Quantum chemical models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media (MOH-H<Subscript>2</Subscript>O-DMSO,M = Li,Na, K)

Models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media have been constructed using Hartree Fock and DFT (B3LYP) quantum chemical methods; the structure and energies of anion complexes are considered. The hydroxide anion in the models is stabilized as complexes of OH^?·H₂O and OH^?· 2H₂O types.     

毛细管区带电泳法测定复方甘草片中的甘草酸、甘草次酸、吗啡和苯甲酸钠

 在紫外检测波长为 2 2 8nm、电压为 14kV、背景电解质为 5 0mmol/L硼砂溶液、内标为氢氯噻嗪的条件下 ,用毛细管区带电泳法对复方甘草片中的甘草酸、甘草次酸、吗啡和苯甲酸钠进行了定量分析。结果甘草酸、甘草次酸、吗啡和苯甲酸钠的相对峰面积 (组分与内标的峰面积之比 )与各自的质量浓度之间呈良好的线性关系 ,上述 4种组分的平均回收率分别为 98 2 % ,97 3% ,97 1%和 97 5 %。方法简便、快速、准确。     

Formation of CaF and AlF in the arc plasma and spectrochemical determination of Ca and Al

Summary The influence of chemical reactions in d.c. arc plasma on the atomic emission determination of traces has been investigated. The effect of added NH₄F on the intensity of spectral lines of Ca and Al was examined. A decrease of the spectral line intensities of Ca and Al in the presence of NH₄F occurred, if the sample had not been mixed in the electrode with NH₄F. The AlF band spectrum, transition A ¹ X ¹ , was observed in absorption of the arc radiation. Further, the axial intensity distribution of Ca, Al, Ga and Ag spectral lines and of the head of the green system of CaF band, has been measured. The depressive effect of fluorine on spectral line intensities of Ca, Al, Ga and Ag has to be connected with the processes in plasma. It is suggested that the formation of fluoride radicals could take part in this effect.

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Bildung von CaF und AlF im Bogenplasma und spektrochemische Bestimmung von Ca und Al

Zusammenfassung Der Einfluß von chemischen Reaktionen im Lichtbogenplasma auf die spektrochemische Spurenanalyse wurde erörtert. Die Wirkung einer Zugabe von Ammoniumfluorid auf die Intensitäten der Spektrallinien des Calciums und Aluminiums wurde untersucht. Wenn die Probe nicht in der Elektrode mit NH₄F gemischt war, wurde eine Intensitätserniedrigung von Ca- und Al-Spektrallinien in Anwesenheit von NH₄F beobachtet. Das AlF-Bandenspektrum, Übergang A ¹ X ¹ , wurde in Absorption der Bogenstrahlung beobachtet. Die Axialverteilung der Linienintensitäten von Ca, Al, Ga und Ag wie auch der Intensität der Kante des grünen Systems der CaF-Banden wurde untersucht. Die depressive Wirkung des Fluors auf die Linienintensitäten von Ca, Al, Ga und Ag sollte mit den Vorgängen im Plasma in Zusammenhang gebracht werden. Es kann vorausgesetzt werden, daß die Bildung der Fluoridradikale bei diesem Effekt eine Rolle spielt.

     

用双氧水绿色氧化环己酮合成己二酸的研究

以30%的双氧水为氧化剂, 钨酸钠与含N或O的双齿有机配体(草酸)形成的络合物为催化剂, 在无有机溶剂、无相转移剂的条件下, 研究了环己酮氧化制己二酸的反应. 研究结果表明, 用廉价的草酸为配体, 最佳反应条件为钨酸钠∶草酸∶环己酮∶30%的双氧水的物质的量比为2.0∶3.3∶100∶350, 在92 ℃下反应12 h, 可制得80.6%的己二酸; 用GC-MS跟踪了氧化过程中三种主要物质环己酮、己内酯及己二酸含量随反应时间的变化关系, 提出了其主要氧化机理为环己酮首先经Beayer-Villiger氧化反应生成己内酯, 己内酯进一步氧化成己二酸.     

甲酰胺与肌醇在氯化钠水溶液中的焓相互作用

应用等温流动微量热法测定298.15 K时甲酰胺与肌醇分子在不同浓度氯化钠水溶液中的混合过程焓变及其稀释焓, 根据McMillan-Mayer理论关联得到各级异系焓相互作用系数(h_xy, h_xxy及h_xyy). 结果表明, 甲酰胺与肌醇分子在氯化钠水溶液中的异系焓对相互作用系数h_xy均为负值, 并且随着氯化钠浓度的增加, h_xy的绝对值逐渐减小.     

Two-dimensional catena–polymer [[[bis (µ-aqua)(bis (µ-cpiap-K2O1:O2)sodium(I))] (µ-chlorido) bis(µ-cpiap-K5N1:O1:O2:O3,O3′)dicopper(II)]bis(µ-aqua)(aqua)bis(cpiap-K2O1,O2)copper(II)] hexa hydrate

The new title two-dimensional hetero-tetra nuclear Cu₃–Na coordination polymer {[NaCu₃Cl(cpiap)₂(H₂O)₃]_n·6nH₂O} (1) consists of crystallographically two-independent copper(II) centers, each bridged by a sodium cation through carboxylate-oxygen of the deprotonated H₃cpiap ligand (H₃cpiap = 2-(carboxyphenyl)iminoaceticpropanoic acid) to Cu^II (2) and Cu^II (2⁻) cations, and through water molecules to Cu^II (1) cation. Cu^II (2) and Cu^II (1) cations are bridged by carboxylate-oxygen atoms of the ligand in a syn-anti mode which, alternate regularly within the chain being bridged by a tetra coordinated sodium cation. Each Cu^II (2) and Cu^II (2⁻) cation in (1) is in an octahedral environment formed by four carboxylate-oxygens from two cpiap³⁻ ligands, one nitrogen atom and a bridging chloride atom. Cu^II (1) cation is in a square pyramidal environment formed by three water molecules and two carboxylate-oxygens from two cpiap³⁻ ligands. The ligand acts simultaneously as monodentate and tridentate toward Cu^II (1) and Cu^II (2) cations respectively. The lattice water molecules involved in OH···O hydrogen bonding are situated in the void spaces between layers. The zigzag chains, which run along the b-axes further construct three-dimensional metal-organic framework via hydrogen bonding and weak face-to-face π-π interactions. Weak CH···O interactions are also present.     

硫酸氢钠催化合成己酸异戊酯的研究

己酸异戊酯是应用最广泛的食用香料之一。通常它是在硫酸催化下由己酸和异戊醇酯化反应而得[1] ,硫酸虽然活性高 ,价廉 ,但选择性差 ,产品质量不好 ,设备腐蚀严重 ,同时产生大量废液 ,污染环境。已发现对甲苯磺酸、磺酸树脂、固体超酸、杂多酸、氯化铁以及过渡金属硫酸盐等均可作为酯化反应的优良催化剂[2～ 7] 。本文探讨了硫酸氢钠催化羧酸的酯化反应 ,结果发现它具有良好的催化性能 ,且后处理方便 ,无污染。1　实验部分在装有分水器、温度计和回流冷凝器的四颈烧瓶中 ,加入一定量分析纯的己酸、异戊醇、甲苯和催化剂硫酸氢钠 (ＮａＨＳＯ…     

A mild and practical method for the regioselective synthesis of N-acylated 3,4-dihydropyrimidin-2-ones. New acyl transfer reagents

The treatment of 3,4-dihydropyrimidin-2-ones with n-BuLi at −78 °C, followed by quenching with various electrophiles furnished N3-substituted derivatives, regioselectively. Further, N1,N3-diacyl derivatives were found to transfer N1-acyl groups to nucleophilic sites.     

Mechanism of the thermal decomposition of hydrophosphites of lithium,sodium and potassium

The thermal decomposition of some M ₂ ^I HPO₃ (M-Li, Na, K) phosphites under nitrogen atmosphere was investigated. A stepwise mechanism of thermal decomposition has been proposed.

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Zusammenfassung Es wurde die thermische Zersetzung von Phosphiten M ₂ ^I HPO₃ (M-Li, Na, K) in Stickstoffatmosphere untersucht. Die Schritte des Mechanismus der thermischen Zersetzung wurden vorgeschlagen.

     

Small angle neutron scattering studies on nonaqueous dispersions of calcium carbonate Part 2. Determination of the form factor for concentric spheres

Colloidal dispersions of calcium carbonate, stabilised primarily by a surface active agent, in both toluene and dodecane have been examined by small angle neutron scattering. A model has been developed to simulate the scattering behaviour of the particles and is based on the idea of a concentric sphere with a homogeneous layer of adsorbed material surrounding a core particle. Computations based on the model show a wide variation of scattering behaviour with variation of the coherent scattering length of the dispersion medium. These predictions were confirmed by experiment. A method is described for analysis of the experimental data which leads to a determination of the thickness of the adsorbed layer, the radius of the core particle and the standard deviation of core particle radius.