溶液中的吸附作用——Ⅴ.糖炭和硅胶从四氯化碳、苯和乙醇的二元混合溶剂中吸附苯甲酸

测定了糖炭和硅胶从四氯化碳、苯和乙醇的二元混合溶剂中吸附苯甲酸的等温线.固定苯甲酸的平衡浓度,以苯甲酸的吸附量与溶剂成分作图,对四氯化碳-苯体系所得曲线与直线呈负偏差,但无最低点;对四氯化碳-乙醇、苯-乙醇体系所得曲线呈U型,有最低点.两种吸附剂的结果均如此.因溶度不能说明全部结果,我们以溶剂与溶质间在表面上的顶替作用作了初步解释.     

用吸附数据对硅胶表面的分形分析

根据一种中孔硅胶对甲酸、乙酸、丙酸和四氯化碳蒸气吸附等温线的单层区域和毛细凝结区域的数据以及自四氯化碳稀溶液中吸附系列脂肪醇的结果计算了该硅胶表面分形维数D.除了由吸附四氯化碳等温线毛细凝结区域所得D值低于2外,由其它吸附数据得出的该硅胶的分维D近似相等(D=2.06±0.05).中孔硅胶低D值可用其孔结构特性解释.     

硅胶自环己烷中吸附环己酮和苯甲酸

用经不同温度处理的亲水硅胶(表面总羟基浓度不同)和甲基化硅胶(只含有缔合羟基或不同表面浓度的自由羟基的硅胶)为吸附剂, 测定了自环己烷中吸附环己酮和苯甲酸的等温线, 以及几种硅胶样品的红外光谱图, 探讨了表面自由羟基和缔合羟基在溶液吸附中的作用.     

硅胶自环己烷溶液中吸附苯甲酸和苯的计量置换吸附模型

在293~313 K温度范围, 研究了硅胶在环己烷溶液中对苯甲酸和苯的吸附. 发现苯甲酸能非常好地服从计量置换吸附模型(SDM-A). 在用SDM-A处理苯的吸附时, 出现折线形的吸附等温线, 折线的转折点正好是单分子层吸附与多分子层吸附的分界点. 基于SDM-A, 研究了吸附热力学, 建立了吸附热力学的计算公式. 发现在环己烷溶液中苯甲酸被硅胶吸附是自发的、放热的熵增大过程, 而苯被吸附是自发的放热的熵减少过程, 苯甲酸的吸附自由能大于苯, 而吸附焓小于苯, 这是因为苯甲酸有更大的亲吸附剂作用和疏溶剂作用的结果.     

自溶液中的吸附XIII.硅胶自环己烷-正脂肪醇和水-正脂肪醇中吸附TRITONX-100

测定了硅胶和活性炭自水、环己烷和正丁醇中吸附TRITON X-100的等温线,提出了TRITON X-100在硅胶-环己烷界面上形成单分子层,在硅胶-水界面上形成双分子层的吸附模型,测定了硅胶自环己烷-正脂肪醇(C2,C4,C8和C12)和水-正脂肪醇(C2和C4)混合溶剂中吸附TRITON X-100的等温线,自环己烷-正脂肪醇中的吸附时,醇的烃链越短,浓度越大,降低TRITON X-100的吸附作用越显著.自水-正脂肪醇中吸附时,正丁醇降低TRITON X-100的吸附作用比乙醇时更显著,但当TRITON X-100的浓度较低时,正丁醇(0.5mol.dm[-3])的存在却使TRITON X-100的吸附有所增加。     

分子连接性指数与溶液吸附自由能的相关性

测定了硅胶自四氯化碳中吸附脂肪醇及活性炭自水中吸附芳香化合物的吸附等温线, 等温线均可用Langmuir方程描述。利用Langmuir参数计算了各体系的吸附标准自由能变化。计算了各种吸附质的分子连接性指数。各种分子的分子连接性指数与吸附标准自由能变化间有相关性, 并给出了相关方程, 同时作了初步的讨论。     

二组分气体在固体上吸附的研究（Ⅲ）：丙酮—正己烷,甲苯—正己…

测定了丙酮－正己烷，甲苯－正己烷，苯－正己烷，正戊烷－正己烷４个二组分气体在硅烷化硅胶上的吸附等温线，并测定了单组分体吸附等温线，实验结果表明，二组分气体在硅烷化硅胶上的竞争吸附的强弱可以通过其且分气体在硅烷化硅胶上第一层吸附热Ｑ１数值的大小预测。     

自溶液中的吸附 ⅩⅢ.硅胶自环己烷-正脂肪醇和水-正脂肪醇中吸附Triton X-100

测定了硅胶和活性炭自水、环己烷和正丁醇中吸附Triton X-100的等温线。提出了TritonX-100在硅胶-环己烷界面上形成单分子层,在硅胶-水界面上形成双分子层的吸附模型。测定了硅胶自环己烷-正脂肪醇(C_2,C_4,C_8和C_(12))和水-正脂肪醇(C_2和C_4)混合溶剂中吸附Triton X-100的等温线。自环己烷-正脂肪醇中吸附时,醇的烃链越短,浓度越大,降低Triton X-100的吸附作用越显著。自水-正脂肪醇中吸附时,正丁醇降低Triton X-100的吸附作用比乙醇时更显著。但当Triton X-100的浓度较低时,正丁醇(0.5 mol·din~(-3))的存在却使TritonX-100的吸附有所增加。     

硅烷化活性炭的吸附性质

本工作测定了25℃和35℃时硅烷化活性炭自水溶液中吸附苯甲酸和苯甲醛的等温线;计算了吸附过程的ΔGⅲ,ΔHⅲ和ΔSⅲ;用Hill-deBoer方程处理了实验结果。所得结果表明:(1)随硅烷化时间延长,苯甲酸和苯甲醛的吸附量(mol.m^-^2)明显增加;-ΔGⅲ和-ΔHⅲ略有升高,ΔSⅲ为正值;(2)吸附分子之间的相互作用很弱,吸附分子与活性炭表面间的作用随硅烷化程度增加而加大;(3)芳香化合物可能是以苯环吸附在炭表面上的。     

非离子表面活性剂的吸附机理和表面胶团化对二氧化硅悬浮…

测定了ＣＡＢ－Ｏ－ＳＩＬ在２９０．７Ｋ和３０４．２Ｋ时自水和１ｍｏｌ／ＬＮａＣｌ溶液中吸附非离子表面活性剂ＴｒｉｔｏｎＸ－１００（ＴＸ１００）的吸附等温线，结果表明，吸附量随温度升高而增加，ＮａＣｌ的存在也使吸附量增加，运用生成表面胶团的吸附理论处理了实验结果，求得了表面胶团化的平衡常数，表面胶团的平均聚集数，临界表面胶团浓度和表面胶团化的标准热力学函数，实验表明，随ＴＸ１００浓度的增大，ＣＡＢ－     

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.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

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.