异喹啉及其衍生物的表面增强喇曼光谱研究

采用表面增强喇曼光谱（ＳＥＲＳ）技术获得了异喹啉及其衍生物（３－羧基异喹啉、１－羧基异喹啉、甲基－３－异喹啉羧酸酯、１－羟基异喹啉、５－羟基异喹啉、１，５－二羟基异喹啉）的ＳＥＲＳ谱图，谱带分析表明由于异喹啉环上取代基不同、取代位置不同，均可导致其ＳＥＲＳ光谱的变化。其中１－羟基异喹啉、甲基－３－异喹啉羧酸酯、３－羧基异喹啉、异喹啉是垂直吸附于银胶表面。而１，５－二羟基异喹啉与５－羟基异喹啉则是通过环上π电子云平躺吸附于银胶表面。     

2－异丙基－1，3－二氢－4（1H）异喹啉酮及其衍生物的合成

异喹啉酮（1）与羟胺反应得异喹啉酮肟（2），再经Schroeter重排合成得到 4-氨基异喹啉的盐（3），进而经催化加氢还原生成其脱烷基产物6.另外 ，异喹啉 酮与NaN3反应合成得到苯并二氮杂Zhuo酮（4），4经还原可生成苯并二氮杂Zhuo（ 5），合成得到的5个新化合物的结构经元素分析、红外、^1H NMR及质谱等方法所 证实。     

2－杂萘满并喹啉衍生物的合成及其抑菌活性

２－杂萘满并喹啉衍生物的合成及其抑菌活性刘永军，刘英（曲阜师范大学化学系曲阜２７３１６５）关键词杂萘满酮，合成，抑菌活性在２－杂萘满酮的化学结构，最常见的杂原子为Ｏ、Ｓ、Ｎ，分别俗称异色满酮、硫代异色满酮、异喹啉酮．自然界中的许多天然或代谢产物如卡拉...     

6,7—取代—1H—苯并（de）异喹啉—1,3（2H）二酮的合成

从二氢苊出发合成了６－溴－７－氨基２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮，６－甲氧基－７－氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮和６，７－二氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮，测定了它们的荧光量子产率，讨论了分子内重原子溴和给电子基对化合物荧光性质的影响。     

盐酸溶液中阴离子表面活性剂在铝表面上的吸附

用失重法研究了盐酸溶液中阴离子表面活性剂十二烷基磺酸钠（ＤＳＡＳＳ），十二烷基苯磺酸钠（ＤＢＳＡＳ）以及十二烷基硫酸钠（ＳＤＳ）在铝表面上的吸附作用，提出这种吸附作用与铝的失重量有关，且符合Ｌａｎｇ－ｍｕｉｒ方程，计算出吸附热，吸附熵和吸附自由能等热力学参数。认为这种吸附主要靠静电作用，根据接触角的变化讨论了阴离子表面活性剂分子在铝表面上的吸附取向。     

交联壳聚糖在锑形态分析中的应用

研究了交联壳聚糖（ＣＣＴＳ）对Ｓｂ（Ⅲ）－吡咯烷二硫代氨基甲酸铵（ＡＰＤＣ）和Ｓｂ（Ⅴ）－ＡＰＤＣ的吸附行为，并探讨了吸附机理。结果表明：在ｐＨ＝２时Ｓｂ（Ⅲ）－ＡＰＤＣ和Ｓｂ（Ⅴ）－ＡＰＤＣ的吸附率分别为９６％和９８％。吸附后，利用Ｓｂ（Ⅲ）和Ｓｂ（Ⅴ）形成氢化物的不同条件分别测定，建立了氢化物发生原子吸收（ＨＧＡＡＳ）测定水中痕量Ｓｂ（Ⅲ）和Ｓｂ（Ⅴ）的方法。该法的检出限为６０ｎｇ／Ｌ，回收率为９５％～１０７％，相对标准偏差为２１％～５６％。     

新型氮杂蒽醌衍生物的设计、合成及抗肿瘤活性

以氮杂蒽醌为母核结构，通过引入卤素和氨基侧链，设计并合成了4种新型的氮杂蒽醌衍生物（AQ-1~4）。其中，以异喹啉为起始原料，依次经氧化，脱水和傅克环酰化反应，制得6,9-取代苯并[g]异喹啉-5,10-蒽醌卤代衍生物（AQ-1和AQ-2）; AQ-F与胺类化合物发生芳环亲核取代反应，合成了6,9-二取代苯并[g]异喹啉-5,10-蒽醌衍生物（AQ-3和AQ-4），其结构经¹H NMR, ¹³C NMR和HR-MS（ESI）表征。采用CCK-8法研究了AQ-1~4对人肺癌细胞（A549），人乳腺癌细胞（MCF 7）和人宫颈癌细胞（Hela）的体外抗肿瘤活性。结果表明：AQ-4的抑制活性最好，IC₅₀分别为14.84 μmol·L^-1, 10.36 μmol·L^-1和10.55 μmol·L^-1。     

锆基金属有机骨架材料用于四甲基硅烷/异戊烷分离

在半导体工业中，从四甲基硅烷（TMS）/异戊烷混合物中高效捕获异戊烷从而获得超高纯度的TMS是非常重要的。在本工作中，我们选择了具有笼结构的MOF-801，通过其对TMS和异戊烷吸附能力的差异，实现了TMS与异戊烷的分离。气体吸附测试结果表明，在298 K和60 kPa时，MOF-801对异戊烷吸附量为2.56 mmol·g^-1，而其对TMS的吸附量为1.20 mmol·g^-1。理想吸附溶液理论（IAST）计算结果表明，MOF-801对TMS/异戊烷（95∶5，体积比）混合物的分离选择性达到105.8。而之后的液相吸附分离实验进一步验证了MOF-801的分离效果，最终可以得到体积分数大于99.98%的TMS。     

杂多酸的固载化Ⅲ．溶剂对H_4SiW_（12）O_（40）·24H_2O在活性

研究了Ｈ＿４ＳｉＷ＿（１２）Ｏ＿（４０）·２４Ｈ＿２Ｏ（ＳｉＷ＿（１２））在水、乙醇、乙酸、乙酸丁酯中在活性炭上的吸附得出，活性炭微孔结构对ＳｉＷ＿（１２）在其表面的吸附起着分子筛作用。水溶剂化的ＳｉＷ＿（１２）分子可顺利进入活性炭１．７ｎｍ左右的微孔，而其它溶剂化的ＳｉＷ＿（１２）分子，则需较大的孔径。提出了ＳｉＷ＿（１２）在活性炭表面吸附的微孔中孔扩散模型。     

巯基棉分离吸附溶出伏安法测定茶叶及茶汤中痕量砷

本文研究了巯基棉纤维（ＳＣＦ）对Ａｓ（Ⅲ）和Ａｓ（Ⅴ）的吸附性能，建立了ＳＣＦ分离Ａｓ（Ⅲ）和Ａｓ（Ⅴ）吸附溶出伏安法测定生物样品中痕量砷的方法。结果表明：在１ｍｏｌ／Ｌ盐酸介质中，ＳＣＦ可定量吸附Ａｓ（Ⅲ），Ａｓ（Ⅴ）不被吸附；用ＫＩ－（ＮＨ２）２ＣＳ预先还原Ａｓ（Ⅴ），通过ＳＣＦ分离，可消除干扰离子对测定砷的影响。方法用于测定桃叶、煤飞灰及番茄叶标样中的砷，其结果与标准值相符；应用此法还测定了几种茶叶及茶汤中的痕量砷和不同价态的砷，结果令人满意。     

银催化的环化反应合成异喹啉的研究进展

含有异喹啉骨架的化合物是一类很重要的含氮杂环化合物,广泛存在于具有生物活性的天然产物、有机材料、以及药物分子中。传统的合成异喹啉的方法需要苛刻的反应条件,因此使用温和,简单的方法构建这一骨架的化合物具有重要的现实意义。银类化合物具有路易斯酸特性能够催化活化三键,利用这一特点并使用含氮的亲核试剂进行分子内亲核加成活化的三键是合成异喹啉衍生物的重要方法。本文主要综述了以2-炔基苄亚胺、2-炔基苄基叠氮、2-炔基苯甲醛肟、2-炔基苯甲醛腙及其（2-（乙炔基）芳基）-1,2,3-三唑为反应物,在银催化条件下构建异喹啉环的研究进展,并对部分反应的机理进行了讨论。     

An expeditious approach to 1-(isoquinolin-1-yl)guanidines via a three-component reaction of 2-alkynylbenzaldehyde, sulfonohydrazide, with carbodiimide

A small library of 1-(isoquinolin-1-yl)guanidine is constructed efficiently via a silver triflate-catalyzed three-component reaction of 2-alkynylbenzaldehyde, sulfonohydrazide, with carbodiimide. The preliminary biological screens of these isoquinoline library members have been evaluated, which show promising results as PTP1B inhibitor and HCT-116 inhibitor.     

Synthesis of H-pyrazolo[5,1-a]isoquinolines via a silver triflate-catalyzed tandem reaction of N′-(2-alkynylbenzylidene)hydrazide with alcohol

A silver triflate-catalyzed tandem reaction of N′-(2-alkynylbenzylidene)hydrazide with alcohol is reported, which generates H-pyrazolo[5,1-a]isoquinoline derivatives in good yields under mild conditions.     

Total synthesis of the antitumor active pyrrolo[2,1-a]isoquinoline alkaloid (±)-crispine A

Addition of a propargyl Grignard reagent to 3,4-dihydro-6,7-dimethoxyisoquinoline, silver(I)-promoted oxidative cyclization, and chemoselective hydrogenation of the pyrrole ring provide a simple three-step route to the antitumor active pyrrolo[2,1-a]isoquinoline alkaloid (±)-crispine A.     

Cp*Co(III) catalyzed annulation of N-Cbz hydrazones for the redox-neutral synthesis of isoquinolines via C–H/N–N bond activation

Abstract

A new cascade oxidative cyclization reaction of N-Cbz hydrazones with internal alkynes has been explored for the preparation of isoquinoline derivatives using Cp*Co^III-catalyst through C–H and N–N bond functionalization. N-Cbz hydrazones are rarely explored as directing group for redox-neutral [4?+?2] cyclization reaction through the cyclometallation and this catalyst system does not require any external oxidizing agent, as well as, silver or antimony salt. The current efficient approach has been utilized for the synthesis of different isoquinoline derivatives with good regioselectivity and yields.     

Comparison of the adsorption orientation for 2-mercaptobenzothiazole and 2-mercaptobenzoxazole by SERS spectroscopy

In this study, the adsorption orientation for 2-mercaptobenzothiazole (MBT) and 2-mercaptobenzoxazole (MBO) on to silver mirror and silver sol substrates have been studied by surface enhanced Raman scattering (SERS). The MBT and MBO were chemisorbed on both silver mirror and silver sol after deprotonation with a tilted orientation to the silver surfaces. The surface enhanced properties of MBT and MBO showed that the substrate of silver mirror was superior to the sliver sol. The SERS spectra of MBT and MBO revealed that both of the MBT and MBO were adsorbed on silver surfaces strongly by a common sulfur molecule and a sulfur atom from MBT and an oxygen atom from MBO. Therefore, the adsorption orientation of MBT and MBO was little tilted perpendicularly to the silver surfaces. The adsorption geometry did not undergo any significant changes in acidic and basic solutions. It showed that the adsorption orientation for MBT and MBO were stable in the both solutions.     

Efficient Pathway for the Preparation of Aryl(isoquinoline)iodonium(III) Salts and Synthesis of Radiofluorinated Isoquinolines

Iodonium compounds play a pivotal role in ¹⁸F‐fluorination of radiopharmaceuticals containing non‐activated arenes. However, preparation of these species is limited to oxidation conditions or exchange with organometallics that are prepared from aryl halides. Herein we describe a novel “one‐pot” process to assemble aryl(isoquinoline)iodonium salts in 40–94 % yields from mesoionic carbene silver complex and Aryl‐I‐Py₂(OTf)₂. The method is general, practical, and compatible with well‐functionalized molecules as well as useful for the preparation of a wide range of ¹⁸F‐labeled isoquinolines resulting in up to 92 % radiochemical conversion. As proof of concept, a fluorinated isoquinoline alkaloid, ¹⁸F‐aspergillitine is prepared in 10 % isolated radiochemical yield from the corresponding phenyl(aspergillitine)iodonium salt.     

Orienting influence of silver crystals upon the growth of surface oxides

Conclusions The orientation of crystals of metallic silver determines the orientation of the crystals formed on the metal oxide and silver peroxide. The cause of the conservation of the orientation is the closeness of the dimensions of their planer cells. The large oxygen ions can be inserted into the surface layer of the metal as a result of the substantial decrease in the dimensions of its atoms during ionization.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 512–515, March, 1967.     

Surface-enhanced Raman scattering and the adsorption behavior of (RS)-phenylsuccinic acid

The surface geometry of (RS)-phenylsuccinic acid molecule was studied by analysis of the SERS spectra of aromatic dicarboxylic acid adsorbed on silver colloid surfaces. For a reliable analysis of the SERS spectrum, we also performed density functional theoretical calculations. The SERS spectral features indicated that the RSPSA molecules should bound to the silver as dicarboxylate, with a strongly tilted orientation with respect to the normal to the surface. Such a tilted orientation was presumed to occur by the simultaneous sigma and pi-type coordination of carboxylate groups to silver surface caused by the steric hindrance and electrostatic repulsion between the two carboxylate groups, and thereby RSPSA on silver was easily displaced with aromatic carboxylic acids. A sigma-type coordination therefore seemed to be more important than a pi-type coordination for aromatic carboxylic acid derivatives to assemble on a silver surface. The large enhancement of in-plane bending, out of plane bending and ring breathing modes in the surface-enhanced Raman scattering spectrum indicates that the molecule is adsorbed on the silver surface in a 'at least vertical' configuration, with the ring perpendicular to the silver surface.     

FT-IR, FT-Raman and SERS spectra of Vitamin C

FT-IR and FT-Raman spectra of Vitamin c have been recorded and analysed. SERS spectrum was recorded is silver colloid. The molecule is thought to adsorb with the lactone ring in a tilted side on orientation with respect to the silver surface.