D-氨基葡萄糖甘氨酸混配金属配合物与DNA作用的光谱研究

研究了４种Ｄ－氨基葡萄糖甘氨酸混配金属配合物的表面增强拉曼光谱（ＳＥＲＳ）,发现它们在银胶上的吸附方式基本相同,因而ＳＥＲＳ光谱相似,用电子光谱、荧光光谱、表面增强拉曼光谱研究了它们与ＤＮＡ的相互作用,发现这４种化合物与ＤＮＡ的作用能力有很大的不同,其中ＧｕＧｌｕＧ、Ｃｏ（Ⅲ）ＧｌｕＧ是值得进一步研究的可能抗癌的药物。     

DNA结合蛋白的分子识别研究:单体酵母转录激活因子GCN4能特异性识别其二聚体的DNA结合位点

一般认为形成二聚是酵母转录激活因子ＧＣＮ４特异性识别其ＤＮＡ结合位点的 前提．以天然蛋白ＧＣＮ４的碱性区（２２６－２５２）作为单体肽ＧＣＮ４－Ｍ,以二硫键Ｓ－Ｓ连接的 肽作为二聚体肽ＧＣＮ４－Ｄ,研究了它们与天然蛋白ＧＣＮ４的结合位点ＡＰ－１和ＣＲＥ的相 互识别作用．ＣＤ和ＩＴＣ实验表明,尽管与二聚体肽ＧＣＮ４－Ｄ相比,单体肽ＧＣＮ４－Ｍ与 ＤＮＡ的结合力较弱,但是,ＧＣＮ４－Ｍ能序列特异性识别ＤＮＡ结合位点ＡＰ－１和ＣＲＥ．     

N-β-萘酚醛-D-氨基葡萄糖席夫碱金属配合物与DNA作用的谱学研究

合成了Ｎ－β－萘酚醛－Ｄ－氨基葡萄糖席夫碱（Ｃ１７Ｈ１９Ｏ６Ｎ,简写为ＮＧ）的Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）、Ｎｉ（Ⅱ）、Ｆｅ（Ⅱ,Ⅲ）、Ｃｏ（Ⅱ,Ⅲ）金属配合物,并用电子吸收光谱、荧光光谱、表面增强拉曼光谱研究了它们与ＤＮＡ的相互作用。探讨了这们与ＤＮＡ的作用方式,发现具有萘环结构的化合物与ＤＮＡ容易发生插入作用,其中Ｃｕ（Ⅱ）ＮＧ,Ｆｅ（Ⅱ）ＮＧ,Ｆｅ（Ⅱ）ＮＧ,Ｃｏ（Ⅱ）ＮＧ,Ｃｏ（Ⅲ）ＮＧ作为抗癌药物有进一步研究的价值。     

N-β-萘酚醛-D-氨基葡萄糖席夫碱甘氨酸金属络合物与DNA作用的谱学研究

1　引　　言席夫碱化合物在抗癌化合物研究中占有重要地位 ,它们与某些金属生成络合物抗癌效果更佳。对化合物与ＤＮＡ相互作用体系的研究可揭示化合物的结构与生物活性的关系 ,许多化合物抗癌能力与它们结合ＤＮＡ时的插入作用紧密相关 ,在前期研究中我们提出ＳＥＲＳ可作为抗癌药物初步筛选法 ,因为氨基酸络合物及ＮＧ系列络合物均表现有抗癌活性 ,本文选择通过ＮＧ系列络合物及氨基酸反应合成的 4种Ｎ Ｂ 萘酚醛 Ｄ 氨基葡萄糖席夫碱甘氨酸混配金属洛合物为研究对象 ,研究了它们与ＤＮＡ作用的光谱变化情况 ,并与ＮＧ系列络合物的研究结…     

钌联吡啶络合物与脱氧核糖核酸分子相互作用的荧光光谱研究与？…

合成了２苯基（４－溴）咪唑「ｆ」邻菲咯啉（简称ＰＩＰⅢ）新的配体及「Ｒｕ（ｂｐｙ）２ＰＩＰ（Ⅲ）」＾２＋新的络合物,用荧光光谱研究了络合物与小牛胸腺ＤＮＡ分子的结合情况,在ｐＨ７．４,络合物与ＤＮＡ作用后,在５８７ｎｍ（λｅｘ＝４７１ｎｍ）产生很强的荧光峰,其发光强度与ＤＮＡ浓度呈线性关系;     

DNA与邻苯二胺-过氧化氢-过氧化物酶体系相互作用的光谱研究

用光谱方法研究了邻苯二胺－过氧化氢－过氧化物酶体系与ＤＮＡ的作用，认为二者之间发生的是嵌插作用。分别用ＵＶ－Ｖｉｓ光谱和荧光光谱求得了形成常数，两种方法具有一致性。讨论了ｐＨ值对嵌插作用的影响。     

DNA与邻苯二胺—过氧化氢—过氧化物酶体系相互作用的光谱研究

用光谱方法研究了邻苯二胺－过氧化氢－过氧化物酶体系与ＤＮＡ的作用，认为二者之间发生的是嵌插作用。分别用ＵＶ－Ｖｉｓ光谱和荧光光谱求得了形成常数，两种方法具有一致性。讨论了ＰＨ值对嵌插作用的影响。     

中位—四（4—N—氰甲基吡啶）卟啉—铜（Ⅱ）络合物及其与脱氧核糖核酸…

本文在银胶活性基质上获得了Ｃｕ（Ⅱ）的中位－四（４－Ｎ－氰甲基吡啶）卟啉络合物Ｃｕ（Ⅱ）ＮＡＣＮ的表面增强喇曼光谱光谱，并与其ＲＲＳ光谱作了比较，讨论了ＰＨ值和Ｃｕ（Ⅱ）ＮＡＣＮ的复合物的ＳＥＲＳ光谱的影响，研究了小牛胸腺双链ＤＮＡ及其变性ＤＮＡ与Ｃｕ（Ⅱ）ＮＡＣＮ的复合物的ＳＥＲＳ光谱，指出Ｃｕ（Ⅱ）ＮＡＣＮ是通过吡啶氮和卟啉核共同与银胶作用的，Ｃｕ（Ⅱ）ＮＡＣＮ是斜向吸附在银表面上的，最佳ＰＨ     

用表面增强喇曼光谱研究8种席夫碱化合物及其对脱氧核糖核酸的作用

研究了Ｎ－β－萘酚醛－Ｄ－氨基葡萄糖夫碱及其７种新金属络合物的表面增强喇曼光谱，探讨了它们的振动光谱特征，发现它们在银胶上的吸附方式并不相同，因而在ＳＥＲＳ光谱中存在着明显差异。用ＳＥＲＳ光谱研究了它们与ＤＮＡ的作用。     

D—氨基葡萄糖单配金属配合物与DNA作用的光谱研究比较

研究了５种Ｄ－氨基葡萄糖金属配合物的表面增强喇曼光谱（ＳＥＲＳ），发现它们在银胶上的吸附方式基本相同，因而有相似的ＳＥＲＳ光谱，并用ＳＥＲＳ光谱研究了它们对ＤＮＡ的作用。     

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%.     

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.     

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.     

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.     

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.