高效离子交换液相色谱法分离绿脓杆菌外膜蛋白

 利用高效ＤＥＡＥ离子交换液相色谱法分离纯化了绿脓杆菌标准菌株ＰＡＯ１外膜蛋白。流动相为ｐＨ８．０Ｔｒｉｓ－ＨＣｌ缓冲液,色谱柱为ＴＳＫｇｅｌ－ＤＥＡＥ－５ＰＷ（０．７５ｃｍ×７．５ｃｍｉ．ｄ．）。通过纯化外膜蛋白,可以为研究绿脓杆菌外膜通透性与抗生素耐药性之间的关系及缩短研究周期提供有效的方法。     

锆—氟—7—碘—8—羟基喹—5—磺酸—EDTA—表面活性剂体系的荧光光度研究

在ＰＨ５．５－７．０的ＨＡｃ－ＮａＡｃ缓冲溶液中，锆与氟、７－碘－８－羟基喹啉－５磺酸、ＥＤＴＡ及十六烷基溴化铵形成五元荧光络合物，其组成为Ｚｒ（Ⅳ）：Ｆ：Ｈ２ＱＳＩ：ＥＤＴＡ：ＣＴＭＡＢ＝１：２：１：１：４。络合物的最大激发波长（λｅｘ）为３６５ｎｍ，最大发射波长为５００ｎｍ。     

用分光光度法连续测定血清中微量铜、锌的研究

研究了在ＴｒｉｔｏｎＸ－１００存在下,在ＰＨ８．０的乙醇介质中,用５－Ｂｒ－ＰＡＤＡＰ作为显色剂,应用分光光度法连续测定血清中的铜,锌。本法具有较高的灵敏度,Ｃｕ＾２＋－５－Ｂｒ－ＰＡＤＡＰ的ε为８．５０＊１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１,Ｚｎ＾２＋－５－Ｂｒ－ＰＡＤＡＰ的ε为９．６５＊１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１。铜线性范围为０－０．４５ｍｇ．Ｌ＾－１,锌线性范围为０－０．４０ｍｇ．     

Base－Catalyzed Rearrangement of 11－Isopropylidene－anti－4，5－Epoxyendo－Tricyclo［6．2．1．0~（2，7）］ Undeca－4，9－Diene－3，6－Dione

Ｂａｓｅ－ＣａｔａｌｙｚｅｄＲｅａｒｒａｎｇｅｍｅｎｔｏｆ１１－Ｉｓｏｐｒｏｐｙｌｉｄｅｎｅ－ａｎｔｉ－４，５－Ｅｐｏｘｙｅｎｄｏ－Ｔｒｉｃｙｃｌｏ［６．２．１．０~（２，７）］Ｕｎｄｅｃａ－４，９－Ｄｉｅｎｅ－３，６－ＤｉｏｎｅＸｉａｏＰｅｉＧＵＡ?..     

STUDIES ON THE SYNTHESIS OF SESAMIN－GROUP LIGNANS V． A CONVENIENT METHOD FOR THE PREPARATION OF 2－ARYL－4－PHENYLOXAZOLES

ＳＴＵＤＩＥＳＯＮＴＨＥＳＹＮＴＨＥＳＩＳＯＦＳＥＳＡＭＩＮ－ＧＲＯＵＰＬＩＧＮＡＮＳＶ．ＡＣＯＮＶＥＮＩＥＮＴＭＥＴＨＯＤＦＯＲＴＨＥＰＲＥＰＡＲＡＴＩＯＮＯＦ２－ＡＲＹＬ－４－ＰＨＥＮＹＬＯＸＡＺＯＬＥＳ￥Ｃｏｒｒｅｓｐｏｎｄｅｎｔａｕｔｈｏｒ．２－ａｒｙｌ－４－ｐｈｅｎｙｌｏｘａｚｏｌｅｓ．Ｔｈｅｏｔｈｅｒｏｌｌｅｂｙｔｈｅｒｅａｃｔｉｏｎｏｆａ－ｍｅｔｈｙｌｐｈｅｎａｃｙｌｂｅｎｚｏａｔｅｗｉｔｈａｍｍｏｎｉｕｍａｃｅｔａｔｅｉｎｂｏｉｌｉｎｇａｃｅｔｉｃａｃｉｄｔｏｆｏｒｍａｆｕｔｕｒｅｏｆ２，４－ｄｉｐｈｅｎｙｌ－５ｍｅｔｈｙｌｏｘａｚｏｌｅａｎｄ２，４－ｄｉｐｈｅｎｙｌ－５－ｒｎｅｔｈｙｌｉｎｄｄａｚｏｌｅｂｏｔｈｉｎａｂｏｕｔ４０％ｙｉｅｌｄ，ｈｉｌｔｔｉｌｌｓｍｅｔｈｏｄｉｓａｐｐｌｉｃａｂｌｅｆｏｒｔｈｅｐｒｅｐａｒａｔｉｏｎｏｆ２－ａｒｙｌ－４－ｐｈｅｎｙｌｏｘａｚｏｌｅｓ．Ｂｙａｎａｌｏｇｙ，ｐｌｉｅｎａｃｙｌｂｅｎｚｏａｔｅｉｓａｌｌｏａｌｌｏｗｅｄｔｏｒｅａｃｔｗｉｔｈａｌｎｍｏｎｉｌｌｍａｃｅｔａｔｅｉｎｂｏｉｌｉｎｇａｃｅｔｉｃａｃｉｄ．Ａｍｉｘｔｕｒｅｏｆ２，４－ｄｉｐｈ     

钛(Ⅳ)-5-Br-PADAP-NaClO_3体系极谱吸附催化波的研究

２－（５－溴－２－吡啶偶氮）－５－二乙氨基苯酚（５－Ｂｒ－ＰＡＤＡＰ）在极谱和伏安分析中的应用已有一些报道。陈林林等曾经研究过Ｔｉ（Ⅳ）－５－Ｂｒ－ＰＡＤＡＰ络合物在稀Ｈ２ＳＯ４－Ｈ２Ｃ２Ｏ４溶液中的极谱行为,但灵敏度不高（１．０×１０－７ｍｏｌ／Ｌ）。我们发现,在ｐＨ４．１左右的ＨＡｃ－ＮａＡｃ底液中,Ｔｉ（Ⅳ）－５－Ｂｒ－ＰＡＤＡＰ－ＮａＣｌＯ３体系产生一灵敏的极谱吸附催化波,二次导数峰电位在－０．８６Ｖ（ｖｓ．ＳＣＥ）左右,波形良好,波高稳定,检测限可达４×１０－１０ｍｏｌ／Ｌ。１　实验部…     

微米级聚酯醚嵌段共聚物微球的制备及其蛋白包裹研究

聚酯 醚嵌段共聚物聚 Ｄ，Ｌ 乳酸 聚乙二醇（Ｐｏｌｙ ＤＬ ｌａｃｔｉｄｅ Ｐｏｌｙｅｔｈｙｌｅｎｅｇｌｙｃｏｌ，ＰＬＡ ＰＥＧ）采用本体聚合法在１８０℃及－９５×１０－２ＭＰａ条件下制得．光谱分析证实产物结构．采用乳液溶剂蒸发法制备ＰＬＡ ＰＥＧ微球，粒径＜５μｍ．以复合乳液技术包裹蛋白．差示扫描量热分析确证ＰＬＡ ＰＥＧ有效包裹蛋白．ＢＣＡ法检测微球蛋白含量．结果表明与均聚物ＰＬＡ比较，ＰＬＡ ＰＥＧ不仅改善了成球条件而且蛋白的包裹效率明显提高．     

口服聚酯聚醚疫苗蛋白微球的制备研究

采用本体聚合法合成不同聚醚含量的聚酯聚醚嵌段共聚物聚 ＤＬ 乳酸 聚乙二醇（Ｐｏｌｙ ＤＬ ｌａｃｔｉｄｅ ｂ ｐｏｌｙｅｔｈｙｌｅｎｅｇｌｙｃｏｌ,ＰＥＬＡ）．ＰＥＬＡ及ＰＬＡ包裹人血清白蛋白（ＨＳＡ）微球采用溶剂挥发法双乳液体系（Ｗ１／Ｏ／Ｗ２）制备．微球球形规整,粒径集中在０５～５０μｍ．用ＣＢＢ法检测微球中蛋白含量,蛋白包裹量达２５％,包裹效率近８０％．从双乳液体系中界面张力角度考察了聚合物囊材的性质、稳定剂的种类及Ｗ１／Ｏ的稳定性等对微球粒径及蛋白包裹量的影响．微球体外释放结果表明ＰＥＬＡ蛋白微球的突释现象不明显,释放速度较为恒定．     

高效液相色谱法测定血清中茶碱浓度

采用高效液相色谱,分析柱：３μｍ,３．３ｃｍ＊４．６ｍｍ,Ｉ．Ｄ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ,ＵＳＡ）;预柱：１０μｍ,１ｃｍ＊２．１ｍｍ,Ｉ．Ｄ（Ｐｅｒｋｉｎ ＥＬｍｅｒ,ＵＳＡ）;以乙酰氨基酚为内标对氯仿－异丙醇（９５：５,Ｖ／Ｖ）提取样品进行了分析,流动相：０．１ｍｏｌ／Ｌ醋酸缓冲液（ＰＨ＝４．５）－甲醇（７０：３０,Ｖ／Ｖ）;检测波长：２７０ｎｍ;流速０．５ｍＬ／ｍｉｎ,３ｍｉｎ即完成一次茶     

酞菁镍—表面活性剂薄膜修饰电极及其催化性能的研究

将酞菁镍（ＮｉＰｃ）掺入阳离子表面活性剂双十二烷基二甲基溴化铵（ＤＤＡＢ）的氯仿溶液中，并涂布于热解石墨电极表面，待氯仿挥发后制得ＮｉＰｃ－ＤＤＡＢ薄膜电极。循环伏安实验表明，在ＫＢｒ溶液中，该薄膜电极有两对良好且稳定的还原氧化峰，第一对峰的Ｅｐｃ１＝－０．６４Ｖ，Ｅｐａｌ＝－０．６０Ｖ（ｖｓ．ＳＣＥ）；第二对峰的Ｅｐｃ２＝－０．８４Ｖ，Ｅｐａ２＝－０．８０Ｖ。本文着重探讨了第二对峰的电化学行为，     

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.     

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.     

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.     

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.