利用粉末微电极检测谷胱甘肽及L-半胱氨酸

本文研究了谷胱甘肽 ( GSH)和 L-半胱氨酸 ( L- cys)在碳粉末微电极上的电化学行为 ,并分别用乙炔黑粉末和 Ketjenblack粉末填充的微电极检测了溶液中GSH和 L- cys的浓度。 GSH和 L- cys在粉末微电极上的检出限分别为 3.4× 1 0 - 6mol/ L和 2 .5× 1 0 - 6 mol/ L,线性范围分别为 3.6× 1 0 - 5～ 4.5× 1 0 - 3mol/ L和 1 .5×1 0 - 5～ 5 .0× 1 0 - 3mol/ L。采用粉末微电极技术完全避免了尿酸和对 -乙酰氨基苯酚对测量谷胱甘肽的干扰 ;0 .0 6mmol/ L的抗坏血酸引起的干扰约为 8%。     

锌电解液中痕量铜、镉、镍和钴的快速同时测定

研究了丁二酮肟 氨 氯化铵 柠檬酸钠 明胶 抗坏血酸体系中Cu(Ⅱ )、Cd(Ⅱ )、Ni(Ⅱ )和Co(Ⅱ )的络合物吸附波 ,建立了同时、快速测定锌电解溶液中这些痕量元素的新方法。Cu(Ⅱ )、Cd(Ⅱ )、Ni(Ⅱ )和Co(Ⅱ )分别在 - 0 44V、- 0 76V、- 1 0 7V和 - 1 2 4V左右产生灵敏的络合物吸附波。信噪比为 3时 ,其检测限分别为 1 0× 1 0 - 8mol/L、1 3× 1 0 - 8mol/L、2 9× 1 0 - 1 0 mol/L和 3 6×1 0 - 1 1 mol/L。铜、镉、镍和钴的浓度分别为 2 0× 1 0 - 8mol/L～ 2 0× 1 0 - 5 mol/L、3 0× 1 0 - 8mol/L～ 3 0× 1 0 - 5mol/L、5 4× 1 0 - 1 0 mol/L～ 5 4× 1 0 - 7mol/L和 6 8× 1 0 - 1 1 mol/L～ 6 8× 1 0 - 8mol/L时 ,与相应峰电流之间有良好的线性关系。方法已用于锌电解液中铜、镉、镍和钴的快速同时测定 ,相对标准偏差分别小于或等于 4 7%、5 1 %、4 9%和 5 3 %。     

流动注射电化学发光法测定半胱氨酸和谷胱甘肽

采用流动注射分析技术研究了半胱氨酸和谷胱甘肽对鲁米诺微弱电化学发光的增敏行为。对影响电化学发光的各因素进行了试验和探讨 ,提出了可能的反应机理 ,并建立一种电化学发光测定半胱氨酸和谷胱甘肽的新方法。半胱氨酸和谷胱甘肽的浓度在 1 .0× 1 0 - 6 mol/L～ 5 .0× 1 0 - 5 mol/L和 1 .0× 1 0 - 6mol/L～ 2 .0× 1 0 - 5 mol/L之间呈良好的线性关系 ,相关系数分别为 0 .993和0 998,检出限分别为 0 .67μmol/L和 0 .72 μmol/L。对 1 .0× 1 0 - 5mol/L的半胱氨酸和谷胱甘肽进行 1 1次平行测定 ,相对标准偏差分别为 4.5 %和 3.7%。     

噻吩甲酰三氟丙酮的电化学性质及应用

在 0 .5mol/LHCl和 0 .2g/L的明胶溶液中 ,利用线性扫描极谱法测定噻吩甲酰三氟丙酮 (简称TTA) ,发现有一还原峰 ,其峰电位是 - 1 .0 0V (vs.SCE)。峰电流与TTA浓度在 2 .5× 1 0 - 5mol/L～ 2 .0× 1 0 - 3mol/L之间存在线性关系 (r=0 .9986) ,检测下限为 1 .0× 1 0 - 5mol/L。利用单扫描极谱法和循环伏安法对极谱峰的电化学性质进行了研究     

泼尼松的示波极谱测定及其电化学行为

基于泼尼松产生的极谱还原波 ,提出了测定泼尼松的单扫描示波极谱法。在0 .1 2 mol/ L HAc-0 .0 8mol/ L Na Ac ( p H 4.6)的缓冲溶液中 ,泼尼松于 -1 .1 3 V处产生一极谱还原波。二阶导数峰电流与其浓度在 2 .4× 1 0 - 6～ 1 .6× 1 0 - 5mol/ L范围内有良好的线性关系 ( r=0 .9991 ,n=8) ,检出限为 8.0× 1 0 - 7mol/ L。测定了片剂中泼尼松的含量。讨论了泼尼松的电化学行为     

土霉素在碳纳米管修饰电极上的电化学行为研究及其测定

研究了土霉素 (OTC)在 MWNT修饰电极上的伏安行为 ,优化了测定参数 ,在此基础上建立了一种直接测定土霉素的电化学分析方法。还原峰电流与土霉素的浓度在 2× 1 0 - 7～ 5× 1 0 - 5mol/L之间有很好的线性关系。开路富集 2 min后的检出限为 5× 1 0 - 8mol/L。用此方法测定了土霉素片剂中土霉素的含量 ,结果满意     

铬蓝黑R-示波计时电位法快速测定天然水中不同形态的铝浓度

本文报道铬蓝黑 R-示波计时电位法快速测定天然水中不同形态的铝。在 0 .5mol/L 乙酸 -乙酸铵 - 1× 1 0 - 3mol/L铬蓝黑 R( p H4.6)底液中 ,铝 -铬蓝黑 R铬合物在 - 0 .80 V电位处产生灵敏切口 ,切口深度与铝浓度成正比 ,线性范围为 8× 1 0 - 7～6× 1 0 - 5mol/L,检测下限为 6× 1 0 - 7mol/L,相对标准偏差为 4.8% ( n=1 0 ,4× 1 0 - 5mol/L Al)。应用该法测定了天然水中不同形态的铝浓度 ,并同 Driscoll的 MIBK-GF/AAS法进行了比较 ,结果基本一致     

辅酶I在钴/玻碳离子注入修饰电极上的电化学行为及其应用研究

辅酶I(NAD)在 0 .0 0 5mol/LTris 0 .0 1mol/LNaCl(pH =7.0 )缓冲溶液中 ,在Co/GC离子注入电极上有一良好的伏安还原峰 ,峰电位Ep=- 1 .0 7V (vs .SCE)。其峰电流与辅酶I (NAD)的浓度在 5 .0× 1 0 -5～ 1 .0×l0 -3 mol/L范围内呈线性关系 ;检出限为 2 .5× 1 0 -5mol/L ;回收率在 98.8%～ 1 0 1 .9%之间。用线性扫描和循环伏安法等方法研究该体系的电化学行为 ,实验表明 :该体系具有吸附性和催化性的不可逆过程。根据Laviron理论 ,求得电极表面反应速率常数Ks=0 .0 77/s;电子转移系数α =0 .4 35。     

中性体系中鲁米诺电化学发光行为

研究了中性体系中鲁米诺的电化学发光行为。通过对Pt电极的预处理 ,以Br-为增强剂 ,在硼酸中性缓冲溶液中 ,0 .75V(vs .Ag)的正矩形脉冲激励下 ,得到鲁米诺良好的电化学发光信号。其强度在 2 .0× 10 -8～ 3.6× 10 -5mol/L之间与浓度存在定量关系 ;检出限可达 8.0× 10 -9mol/L。     

紫草素的电化学研究

建立了测定紫草素的单扫描极谱分析方法;在0.03mol/LNa2CO3+0.2mol/LNaOH(pH=12.63)底液中,紫草素于-0.60V(SCE)处有一灵敏的二次导数还原峰,电流峰高与浓度在7.0×10-8～5.6×10-7mol/L和6.0×10-7～4.2×10-5mol/L范围内呈线性关系,检出限为3.5×10-8mol/L;用于中药紫草中紫草素的测定,结果良好;同时还研究了紫草素的电极反应机理.     

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.     

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%).     

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.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.