汞配合物为载体的高灵敏PVC膜碘离子选择电极研究

研究了基于四醋酸·双 ( 5 甲基 1,3 ,4 噻二唑 2 硫 ) -烷基合汞 (Ⅱ )配合物为中性载体的阴离子选择性电极 .这类电极对碘离子响应具有高灵敏和高选择性 ,并且呈现反Hofmeister序列行为 ,其选择性次序为 :I->SCN->ClO-4>Br->NO-3>Cl->AcO->SO2 -4.其中由四醋酸·双 ( 5 甲基 1,3 ,4 噻二唑 2 硫 ) -丁烷合汞 (Ⅱ)配合物为载体的电极在pH为 3 .0磷酸盐缓冲条件下对I-的线性响应范围为 4.0× 10 -8～ 1.0× 10 -2 mol/L ,检测限为 2 .0× 10 -8mol/L ,斜率为 -5 9.1mV/pcI- .通过紫外 -可见光谱和交流阻抗测试技术研究了电极的响应机理 .结果表明 ,配合物中心金属原子的结构以及载体本身的结构与电极的响应行为之间有非常密切的构效关系 .将该电极应用于嘉陵江水和缙云山泉水的测定 ,其结果令人满意     

新型镍配合物中性载体高选择性水杨酸根离子电极的研究

首次研究了基于苯甲醛丙氨酸合镍(Ⅱ)金属配合物[Ni(Ⅱ) -BBAA]为中性载体的PVC膜电极。该电极对水杨酸根(Sal -)具有优良的电位响应性能和选择性并呈现出反Hofmeister选择性行为 ,其选择性次序为Sal->ClO-4>SCN->I-> -2NO> 3-NO>Br->Cl->SO32- >SO42-。在pH5.0的磷酸盐缓冲体系中 ,电极电位呈现近能斯特响应 ,线性响应范围为2.2×10 -5～1.0×10 -1mol/L,斜率为 -55.8mV/dec(20℃) ,检出限为8.0×10-6 mol/L。采用交流阻抗技术和紫外可见光谱技术研究了电极的响应机理 ,结果表明配合物中心金属原子的结构以及载体本身的结构与电极的响应行为之间有非常密切的构效关系。该电极具有响应快、重现性好、检出限低、制备简单等优点。将电极用于药品分析 ,其结果令人满意     

聚氯乙烯膜依诺沙星选择电极的研制与应用

以盐酸依诺沙星与四苯硼酸盐生成的分子缔合物制成新型PVC膜依诺沙星选择电极,应用于依诺沙星药片的含量测定。在pH 2.2～6.5范围内,电极的能斯特响应范围为5.0×10~(-5)～1.0×10~(-2)mol/L,斜率为58.0mV/pc,检出限为4.2×10~(-6)mol/L。该电极响应速度快,重现性好。3次测定的平均回收率为97.5％,RSD为1.0％,结果与紫外分光光度法基本一致。     

聚亚甲基蓝和纳米金修饰玻碳电极的葡萄糖生物传感器

用循环伏安法在玻碳电极上电聚合一层稳定的亚甲蓝聚合物膜,研究了这层膜在0.1mol/L磷酸缓冲溶液(pH7.0)中的电化学性质。用纳米金溶胶与聚乙烯醇缩丁醛(PVB)构成复合固酶基质,采用溶胶-凝胶法固定葡萄糖氧化酶(GOD)于亚甲蓝修饰的玻碳电极表面,制成了新型葡萄糖生物传感器。实验发现,加入纳米金后提高了酶电极对葡萄糖的电流响应,所制备的传感器具有响应快、灵敏度高、稳定性好,对葡萄糖的线性响应范围为1×10-6~3×10-3mol/L,检出限为5×10-7mol/L。并具有抗尿酸、抗坏血酸干扰的特点。     

肿瘤标记物1-甲基鸟苷的微分脉冲伏安法的研究

建立一种灵敏的测定修饰核苷1 甲基鸟苷(1 MG)的电化学分析方法.在pH为2.00的BR缓冲液中,用循环伏安法(CV),线性扫描伏安法(LSV),方波伏安法(SWV),微分脉冲伏安法(DPV)等现代电化学技术研究了肿瘤标记物1 甲基鸟苷在玻碳电极(GCE)上的伏安行为.实验结果表明,pH为2.00的BR缓冲液中,1 甲基鸟苷在+1.16V(vs.甘汞)电位处产生一个灵敏的微分脉冲阳极氧化峰,该氧化峰的峰电流值与1 甲基鸟苷的浓度在4.0×10-7～1.0×10-5mol/L范围内呈良好的线性关系,最低检测限达(定义为D=2σ/K)6.6×10-8mol/L.将该法应用于兔血清及尿样中1 甲基鸟苷的测定,回收率在96.0%～102.0%之间,5次测定的相对标准偏差(RSD)均小于3 5%.并初步研究了1 甲基鸟苷的电化学机理.     

Nafion-甲基紫精修饰电极抗坏血酸氧化酶生物传感器的研究

本文用Nafion-甲基紫精修饰电极为基底,以牛血清白蛋白和戊二醛为交联剂,将抗坏血酸氧化酶固定在电极上,制成修饰电极抗坏血酸氧化酶生物传感器。用这种生物传感器测定人体血清中抗坏血酸,线性范围在7.5×10~(-4)～7.5×10~(-7)mol/L之间,响应时间为5s,检测下限为2.5×10~(-7)mol/L。该传感器具有选择性好、灵敏度高和响应时间短等特点。     

聚氯乙烯膜普鲁卡因选择电极的研制与应用

研制了一种以普鲁卡因碘化物与碘化铋形成的缔合物为电活性物质的PVC(聚氯乙烯 )膜普鲁卡因选择电极 ,测定了普鲁卡因注射液的含量 ;电极的线性响应范围1.0×10 -1～6.3×10 -5mol/L,级差电位为45mV/pc ,检出限为3.4×10-5 mol/L ;该电极响应迅速 ,测定结果与药典法相符     

溶胶凝胶溴离子选择电极的研制与应用

报道了一种以溶胶凝胶为载体的溴离子选择电极。电极信号响应线性范围为1 .0× 1 0 - 1～ 1 .0× 1 0 - 5mol/L,斜率为 5 7m V/pc;检出限为 2 .5× 1 0 - 6 mol/L。该电极响应快 ,体积小 ,稳定性和重现性好。电极用作测定溴离子浓度 ,结果令人满意     

长链S-烷基双硫腙为载体的碳酸氢根离子电极

以溴化S 十六烷基双硫腙载体制备了碳酸氢根离子选择性电极 ,选择性次序为 :ClO-4 >SCN->I-～HCO-3 >ClO-3 ～NO-3 >Ac->NO-2 >Cl->H2 PO-4 >SO2 -4 。膜配比 (质量百分比 )为溴化S 十六烷基双硫腙 (SHDTZ)·HCO-3 ∶邻苯二甲酸二异辛酯∶PVC =2 .5∶65.0∶32 .5电极性能最佳。 32℃时 ,在pH 8 30 .1mol/L三乙醇胺 硫酸缓冲溶液中 ,HCO-3 离子浓度在 1 .0× 1 0 -2 ～ 1× 1 0 -5mol/L范围与电极电位呈线性响应 ,检测限为 5.0× 1 0 -6mol/L;斜率为 54± 2mV/decade。研究了HCO-3 离子与载体的作用机理。用该法测定了人体血清中HCO-3 ,结果与滴定法一致。     

聚L-谷氨酸/石墨充蜡修饰电极测定多巴胺

用充蜡石墨电极 (WGE)在L 谷氨酸 (GA)无水乙醇溶液中恒电位于 1.6V(vs.SCE)氧化制备了一种聚GA修饰电极 (GA/WGE) ,该电极可用于肾上腺素 (EP)和抗坏血酸 (AA)共存下对多巴胺 (DA)的测定。该电极的灵敏度和选择性主要取决于阳极极化电位与极化时间、富集电位和溶液的pH。DA在该电极上呈现一对循环伏安峰 ,Em=0 .14 5V ,为 1电子 / 1质子的准可逆氧化还原过程。AA和EP也能够在电极上富集和催化氧化 ,伏安峰分别在 0 .30V和 0 .17V。当AA浓度小于 0 .1mmol/L时 ,电极对AA基本不响应 ,可以用DA的氧化峰电流做定量分析。线性范围为 2 .0× 10 -4～ 5 .0× 10 -7mol/L ;检出限为 2 .5× 10 -7mol/L。当AA的浓度较大或在AA、EP共存下 ,可利用DA氧化的再还原峰电流做定量分析。线性范围为 1.0× 10 -4～ 2 .5× 10 -6mol/L ;检出限为 7.5× 10 -7mol/L。该电极制作简便 ,重现性良好 ,定量结果也令人满意     

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.     

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.     

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.     

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.