四唑盐细胞活力指示剂研究进展

四唑盐类化合物是细胞生物学、细胞与分子毒理学及临床诊断领域用于测定细胞活力的生物指示剂。分别综述了:1)四唑盐及其性质;2)甲臜及其四唑盐的制备方法;3)四唑盐的发展阶段、市场需求以及商品化四唑盐基于比色技术在细胞毒性、抗菌药物的筛选及抗菌药敏实验等方面的应用,并对其发展前景进行了展望。     

On the Reaction of Acylium Salts with Isocyanates

Alkyl isocyanates ( 3 ) react with acylium salts ( 2 ) in a 2:1 ratio to furnish 3,4-dihydro-2,4-dioxo-2H-1,3,5-oxadiazinium salts 4. These cyclic N-acyliminium salts are decomposed with catalytic amounts of water to give either oxadiazinium salts 5 or pyrimidinium salts 7. With aqueous base compounds 4 are transformed into acylureas 6. Hetero substituted open chain N-acyliminium salts ( 8a , 11c , 12c , 13f , 15g , 16a ) are produced from 4 by treatment with heteronucleophiles such as methanol, p-anisidine, p-cresol, thiophenol, 1,3-dimethylurea, or benzohydrazide, respectively. Excess of nucleophile furnishes further degradation products of 4 , e.g. oxonium salts ( 9a ) and iminium salts ( 14f ).     

锂离子电池电解质锂盐研究进展

介绍了锂离子电池电解质锂盐的化学和电化学。综述了近年来在新型电解质锂盐研究与探索方面的成果。新型电解质锂盐主要包括三类化合物 :(1 ) Li TFSI及其类似物 ;(2 )络合硼酸锂 ;(3 )络合磷酸锂。文章最后阐述今后电解质锂盐研究的可能发展方向及研究方法     

Thermal cationic curing with benzylammonium salts

Novel cationic initiators, benzylanilinium salts, were synthesized from benzylchloride and N,N-dimethylaniline followed by exchange of counter anion with SbF₆⁻. Benzylanilinium salts showed thermal latency as initiator in the cationic polymerization of glycidyl phenyl ether. The electrophilic characteristic of the benzyl group of benzylanilinium salts were estimated by the reaction of D₂O using ¹H NMR. The electrophilic characteristics of the benzyl group in benzylanilinium salts depended on the p-substituents (benzyl position in benzylanilinium salts). Cationic curing systems, consisting of benzylanilinium salts and the polymer containing oxirane moieties, were proposed and some properties of films obtained by this systems were evaluated. It was found that cationic curing systems had some better properties, especially resistance to acid, than those of the melamine curing systems and that anilinium salts were more useful than benzylpyridinium salts as the initiators for cationic curing systems for coatings.     

Regioselective lipase-catalyzed transesterification of tributyrin. Influence of salt hydrates on acyl migration

The influence of the nature of solid salt hydrates on the rate of hexanoic acid catalyzed acyl migration in 1,2-dibutyrin has been examined in hexane. The results show that the rate of acyl migration is faster when hydrogen phosphate salts are included compared to sulfate salts. The rate is essentially the same in the presence of sulfate salts and without salts. In regioselective lipase-catalyzed acidolysis of tributyrin with hexanoic acid, the use of hydrogen phosphate salts to control water activity leads to a higher rate of migration than the use of sulfate salts. Minor differences are observed in interesterification with ethyl hexanoate.     

Reverse osmosis separation of inorganic salts using polyvinylalcohol membranes

Permeabilities and fluxes of fifty-four mono-, divalent anions and cations of sodium and chloride salts have been tested under experimental conditions of 50 bar and room temperature through asymmetric polyvinylalcohol membranes crosslinked with formaldehyde. The following percent rejections among these salts are given: sodium salts of divalent anions (70–80%), chloride salts of divalent cations (30–40%), H₂ SO₄ (30%), sodium salts of monovalent monoatomic anions, chloride salts of monovalent cations (15– 30%) and HCl, HNO₃, NaOH, KOH (10–20%). Sodium salts of monovalent polyatomic anions gave higher rejections than those of monovalent monoatomic anions. Higher rejection of divalent anions than that of divalent cations of chloride salts suggests that the membrane surface is negatively charged.     

季铵盐链长及用量对CnTA+/蒙脱石纳米复合物吸附PAEs的影响

用具有相同结构但不同烷基碳链长度的系列季铵盐制得C_nTA⁺/蒙脱石纳米复合物,并对水溶液中邻苯二甲酸酯进行吸附实验。探讨了季铵盐烷基碳链链长和用量对制得的C_nTA⁺/蒙脱石纳米复合物吸附水溶液中PAEs效果的影响。结果表明:C_nTA⁺/蒙脱石纳米复合物能有效地吸附溶液中的PAEs,季铵盐烷基碳链链长及用量均对C_nTA⁺/蒙脱石纳米复合物的吸附效果产生影响。当季铵盐用量较低时,随着季铵盐烷基链长的增加,PAEs的吸附去除率增加;增大季铵盐用量,随着季铵盐烷基链长的增加,PAEs的吸附去除率先增大后减小。     

Extractable metal salts of carboxylic acids in Green River oil shale

A study of solvent-extractable metal salts of carboxylic acids from Colorado Green River oil shale is presented. Sodium was found to be the most abundant cation present in these acid metal salts. Identification of individual components is based on combined gas Chromatographic and mass spectrometric results obtained for their respective volatile methyl esters. Normal acid salts (C₁₁ to C₃₄), isoprenoid acid salts (C₁₅ to C₁₇, C₁₉ to C₂₂), nonisoprenoid branched acid salts (C₁₄ to C₁₉), terpenoid acid salts (C₃₀ to C₃₂), and α,ω-dicarboxylic acid salts (C₁₁ to C₂₉) were identified. Small concentrations of cyclohexyl acid salts and aromatic acid salts were also found. The high even-odd predominance for the distribution of normal acid salts indicates a mild thermal history for Green River oil shale. Some acid salts (45.6 wt%) were not identified because of nonvolatility of their methyl esters.     

二烷基次膦酸盐类阻燃剂的结构设计与合成方法研究进展

综述了二烷基次膦酸盐类阻燃剂的结构设计和合成方法的研究进展,根据其结构中烷基的不同进行了分类,可分为含直链、支链、芳环、杂环以及二聚体的次膦酸盐,并对其合成方法进行了归纳,通过对比AlCl3催化反应法、格氏试剂法和自由基加成法3种合成二烷基次膦酸盐类的方法发现,AlCl3催化法产率较低,污染问题突出;格氏试剂法步骤繁多,工艺复杂;自由基加成法相对工艺简单、产率高,适合大规模生产等特点。     

Alkylation of Ammonium Salts Catalyzed by Imidazolium‐Based Ionic Liquid Catalysts

Quaternary ammonium salts were synthesized from ammonium salts and dialkyl carbonates over imidazolium ionic liquid catalysts. The reaction gave almost stoichiometric amounts of the quaternary ammonium salts for halides and nitrates. It was found that the electron‐donating property of the alkyl moieties of ammonium cations, the electrophilic nature of the alkyl group of the carbonate, the acidity of the acid that the anion of the ammonium salt corresponds to, and the steric hindrance of the ammonium salts and the dialkyl carbonates are the key factors that influence the yields of quaternary ammonium salts. Strong electron‐donating alkyl groups on the nitrogen atom of the ammonium salt, electron‐withdrawing groups on the methylene carbon of dialkyl carbonate, and weaker steric hindrance of the starting ammonium salts and dialkyl carbonates favor the alkylation reaction of ammonium salts.     

太阳能光热发电中熔盐蓄热储能循环系统的设计开发

分析了熔盐蓄热储能技术,讨论了光热发电中使用的熔盐混合物特性,介绍了采用熔盐蓄热储能技术的太阳能光热发电站的结构和型式。开发了熔盐蓄热储能循环系统的工艺流程,并对熔盐的流量与流速、熔盐膜壁温度、熔盐分解物、熔盐结垢堵塞等问题及其相互之间的关系进行了研究,给出了熔盐管路预热与保温、熔盐贮罐内防固化、惰性气体密封装置和安全保护措施等的设计原则。     

Ene Reactions and [2+2]Cycloadditions of Nitrilium Salts with Alkenes

N-Alkylnitrilium salts ( 1 ) undergo ene reactions with electron-rich di- and higher substituted alkenes 2 to afford either 2-azoniaallene salts ( 3, 6, 9, 11 ) (the nitrilium salt reacting as ene and the alkene reacting as enophile) or 1-azonia-1,4-pentadiene salts ( 10, 12 ) (the alkene reacting as ene and the nitrilium salt reacting as enophile). Competing with ene reactions tri- and tetrasubstituted alkenes and N-alkylnitrilium salts undergo [2+2]cycloaddition to furnish azetinium salts ( 8, 13 ). In solution, alkyl substituted 2-azoniaallene salts tautomerize to 2-azonia-1,3-butadiene salts ( 4, 5, 7 ). The constitutions of the 2-azoniaallene salt 6c and the azetinium salt 8 were secured by X-ray crystallographic analyses.     

Some reactions of 1,3-Dichloro-2-azoniaallene Salts with heteronucleophiles

1,3-Dichloro-2-azoniaallene hexachloroantimonates ( 1 ) reacted with H₂S to give 1,2,4-dithiazolium salts 2 . With hydrazines 1,2,4-triazolium salts ( 3, 4 ) were formed. 1,3-Dimethylurea, respectively 1,3-dimethylthiourea or ethyl allophanate, reacted with 1 to afford 2-oxo- or 2-thioxo-1,3,5-triazinium salts ( 5–7 ). With diphenylmethaneimines imino substituted 2-azoniaallene salts 8 were produced. From chloroacetonitrile dichloropyrimidines 9 , and from the tricyanomethyl anion a hexatriene 10 and a triazine 11 could be prepared. The 1,5-dichloro substituted 2-azoniaallene salts 12 reacted as bifunctional electrophiles with nucleophiles such as benzophenone hydrazone or anilines, to furnish 1,3,5-triazinium salts 14 . Against benzohydrazide the allene 12j behaved as trivalent electrophile giving the bicyclic 1,3,5-oxadiazinium salt 13j , the constitution of which has been secured by a crystal structural analysis. The vinyl-2-azoniaallene salt 1i cyclized on heating to the 1,3-thiazinium salts 16, 17 . From 17 the triazinium salts 18 were prepared with alcohols.     

Surface Activity and Performance Properties of Gemini Salts of Linear Alkylbenzene Sulfonate in Aqueous Solution

Gemini salts of linear alkylbenzene sulfonate (LABS) were prepared by neutralization of sulfonic acid with a series of low-molecular-weight diamines in aqueous solution. The equilibrium surface activity of Gemini salts of LABS was determined by measuring the surface tension as a function of surfactant concentration to determine the critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), and the area per molecule at the air-water interface (Ų). Electrical conductivity was measured as a function of surfactant concentration to determine the CMC and counterion binding. Dynamic surface tension was measured using a bubble pressure tensiometer to infer the rate at which the surfactant migrates to the air-water interface. Equilibrium interfacial tension against mineral oil was measured using a spinning drop tensiometer. Dynamic interfacial tension was measured using a drop volume tensiometer. The surface tension, CMC, and interfacial tension of Gemini salts of LABS decreased compared to monovalent organic and inorganic salts. The CMC decreases with increasing molecular weight of the diamine spacer group. Dynamic surface and interfacial tension of Gemini salts of LABS are lower than monovalent salts. The foam volume of Gemini salts of LABS was determined using a high shear blender test. The foam volume of Gemini salts of LABS is lower than monovalent salts and depends on the size of the spacer group. Hard-surface cleaning was measured using artificial soil applied to white Formica tiles. Soil removal was determined by optical reflectance as a function of abrasion cycles. Gemini salts of LABS show reduced hard-surface cleaning performance compared to monovalent salts. Detergency of different types of soils on cotton and polyester/cotton fabric was determined by optical reflectance measurements. Gemini salts of LABS show improved cleaning performance compared to monovalent salts. Cleaning performance increases with increasing molecular weight of the diamine spacer group. In situ neutralization of LABS with organic diamines is a simple and efficient way to prepare anionic Gemini surfactants for industrial scale applications.     

Preparation, surface-active and antielectrostatic properties of multiple quaternary ammonium salts

A series of new cationic surfactants, bis-quaternary ammonium salts and tris-ammonium salts, were prepared from N,N-dimethyldodecylamine and a product of the reaction of epichlorohydrin with ethyl-, propyl-, butyl-, pentyl-, hexyl-, and octylamine (in the xase of bis-ammonium salts) or the hydrochloride of diethyl-, dipropyl-, dibutyl-, or dihexylamine (in the case of tris-ammonium salts). The obtained multiple salts were examined with respect to their surface-active properties: Critical micelle concentrations (CMC), effectiveness of surface tension reductions (γ_CMC), and adsorption efficiencies (pC₂₀) were measured. All these surfactants showed good water solubility and low CMC of more than one order of magnitude lower than those of corresponding monoalkylammonium salts. They also showed good foaming properties, but worse wetting capability. The obtained multiple salts showed excellent antielectrostatic properties.     

Surface active N-acylglutamate: II. Physicochemical properties of long chain N-acylglutamic acids and their sodium salts

The physicochemical properties of long chain N-acylglutamic acids (AGA) and their sodium salts (AGS_n) are described. The solubility, Krafft point, pH value, critical micelle concentration, surface tension and foaming power were measured. The properties of the optically active AGA or AGS_n differed from those of the corresponding racemates, especially in solubility. The monosodium salts generally had high Krafft points, but monosodium N-oleoylglutamate had a low Krafft point. The monosodium salts hydrolyzed in the diluted aqueous solution to liberate the AGA. The aqueous solutions of the monosodium salts had low surface tensions and good foaming properties. The disodium salts were highly soluble in water, while surface tensions and foaming properties were inferior to those of the corresponding monosodium salts.     

Preparation of bulk and supported heteropolyacid salts

We describe the preparation of bulk and supported cesium and ammonium heteropolyacid and acid salts of 12-tungstophosphoric acid. Novel synthetic schemes to prepare supported forms of insoluble cesium- and ammonium-acid salts are discussed, and their behavior in model compound isomerization and alkylation reactions is described. In particular, we discuss the egg-white morphology associated with Cs-acid salts supported on silica extrudates prepared by a novel in situ-reaction/precipitation route. We also describe hydrothermal techniques developed for directly preparing the ammonium-acid salts of 12-tungstophosphoric acid and the extension of that technique to other heteropolyacid salts.     

燃烧催化剂对EMCDB推进剂交联固化反应的催化作用

设计了一种研究燃烧催化剂对EMCDB推进剂交联固化反应催化作用的实验方法，比较了十多种铅盐、铜盐对交联固化反应催化活性的强弱，筛选出了可用作粒铸EMCDB推进剂燃烧催化剂的铅盐、铜盐。实验结果表明，某些铅盐对交联固化反应有较强的催化加速作用，铜盐和炭黑对交 联固化反应没有明显的催化加速作用，只有对交联固化反应催化加速作用很小的铅盐才能用作EMCDB推进的燃料催化剂。     

A new family of ionic liquids based on the 1-alkyl-2-methyl pyrrolinium cation

Five new salts based on 1-alkyl-2-methyl pyrrolinium ion are reported, two involving the iodide ion and three involving the bis(trifluoromethanesulfonyl) amide ion. The iodide salts have melting points around 100 °C, while the amide salts have melting points around room temperature. Two of the amide salts can be easily quenched into the glassy state and exhibit glass transition temperatures around −70 °C. The 2-methyl pyrrolinium cation bears structural similarities to the aromatic imidazolium cations on one hand and the cyclic ammonium cation family based on the pyrrolidinium cation on the other. The properties of the salts reported here are compared within these two related families of salts.     

取代芳基磷酸金属盐类成核剂对聚乳酸结晶的影响

通过示差扫描量热仪（DSC）和偏光显微镜（POM）考察了取代芳基磷酸金属盐类成核剂对聚乳酸结晶行为的影响。结果表明：取代芳基磷酸一价盐和三价盐可以较好的改善聚乳酸的结晶，其中取代芳基磷酸锂盐的效果最好，使结晶温度提高了4℃。取代芳基磷酸二价盐对于聚乳酸结晶的改善并不明显。对取代芳基磷酸金属盐类成核剂浓度效应的研究发现：1％为其在聚乳酸中的饱和添加浓度。针对滑石粉和取代芳基磷酸锂盐进行了复配研究，发现复配后的成核剂可以更好的促进聚乳酸的结晶。