十八烷基二甲基氯化铵水溶液动态表面张力及吸附动力学研究

使用最大气泡法测定了十八烷基二甲基氯化铵（C_(18)DAC）水溶液的动态表 面张力，考察了浓度、温度等对其DST的影响，详细表征了DST随时间的变化过程， 计算了动态表面张力的各种参数（n，t_i，t~*，t_m，R_(1/2)）。结合Word- Tordai方程计算了表观扩散系数（D_a）和吸附势垒（E_a），对其吸附动力学模式 进行了研究，探讨了DST参数的物理意义。结果表明，t~*值越小，吸附势垒E_a越 大，宏观扩散系数D_a越小，表面活性剂分子越不易吸附在溶液表面；C_(18)DAC低 浓度时吸附属于扩散控制模式，高浓度时属于混合控制模式；高浓度时，在吸附初 期（t → 0）为扩散控制模式，吸附后期（t → ∞）为混合控制模式。     

十八烷基二甲基氯化铵水溶液动态表面张力及吸附动力学研究

使用最大气泡法测定了十八烷基二甲基氯化铵（C_(18)DAC）水溶液的动态表 面张力，考察了浓度、温度等对其DST的影响，详细表征了DST随时间的变化过程， 计算了动态表面张力的各种参数（n，t_i，t~*，t_m，R_(1/2)）。结合Word- Tordai方程计算了表观扩散系数（D_a）和吸附势垒（E_a），对其吸附动力学模式 进行了研究，探讨了DST参数的物理意义。结果表明，t~*值越小，吸附势垒E_a越 大，宏观扩散系数D_a越小，表面活性剂分子越不易吸附在溶液表面；C_(18)DAC低 浓度时吸附属于扩散控制模式，高浓度时属于混合控制模式；高浓度时，在吸附初 期（t → 0）为扩散控制模式，吸附后期（t → ∞）为混合控制模式。     

不同结构烷基苯磺酸钠水溶液的泡沫性能及动态表面张力

研究了一系列直链三取代和支链双取代烷基苯磺酸钠水溶液的动态表面张力(DST)和泡沫性能, 考察了分子结构变化对烷基苯磺酸钠水溶液的DST和泡沫性能的影响. 探讨了动态表面张力参数(t*, n, R1/2)的变化规律及其与泡沫性能的关系. 结果表明, 随着取代烷基链长度增加, t*和n值增大, R1/2减小, 动态表面活性降低. 由于双取代支链烷基苯磺酸钠分子具有特殊的柔性长支链, 使得吸附膜排列紧密、膜弹性增大, 因而其泡沫稳定性明显优于多取代直链烷基苯磺酸钠的稳定性. 在气流法产生泡沫的过程中, 动态表面张力是控制起泡高度的关键因素.     

蓖麻油酸甲酯乙氧基化物水溶液的动态表面张力

用最大气泡压力法分别测定了不同环氧乙烷(EO)加合数(10、12、14、16、20)的蓖麻油酸甲酯乙氧基化物(ECAME)水溶液的动态表面张力(DST)。考察了浓度、温度和无机电解质对DST的影响,探讨了不同浓度时DST参数(动态表面张力特性参数n,平衡时间t^*,曲线最大斜率R_1/2)的变化规律。结果表明,随着EO数由10增加到20,DST不断增大;随着浓度由0.5×10^-5 mol/L增加到10×10^-5 mol/L,n由3.02减小到1.05,t^*值由14.45减小到2.29,R_1/2由0.43增大到6.44,则动态表面活性增大,DST降低;随着温度由25 ℃升高至45 ℃,DST降低;吸附初期DST曲线随无机电解质浓度的增大而升高,吸附后期DST曲线随无机电解质浓度的增大而降低。和常规的脂肪酸甲酯乙氧基化物(FMEE)相比,ECAME的动态表面活性更加优异,这为开拓ECAME的应用指明了新的方向。     

一种磺酸聚醚型表面活性剂的制备及动态表面张力

通过3-氯-2-羟基丙磺酸钠(NaCHPS)和1-氯-3-丁氧基-2-丙醇(CBP)之间溶液共缩聚,合成了一种新型磺酸聚醚表面活性剂—环氧丙磺酸缩水甘油丁基醚共聚物。采用红外、核磁等测试技术对其结构进行了表征。测定了不同质量浓度、不同结构的磺酸聚醚水溶液的动态表面张力(DST),并用Rosen经验方程对DST进行了分析。结果表明,磺酸聚醚的数均分子量为900～1 600,其溶液浓度越高,DST达到介平衡越快,则DST分析曲线越低;当质量浓度从56．4 mg/L增大到3 611 mg/L时,R_(1/2)值从11．04 mN/(m·min)增大到7 662．5 mN/(m·min);磺酸聚醚的动态表面活性随着磺酸聚醚中CBP含量的增加而增强。     

烷基聚葡糖苷溶液的表面吸附平衡的动力学

用吊片法和气泡最大压力法分别测定了烷基聚葡糖苷（APG）C9.6G1.3水溶液的平衡和动态表面张力，研究了APG水溶液表面的吸附平衡、动力学及其影响因素。测得其cmc(临界胶束浓度）为0.032g/L。吸附过程由初始的扩散控制转变到势垒控制，吸附势垒为4－7kJ/mol。温度升高，平衡和动态表面张力均减小，吸附量增加；加入无机盐，平衡和动态表面张力增大，吸附量亦增加；醇类的吸附使动态表面张力下降速度加快，表明APG与醇分子间有协同吸附作用。     

短链醇、胺和酸等物质水溶液表面张力关联式的新探讨

提出了一种新的单参数表面张力关联式，并将其应用于短链醇、胺和酸等物质（如乙醇、正丙胺、正丙醇、正丁醇和正己酸）水溶液的表面张力数据处理。结果表明：在较大的浓度范围内，公式能真实地反映这些物质表面张力随浓度的变化规律。     

不同分子量的聚缩水甘油苯基醚磺酸钠的合成及表面性能

用正丁基锂作催化剂,合成了不同分子量的聚缩水甘油苯基醚预聚体(PPGE),分别用浓H2SO4进行磺化,制得了可作为高分子表面活性剂的不同磺化度聚缩水甘油苯基醚磺酸钠(SPPGE)。研究了其结构与表面性能间的关系。结果表明,PPGE的分子量为1000~3000,SPPGE的磺化度为150%~250%,随着SPPGE质量浓度从2.5 g/L增至20.0 g/L,SPPGE的动态表面活性随之而增大,DST达到介平衡越快,DST曲线越低。在研究的浓度范围内,吸附初期属扩散控制吸附,后期属混合动力吸附,且浓度越高,吸附势垒εa越大,有效扩散系数Deff越小。3种不同磺化度的SPPGE的临界胶束浓度和最小表面张力值随磺化度变化不大,CMC值均在11.0 g/L左右,改变磺酸聚醚的分子量可以有效改变磺酸聚醚的表面活性,其中Mn为1595的表面张力曲线最低,其CMC值为10.9 g/L,γm in为48.93 mN/m。     

烷基聚葡糖苷溶液的表面吸附平衡与动力学

用吊片法和气泡最大压力法分别测定了烷基聚葡糖苷 (APG) C9.6 G1 .3水溶液的平衡和动态表面张力 ,研究了 APG水溶液表面的吸附平衡、动力学及其影响因素 .测得其 cmc(临界胶束浓度 )为 0 .0 3 2 g /L .吸附过程由初始的扩散控制转变到势垒控制 ,吸附势垒为 4～ 7k J/mol.温度升高 ,平衡和动态表面张力均减小 ,吸附量增加 ;加入无机盐 ,平衡和动态表面张力增大 ,吸附量亦增加 ;醇类的吸附使动态表面张力下降速率加快 ,表明 APG与醇分子间有协同吸附作用     

液态金属和合金表面张力的预测

用人工神经网络预测了液态纯金属的表面张力， 在Ｂｕｔｌｅｒ 方程的基础上用Ｃ＋ ＋ 语言编制了由合金熔体热力学参数和纯组元表面张力计算液态合金表面张力的计算程序—ＳＴＣＢＥ。一批Ｓｎ 基、Ａｇ 基和Ｃｕ 基二元合金的计算值与实验值吻合很好， 预测了１４００ Ｋ时二元液态合金ＣｕＲＥ（ＲＥ：Ｃｅ，Ｐｒ，Ｎｄ）的表面张力。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.