反相液相色谱中温度对蛋白分子构象变化的新表征

液相色谱中溶质计量置换保留模型的Ｚ值可用来对反相高效液相色谱中热变蛋白的分子构象进行表片。发现在异丙醇－甲酸４４％（Ｖ／Ｖ）－水体系为流动相对完全变性蛋白的Ｚ值随温度升高而降低。且Ｚ值与绝对温度例数（１／Ｔ）成正比，因此蛋白分子构象变化可用Ｚ对１／Ｔ作图所得两条直线的斜率差值来表征，差值愈大，蛋白分子构象变化愈甚。该两直线的交点即为蛋白分子构象的突变温度。与通常采用的１ｇＫ＇对１／Ｔ的作图相比，用     

一种在线液—液萃取微型多用分相器的设计和应用：IV.流动注射液— …

设计了在线液－液萃取多用重分布相器及相应流动注射流路系统与ＩＣＰ－ＡＥＳ法联用。具有良好的分析性能，通过对矿石中某些重稀土元素在硝酸介质中被ＴＢＰ萃取的应用研究表明钇，镱，铒的检出限（３σ）分别为６．８ｎｇ／ｍＬ，０．２ｎｇ／ｍＬ和１．５ｎｇ／ｍＬ，精密度（ＲＳＤ％）分别为０．２４，０．４７和１．８，进样频率为２５－３０个／ｈ。     

一种在线液-液萃取微型多用分相器的设计和应用 Ⅳ.流动注射液-液萃取电感耦合等离子体原子发射光谱法测定矿石中稀土元素

设计了在线液－液萃取多用重力分相器及相应流动注射流路系统与ＩＣＰ－ＡＥＳ法联用，具有良好的分析性能．通过对矿石中某些重稀土元素在硝酸介质中被ＴＢＰ萃取的应用研究表明钇、镱、铒的检出限（３σ）分别为：６．８ｎｇ／ｍＬ、０．２ｎｇ／ｍＬ和１．５ｎｇ／ｍＬ．精密度（ＲＳＤ％）分别为０．２４、０．４７和１．８．进样频率为２５～３０个／ｈ．     

SAPO－5，－11和－34分子筛模板剂的脱除及其结构的热致变化

用水热法合成了ＳＡＰＯ－５，－１１和－３４硅磷酸铝类分子筛。并对经不同温度焙烧处理的样品进行表征，结果表明：分子筛中模块剂的热分解过程与其结构和孔大小有较大的关系。在ＳＡＰＯ－５和ＳＡＰＯ－３４分子筛中，外部联接的Ｔ－Ｏ－Ｔ键的反对称伸缩振动峰（１２４０ｃｍ~（－１）－１０３８ｃｍ~（－１））和其对称伸缩振动（７３４ｃｍ~（－１）－６００ｃｍ~（－１））及双环的变形振动（６００－５００ｃｍ~（－１））的吸收峰对样品的结晶度比较敏感。但在ＳＡＰＯ－１１中，分子筛骨架中Ｔ－Ｏ－Ｔ反对称伸缩振动（１２２５ｃｍ~（－１）和１０３８ｃｍ~（－１））随结晶度的下降而基本保持不变，但内四面体（ＴＯ_４）的对称伸缩振动，反对称伸缩振动峰及Ｔ－Ｏ弯曲振动峰随样品焙烧温度的升高而减弱并分裂。红外吸收带向低频方向移动。ＳＥＭ－ＥＤＡＸ结果表明：随样品焙烧温度的升高，结晶度下降，分子筛晶形变得不规则，晶面越来越粗糙，但结晶度的下降并非由于其中ＰＯ_４四面体的热分解所引起，而是由外部联结的Ｔ－Ｏ－Ｔ键的断裂，双环被破坏及骨架元素间的重排所引起。     

新型梳状聚合物电解质的离子导电性 Ⅱ.侧链是分子量为550的聚乙二醇单甲醚

以乙烯／马来酸酐共聚物为骨架，聚乙二醇单甲醚（Ｍ＝５５０）为侧链，通过两步酯化，合成了梳状乙烯／马来酸酐共聚物多缩乙二醇酯，用ＩＲ、元素分析、交流复阻抗谱等对产物及其ＬｉＣｌＯ４盐复合物进行了研究。结果表明：所合成的产物为非晶的梳状聚合物，并严格按反应方程式生成半酯。盐浓度与电导率的关系在所研究的浓度范围内存在两个峰，一峰在Ｏ／Ｌｉ＋＝８；另一峰在Ｏ／Ｌｉ＋＝３０。用侧链ＰＥＯ玻璃化转变温度作Ｔ０，以ｌｏｇσ对１／Ｔ－Ｔ０作图，电导率与温度关系呈典型的ＶＴＦ行为，该体系室温电导率最高可达２．５８×１０－５Ｓ／ｃｍ。     

液相色谱手性柱的温度效应

使用脲衍生型手性色谱柱作正相色谱,在不同温度下拆分３,５－二硝基苯甲酰氨基酸丁酯对映体。结果表明,柱温在－６℃至４０℃间变化时,ｌｎｋ＇与１／Ｔ以及ｌｎα与１／Ｔ皆呈直线关系。随着柱温的下降,相对保留值α上升,但部分化合物的Ｒｓ－Ｔ曲线在低温时出现转折。     

以混合模板剂合成TS—1分子筛及其性能研究

以四丁基溴化铵（ＴＢＡＢｒ）＋四乙基氢氧化铵（ＴＥＡＯＨ，ｎ（ＴＢＡ＾＋）／ｎ（ＴＥＡ＾＋）＝１）或以四丙基溴化铵（ＴＰＡＢｒ）＋ＴＥＡＯＨ为模板剂，钛酸四丁酯和正硅酸乙酯为原料，于１７０℃水热合成出ＴＳ－１分子筛。对合成的ＴＳ－１样品进行了ＸＲＤ，ＦＴ－ＩＲ，ＳＥＭ和ＢＥＴ比表面积分析，证实了样品中钛已进入Ｓｉｌｉｃａｌｉｔｅ－１骨架。选择戊烷氧化为探针反应，考察了ＴＳ－１的催化活性。结果表明以     

吸附溶出伏安法测定水中痕量镉

报道了测定痕量镉的一种新方法．在０．０１ｍｏｌ／ＬＨＡｃ－０．０１ｍｏｌ／ＬＮａＡｃ－１．２×１０－５ｍｏｌ／Ｌ乙醛酸缩氨基硫脲（ＧＡＴＳＣ）体系中，Ｃｄ－ＧＡＴＳＣ产生一灵敏的吸附还原波，波的峰电位是－０．４３Ｖ（ｖｓ·ＳＣＥ），峰电流与镉的浓度在１．０×１０－８～８．０×１０－７ｍｏｌ／Ｌ范围内成直线关系．此法用于测定水中痕量镉，结果令人满意。     

聚环氧乙烷环氧丙烷—盐复合物的结构和导电性

制备了室温电导率较高（１０＾－４Ｓ·ｃｍ＾－１），力学性能较好的环氧乙烷和环氧丙烷共聚物－Ｌｉ－ＣｌＯ４复合物薄膜，研究了共聚物组成对结晶及对复合物室温电导率的影响，考察了高氯酸锂浓度对复合物室温电导率的影响以及复合物电导的温度依赖关系，发现复合物中没有结晶配合物，其结晶度随聚合物结构和盐含不同而变化，室温下呈弹性体。     

Ti—Si沸石表面吸附物种的TPSR—TPD研究

氯丙烯在不同催化剂表面上吸附的ＴＰＤ结果表明在ＴＳ－１上有三重附峰，而在ＴｉＯ２／Ｓｉｌｉｃａｌｉｔｅ上仅有单峰，Ｈ２Ｏ２或分子Ｏ２在催化剂表面吸附后，在脱附物种中可用质谱检测到原子Ｏ（１６）物种；说明Ｈ２Ｏ２或分子Ｏ２在样品表面存在解离吸附；并发现解离子分子Ｏ２的活性很低，ＴＳ－１能同时吸附内烯和Ｈ２Ｏ２，而在ＳｉＯ２／Ｓｉｌｉｃａｌｉｔｅ表面的吸附却与吸附顺序有关，环氧化活性顺序如下：ＴＳ－１     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.