冬凌草甲素和冬凌草乙素与谷胱苷肽的迈克尔加成反应

采用紫外光谱动力学方法测定了抗肿瘤对映贝壳杉烯二萜冬凌草甲素和冬凌草乙素与谷胱苷肽迈克尔加成反应的级数、速率常数和平衡常数.结果表明,冬凌草甲素和冬凌草乙素与与谷胱苷肽迈克尔加成反应符合二级动力学方程,25℃下的速率常数分别为16.196 0L·(mol·s)-1和7.480 5L·(mol·s)-1,平衡常数分别为177.98L/mol和85.60L/mol.冬凌草甲素与谷胱苷肽迈克尔加成反应速率和反应程度均比冬凌草乙素的大得多,反应活性更好.对映贝壳杉烯二萜通过与机体发生迈克尔加成反应而产生抗肿瘤作用;因此,冬凌草甲素可能比冬凌草乙素具有更好的抗肿瘤活性.     

紫草素的电化学伏安行为研究

紫草素在0.2 mol/L HAc-NaAc缓冲溶液(pH4.3)中,产生灵敏的线性扫描极谱峰,峰电位EP=-0.186 V(vs.Ag/AgCl)。峰电流与紫草素浓度在5×10-7~1×10-5mol/L范围内呈良好的线性关系。可用于紫草中紫草素含量的测定。用线性扫描和循环伏安法测试表明,该体系属具有反应物吸附性的可逆过程体系。     

钯掺杂聚精氨酸修饰电极同时测定5-羟基色氨酸和多巴胺

制备了钯掺杂聚L-精氨酸修饰玻碳电极(Pd-PA/GCE),研究了5-羟基色氨酸(5-HTP)和多巴胺(DA)在该修饰电极上的电化学行为,建立了同时测定5-HTP和DA的电化学新方法。在pH=2.0的磷酸缓冲溶液中,扫描速率为160mV/s时,DA在该电极上产生一对氧化还原峰,峰电位分别为0.515V和0.464V;5-HTP在该电极上产生一个氧化峰,峰电位为0.643V,两者的氧化峰电位差达128mV。在最优条件下,同时测定5-HTP和DA的线性范围分别为:9.00×10-7~1.00×10-5 mol/L、1.00×10-5~4.00×10-5 mol/L(5-HTP);7.00×10-7~1.00×10-5 mol/L、1.00×10-5~4.00×10-5 mol/L(DA)。检出限分别为7.0×10-7 mol/L和5.0×10-7 mol/L。方法可用于药剂中5-HTP和DA的测定。     

血红蛋白-维生素B6-ONOO-体系的荧光特性及ONOO-分析

在中性pH值的缓冲溶液中,血红蛋白作催化剂,维生素B6与过氧亚硝酸活性氧(ONOO-)发生反应,维生素B6原来位于391 nm处的强烈的荧光发射峰消失,而在384 nm和424 nm处出现了两个新的荧光峰.据此建立了血红蛋白一维生素B6体系高灵敏检测ONOO-活性氧的新方法.方法的线性范围为5.24×10-8～2.62×10-6mol/L,检出限为2.62×10-9mol/L,对1.31×10-7mol/L的ONOO-溶液测定的相对标准偏差为3.75%(n=7).     

聚L-甲硫氨酸修饰电极的制备及对尿酸的测定

在pH9.5的磷酸盐缓冲溶液中,利用循环伏安(CV)法制备了聚L-甲硫氨酸修饰玻碳电极(PLMet/GC/CME)。研究了尿酸(UA)在该电极上的电化学行为,建立了伏安法测定UA的新方法。在pH5.0的磷酸缓冲溶液中,扫描速率为200 mV/s,循环扫描电位在-0.3~1.0 V时,UA在PLMet/GC/CME上产生一个灵敏的氧化峰,峰电位位于0.52 V(vs.Ag/AgCl)。用CV法、线性扫描伏安(LSV)法和示差脉冲伏安(DPV)法对UA进行测定,测定的线性范围分别为2.50×10-6~1.00×10-4mol/L、5.00×10-6~1.00×10-4mol/L和8.00×10-7~1.00×10-4mol/L;检出限分别为8.0×10-7mol/L(CV、LSV法)和5.0×10-7mol/L(DPV法)。用LSV法对尿样中的UA进行测定,结果满意。     

聚赖氨酸修饰电极在抗坏血酸共存时测定肾上腺素

在pH8.0磷酸盐缓冲溶液(PBS)中利用循环伏安法制备了聚赖氨酸修饰电极,在pH4.0 PBS中,聚赖氨酸膜对肾上腺素(EP)的电化学氧化具有明显的催化作用.利用循环伏安法测定EP还原峰电流可排除抗坏血酸(AA)干扰.肾上腺素还原峰电流与其浓度分别在6.3×10-7mol/L~1.0×10-5 mol/L与1.0×10-5mol/L~1.2×10-4 mol/L范围内呈良好线性关系,相关系数分别为0.9978与0.9975,;检出限(S/N=3)为7.2×10-8mol/L.该方法具有良好的灵敏度、选择性,已用于针剂样品分析.     

对硫磷在纳米氧化铝薄膜修饰电极上的电化学行为及其测定

制备了纳米氧化铝修饰玻碳电极(nano-Al2O3/GCE/CME),用循环伏安法(CV)、线性扫描伏安法(LSV)研究了对硫磷(TP)在nano-Al2O3/GCE/CME上的电化学行为.实验表明,该修饰电极与裸电极相比能显著提高TP的氧化还原峰电流并降低其氧化峰电位.在0.1 mol/L HAc-NaAc缓冲溶液(pH =5)中,TP在该修饰电极上产生1个不可逆的还原峰( Epc1=-0.567 V)和1对可逆氧化还原峰( Epa2=0.018 V和Epc2=-0.008 V) ,氧化峰电流与TP的浓度在2.5×10-9～1.0×10-7 mol/L和1.0×10-7～1.0×10-5 mol/L范围内具有良好的线性关系,回归方程分别为: ip(μA)=0.2529+4.201C(μmol/L), r=0.9984和ip(μA)=0.6752+0.3181C(μmol/L), r=0.9946.开路富集30 s后,检出限为1.0 ×10-9 mol/L(S/N=3).在1.0×10-5 mol/L TP试液中连续测定10次,其RSD为3.8%.用此方法测定了蔬菜中TP的含量,回收率为95. 6%～100.5% ,结果满意.     

阳极微分脉冲伏安法测定麦迪霉素

探讨了不同pH溶液中,麦迪霉素在玻碳电极上的伏安行为。在pH=7.0的NH_4Ac溶液中,麦迪霉素有一个灵敏的氧化峰,阳极微分脉冲扫描峰电位为 0.81V(vs·SCE)。其浓度在10×10~(-7)～1.5×10~(-5)mol/L范围内与微分脉冲伏安峰电流呈线性关系,检测限为5×10~(-8)mol/L。     

靛红在碳糊电极上的阴极吸附伏安法研究

利用极谱分析仪,在0.40 mol/L的HAc-NaAc(pH 6.0)缓冲液中,发现靛红在碳糊电极(CPE)上有一灵敏的吸附伏安还原峰,峰电位为-0.44 V(vs.SCE)。该还原峰的二阶导数峰电流与靛红的浓度在4.0×10-8~1.0×10-7mol/L(富集90 s)范围内成良好的线性关系,相关系数为0.9954,检出限为8.0×10-9mol/L(S/N=3,富集110 s)。探讨了靛红在碳糊电极上的伏安性质和电极反应机理,并且成功应用于中草药青黛中靛红含量的测定。     

单层碳纳米管修饰电极上盐酸曲普利啶的电化学行为及其应用研究

应用循环伏安法研究了盐酸曲普利啶在碳纳米管修饰电极上的电化学行为.结果表明:在0.1 mol/L磷酸盐缓冲溶液(pH 6.9)中,盐酸曲普利啶产生一灵敏的氧化峰,其峰电位为0.81 V(vs.Ag/AgCl),峰电流与盐酸曲普利啶在1.0×10-6～1.3×10-4 mol/L浓度范围内呈线性关系,检出限为5.0×10-7mol/L,已用于片剂中盐酸曲普利啶的测定.     

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.