Synthesis of Copper-Based Nanostructures in Liquid Environments by Means of a Non-equilibrium Atmospheric Pressure Nanopulsed Plasma Jet

The influence of the liquid composition on the chemical and morphological properties of copper-based nanostructures synthesized by a non-equilibrium atmospheric plasma treatment is investigated and discussed. The synthesis approach is simple and environmentally friendly, employs a non-equilibrium nanopulsed atmospheric pressure plasma jet as a contactless cathode and a Cu foil as immersed anode. The process was studied using four distinct electrolyte solutions composed of distilled water and either NaCl?+?NaOH, NaCl only or NaOH only at two different concentrations, without the addition of any copper salts. CuO crystalline structures with limited impurities (e.g. Cu and Cu(OH)₂ phases) were produced from NaCl?+?NaOH containing solutions, mainly CuO and CuCl₂ structures were synthesized in the electrolyte solution containing only NaCl and no synthesis occurred in solutions containing only NaOH. Both aggregated and dispersed nanostructures were produced in the NaCl?+?NaOH and NaCl containing solutions. Reaction pathways leading to the formation of the nanostructures are proposed and discussed.     

采用金属有机骨架材料M(HBTC)(4,4'-bipy)·3DMF(M=Ni,Co,Zn)催化CO2与环氧丙烷的环加成反应

采用溶剂热法合成了三种M(HBTC)(4,4’-bipy)·3DMF (M = Ni, Co, Zn, HBTC = 1,3,5-均苯三甲酸, 4,4’-bipy = 4,4′-联吡啶)结构的支柱层金属有机骨架材料(MOFs). 首次采用溶剂热和微波法合成了Zn(HBTC)(4,4’-bipy)·3DMF, 并采用多种物理化学方法对其进行了表征. M(HBTC)(4,4’-bipy)·3DMF中包含有M2+离子的蜂窝网格层和BTC单元, BTC单元与4,4’-联吡啶柱进一步交联形成三维多孔骨架材料. 在采用烷基铵卤化物作为助催化剂和无溶剂的条件下, 所有MOFs材料均对催化固定CO2与环氧化合物环加成制备环状碳酸酯反应表现出非常好的协同催化性能, 其催化活性高低顺序为: Zn ＞ Co ＞Ni, 这可通过酸-碱双功能特性进行解释. 采用微波法合成的Zn(HBTC)(4,4’-bipy)·3DMF材料表现出与常规催化剂相似的物理化学性质和催化性能. 考察了不同制备参数的影响和材料的重复使用性能, 并提出了该反应的可能机理.     

Glycine sodium nitrate

The glycine mol­ecule in the title compound, Na(NO₃)·C₂H₅NO₂, exists in the zwitterionic form. The Na atom exhibits eightfold coordination and the polyhedron may be visualized as a distorted hexagonal bipyramid. The glycine mol­ecules are linked through head-to-tail hydrogen bonds and are found `sandwiched' between the Na(NO₃) layers.     

Green chemical multicomponent approach for the synthesis of C3-pyranopyrazole-substituted coumarins

An efficient and rapid method was developed for the synthesis of C3-pyranopyrazole-substituted coumarins from one-pot five-component reaction of β-keto ester, hydrazine, O-hydroxy aromatic aldehydes, 6-methyl, 4-hydroxy pyranone and aromatic aldehyde in the presence of tri-ethylamine in solvent-free conditions. The microwave-assisted method reported herein offers advantageous shorter reaction times, higher yields and cleaner reaction compared with conventional heating methods.     

Enantioselective synthesis of oseltamivir phosphate

The key steps in the enantioselective synthesis of Tamiflu include an asymmetric Diels-Alder reaction, Mitsunobu inversion using Fukuyama modified Weinreb reagent, carbamate directed epoxidation. Epoxide opening with trimethylsilyl azide furnished a 3:1 mixture of regioisomers that converged to afford the same aziridine. Attempted preparation of the unsaturated ester regioselectively using 2-iodoxybenzoic acid (IBX) following Nicolaou’s protocol failed. The unsaturated ester was prepared by phenylselenylation followed by selenoxide elimination.     

Influence of pH and microwave calcination on the morphology of KGd(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> particles derived by Pechini Sol–Gel method

KGd(WO₄)₂ (KGW) particles were synthesized at 3.5, 5.5 and 7.5 pH values by Pechini polymeric complex sol–gel method using potassium nitrate, gadolinium nitrate, ammonium paratungstate, citric acid and ethylene glycol as starting materials. Deionized water was used as solvent. Polymeric precursor gel was formed with citric acid as complexing agent and ethylene glycol as binder. Synthesized gel was analyzed by FT-IR spectroscopy. Prepared precursor gels were further annealed using resistive and microwave processes at 550 and 700 °C, respectively. The properties of heat treated samples were characterized by powder XRD, FT-IR, Raman and SEM analysis to understand the crystallinity, organic liberation, tungstate ribbon formation and surface morphology, respectively. The phase formation and different phases of intermediate oxides in pre-fired samples were investigated by powder XRD. Organic liberation in the samples in relation to temperature, and the carbon content in the pre-fired powder was analyzed using FT-IR spectrum. Raman spectrum reveals the formation of tungsten ribbons as well as the quality of the samples. The morphological changes at different synthesis conditions were observed with SEM micrographs.     

Pb,Sr and Ba calix[6]arene hexacarboxylic acid octahedral complexation: a dramatic effect of dealkylation

Calix[6]arene hexacarboxylic acid binds instantly and with low symmetry to Pb, Sr and Ba. Later a highly symmetric up-down alternating conformation emerges. The solution structures are identical to their p-tert-butylcalix[6]arene hexacarboxylic acid counterparts. With either receptor, an octahedral cage is formed around the metal. The transformation from low to high symmetry however proceeds at significantly faster rates for the de-t-butylated host.     

Camouflaging Structural Diversity: Co‐crystallization of Two Different Nanoparticles Having Different Cores But the Same Shell

Two ligand‐protected nanoscale silver moieties, [Ag₄₆(SPhMe₂)₂₄(PPh₃)₈](NO₃)₂ and [Ag₄₀(SPhMe₂)₂₄(PPh₃)₈](NO₃)₂ (abbreviated as Ag₄₆ and Ag₄₀, respectively) with almost the same shell but different cores were synthesized simultaneously. As their external structures are identical, the clusters were not distinguishable and become co‐crystallized. The occupancy of each cluster was 50 %. The outer shell of both is composed of Ag₃₂S₂₄P₈, which is reminiscent of fullerenes, and it encapsulates a well‐studied core, Ag₁₄ and a completely new core, Ag₈, which correspond to a face‐centered cube and a simple cube, respectively, resulting in the Ag₄₆ and Ag₄₀ clusters. The presence of two entities (Ag₄₀ and Ag₄₆ clusters) in a single crystal and their molecular formulae were confirmed by detailed electrospray ionization mass spectrometry. The optical spectrum of the mixture showed unique features which were in good agreement with the results from time‐dependent density functional theory (TD‐DFT).     

CuSO4/sodium ascorbate catalysed synthesis of benzosuberone and 1,2,3-triazole conjugates: Design,synthesis and in vitro anti-proliferative activity

A novel series of conjugates of benzosuberone and 1,2,3-triazole i.e. 3-(4-phenyl-1H-1,2,3-triazol-1-yl)propyl-9-chloro-2,3-dimethyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylic acids (8a-j) were synthesized in good to excellent yields catalysed by CuSO₄ under milder reaction conditions and evaluated for their anti-proliferative activity. The structural elucidation of the prepared compounds was carried out using IR, ¹H NMR, ¹³C NMR and Mass spectral analysis. The newly synthesized derivatives (8a-j) were evaluated for their anti-proliferative activity against four human cell lines and the novel derivatives showed moderate to excellent activity. The obtained results suggest that these compounds can be considered as new hits for anti-proliferative drug development programme and further SAR studies can help obtain better anticancer agents.     

Single step modification of copper electrode for the highly sensitive and selective non-enzymatic determination of glucose

A non-enzymatic sensor was developed for the determination of glucose in alkaline medium by anodisation of copper in sodium potassium tartrate solution. The morphology of the modified copper electrode was studied by scanning electron microscopy, and its electrochemical behavior by cyclic voltammetry and electrochemical impedance spectroscopy. The electrode enables direct electrocatalytic oxidation of glucose on a CuO/Cu electrode at 0.7 V in 0.1 M sodium hydroxide. At this potential, the sensor is highly selective to glucose even in the presence of ascorbic acid, uric acid, or dopamine which are common interfering species. The sensor displays a sensitivity of 761.9 μA mM^?1 cm^?2, a linear detection range from 2 μM to 20 mM, a response time of <1 s, and a detection limit of 1 μM (S/N = 3). It was tested for determination of glucose level in blood serum.