations that their determination is impossible in the presence of each other, so multivariate calibration methods as chemomatrics methods were used for this determination. There are some disadvantageous for multivariate calibration methods that can be solved by a new and simple method called net analyte signal standard addition method. This method has some advantages, such as: the use of a full voltammogram, realization in a single step, therefore it does not require calibration and prediction steps and only a few measurements are required for the determination.     

Separation of glucose and pentose sugars by selective enzyme hydrolysis of AFEX-treated corn fiber

A process was developed to fractionate corn fiber into glucose- and pentose-rich fractions. Corn fiber was ammonia fiber explosion treated at 90 degrees C, using 1 g anhydrous ammonia pergram of drybiomass, 60% moisture, and 30-min residence time. Twenty four hour hydrolysis of ammonia fiber explosion-treated corn fiber with cellulase converted 83% of available glucanto-glucose. In this hydrolysis the hemicellulose was partially broken down with 81% of the xylan and 68% of the arabinan being contained in the hydrolysate after filtration to remove lignin and other insoluble material. Addition of ethanol was used to precipitate and recover the solubilized hemicellulose from the hydrolysate, followed by hydrolysis with 2% (v/v) sulfuric acid to convert the recovered xylan and arabinan to monomeric sugars. Using this method, 57% of xylose and 54% of arabinose available in corn fiber were recovered in a pentose-rich stream. The carbohydrate composition of the pentose-enriched stream was 5% glucose, 57% xylose, 27% arabinose, and 11% galactose. The carbohydrate composition of the glucose-enriched stream was 87% glucose, 5% xylose, 6% arabinose, and 1% galactose, and contained 83% of glucose available from the corn fiber.     

Cauliflower‐like NiCo2O4−Zn/Al Layered Double Hydroxide Nanocomposite as an Efficient Electrochemical Sensing Platform for Selective Pyridoxine Detection

In the present study, a cauliflower‐like NiCo₂O₄?Zn/Al layered double hydroxide (NiCo₂O₄?Zn/Al LDH) nanocomposite was used as a novel electrode material for the sensitive and selective determination of pyridoxine (vitamin B₆). The structure and morphology of the as‐prepared nanocomposite were characterized by X‐ray diffraction (XRD), FT‐IR, field emission scanning electron microscopy (FESEM) and energy dispersive X‐ray spectroscopy (EDX). The NiCo₂O₄?Zn/Al LDH nanocomposite exhibited excellent electrocatalytic ability in the oxidation of pyridoxine, which could result from the synergistic effect of the two components. The developed sensor also provided a selective determination of pyridoxine in the presence of other species such as vitamins (B₁, B₂, B₁₂ and ascorbic acid), inorganic ions and biomolecules. The fabricated sensor showed a good linear response for pyridoxine over the concentration ranges 2×10^?7–2.0×10^?4 mol L^?1 with a low detection limit of 8.6×10^?8 mol L^?1. Finally, the proposed method was successfully applied for the determination of pyridoxine in commercial tablets and plasma samples with satisfactory results. Furthermore, this novel sensor displayed superior benefits in terms of stability, sensitivity, repeatability and cost. The present work aims to expand NiCo₂O₄ based nanocomposites to sensor fields and promote the development of pyridoxine sensors.     

Electron spin resonance spectra of nitrogen heterocyclic radical ions

Abstract

We introduce a representative benchmark database of 20 cycloreversion reaction energies obtained by means of the high-level W1 thermochemical protocol. We use these benchmark values to assess the performance of a variety of contemporary DFT, double-hybrid DFT (DHDFT), standard ab initio, and compound thermochemistry methods. We show that this set of reaction energies provides an extremely challenging test for nearly all of the considered DFT and DHDFT methods. For example, about 80% of the considered functionals result in root-mean-square deviations (RMSDs) above 10 kJ mol^?1. The best DFT and DHDFT procedures are ωB97X and DSD-PBEP86-D3, with RMSDs of 4.7 and 7.9 kJ mol^?1, respectively. Coupled with the fact that the barrier heights for these reactions also pose a significant challenge for many DFT methods, this work shows that only a handful of functionals can quantitatively describe all aspects of the potential energy surface of this important class of reactions. In addition, this work shows that London dispersion effects are particularly large for this class of reactions. For example, empirical D3 dispersion corrections reduce the RMSDs for the DFT and DHDFT procedures by amounts ranging from 3.5 (PBE and B2K-PLYP) to 22.0 (BLYP) kJ mol^?1.     

Synthesis,tautomeric stability,spectroscopy and computational study of a potential molecular switch of (Z)-4-(phenylamino)pent-3-en-2-one

The (Z)-4-(phenylamino) pent-3-en-2-one (PAPO) was synthesised applying carbon-based solid acid and described by experimental techniques. Calculated results reveal that its keto-amine form is more stable than its enol-imine form. A relaxed potential energy surface scan has been accomplished based on the optimised geometry of NH tautomeric form to depict the potential energy barrier related to intramolecular proton transfer. The spectroscopic results and theoretical calculations demonstrate that the intramolecular hydrogen bonding strength of PAPO is stronger than that in 4-amino-3-penten-2-one)APO(. In addition, molecular electrostatic potential, total and partial density of stats (TDOS, PDOS) and non-linear optical properties of the compound were studied using same theoretical calculations. Our calculations show that the title molecule has the potential to be used as molecular switch.     

Multi-objective optimization of pin fin to determine the optimal fin geometry using genetic algorithm

In this study, one dimensional heat transfer in a pin fin is modeled and optimized. We used Bezier curves to determine the best geometry of the fin. The model equations are solved to analyze the heat transfer. Total heat transfer rate and fin efficiency factor are considered as two objective functions and multi-objective optimization carried out to maximize heat transfer rate and fin efficiency simultaneously. Fast and elitist non-dominated sorting genetic algorithm (NSGA-II) is used to determine a set of multiple optimum solutions, called ‘Pareto optimal solutions. The optimized results are presented with Pareto front which demonstrate conflict between two objective functions in the optimized point, both energy conservation and thermal analysis are carried out to verify the solution method and the results shows good precision.     

Efficient One‐Pot Synthesis of β‐Acetamido Carbonyl Compounds Using Fe3O4 Nanoparticles

A new, one‐pot condensation of aldehydes, enolizable ketones and esters, AcCl, and MeCN, in the presence of Fe₃O₄ nanoparticles (nano‐Fe₃O₄) as an efficient catalyst, for the preparation of β‐acetamido carbonyl compounds at room temperature is described.