杯芳烃膜电极研究

用吸附法将 C-十一烷基间苯二酚杯 [4]芳烃固定在玻碳电极上制成杯芳烃膜电极 ,对DL-去甲肾上腺素、尿酸、DL-酪氨酸、邻苯二酚进行了测定 ,该电极对 DL-去甲肾上腺素和邻苯二酚具有良好的响应 ,其线性范围分别为 4.0× 1 0 -5～ 8.0× 1 0 -4 和 2 .0× 1 0 -4 ～ 2 .0× 1 0 -3mol·L-1,检测下限分别为 1 .2 5× 1 0 -5和 1 .0× 1 0 -5mol· L-1,对尿酸、DL -酪氨酸没有响应 ,试验发现杯芳烃膜电极不但具有选择性 ,而且有较快的响应速度、良好的重现性和稳定性。     

基于十六烷基三甲基溴化铵存在下铅、银离子的高灵敏度电化学测定

报道了在适量十六烷基三甲基溴化铵 (CTMAB)存在下 ,高灵敏度测定水体中铅、银离子的化学修饰碳糊电极。在pH 2 .5 0 .1mol LKNO3溶液中 ,铅、银离子在钠型蒙脱石修饰碳糊电极上通过离子交换而富集 ,同时被还原。在阳极扫描过程中 ,分别在 - 0 .5 2V和 0 .2 3V(vs.SCE)处出现灵敏的溶出峰。详细研究了测定水样中铅、银离子的条件 ,如介质的pH、CTMAB用量、修饰剂用量、富集电位和时间等。该修饰电极连续测定铅、银离子的线性范围为 5 .0× 10 - 9mol L～ 1.0× 10 - 7mol L(Pb2 + )和 8.0× 10 - 9mol L～ 1.0× 10 - 7mol L(Ag+ ) ,富集 4min后检出限分别为 1.0× 10 - 1 0 mol L(Pb2 + )和 3.0× 10 - 1 0 (Ag+ )。     

Nafion修饰电极伏安法测定痕量镉

化学修饰电极 (ＣＭＥｓ)制备简单、灵敏度高、选择性好、响应迅速 ,用其取代有毒的汞电极已广泛用于分析化学中[1～ 4] 。用ＣＭＥｓ测定Ｃｄ2 +的报道很多[5～7] ,未见用Ｎａｆｉｏｎ修饰电极测定Ｃｄ2 +的报道。本文研究了Ｃｄ2 +在Ｎａｆｉｏｎ修饰电极上的溶出伏安行为 ,建立了用Ｎａｆｉｏｎ修饰电极测定实际水样中Ｃｄ2 +的方法。本方法简便快速 ,灵敏度高 ,Ｃｄ2 +在 2× 1 0 - 9ｍｏｌ/Ｌ到 5× 1 0 - 7ｍｏｌ/Ｌ线性关系良好 ,检出限为 5× 1 0 - 1 1 ｍｏｌ/Ｌ ,用于实际水样测定 ,平均回收率为 99.75 %。1　实验部分1 .1　试剂1…     

锇-聚乙烯吲哚配合物修饰电极对肾上腺素的电催化氧化

研究了配位聚合物锇 -聚乙烯吲哚 [Os( bpy) 2 ( PVI) 1 0 Cl]Cl和 Nafion双层膜修饰玻碳电极的电化学特性 ,该膜对肾上腺素 ( EP)的电化学氧化有催化作用 ,在通常的生理条件下 ( p H7.0 ) ,催化电流与 EP浓度在1 .0× 1 0 - 6～ 8.6× 1 0 - 5 mol/L范围内呈良好的线性关系 ,相关系数为 0 .9987.Nafion膜排除了抗坏血酸( AA)的干扰 ,表现出较高的灵敏度、选择性及良好的稳定性 .该电极可在 +2 50 m V下进行 EP的安培法测定 .用旋转圆盘电极对电催化过程的动力学进行了研究 ,催化速率常数 kch为 3 .53× 1 0 3mol- 1 · L· s- 1 .在较高 EP浓度下 ,催化电流与浓度的关系表现出 Michaelis-Menten型响应 ,Michaelis-Menten常数 Km 为1 .4 7mmol/L.     

二硫代氨基甲酸螯合树脂化学修饰电极的制备及银离子的测定

将纯石墨电极经三氧化二铝抛光与浓硝酸和浓硫酸(1+1)混合酸使其极性化,之后于1 g·L-1聚氯乙烯(PVC)环己酮溶液10μL中浸渍片刻,取出,用红外灯照射烘干30 min,冷却后,将电极置于含有哌嗪、K3PO4及二甲基甲酰胺(DMF)(2:1:8)的混合液中使其反应;最后在氢氧化钠存在下与二硫化碳反应,用水洗至中性,即制成修饰有二硫代氨基甲酸螯合树脂的石墨电极,将其用于银的测定。与未修饰的电极相比此电极具有较高的灵敏度和较好的选择性,在1．0×10-8～1．0×10-5mol·L-1范围内,峰电流与浓度呈线性关系,检出限为5．0×10-9mol·L-1。     

聚酰胺修饰碳糊pH电极测定高酸溶液中的氢

将石蜡、石墨粉和聚酰胺按 5∶ 1∶ 2质量比混匀 ,制成全固型聚酰胺修饰碳糊氢电极。它在 1 %～ 1 0 %KNO3 溶液中 ,对 H+ 的线性响应范围为 1 .1 0× 1 0 - 5～7.0 2 mol/L (相关系数为 0 .9993 ) ,响应时间为 3 0～ 90 s,响应斜率为 3 0 .3 m V/p H,检出限为 5 .0 1× 1 0 - 6mol/L。对常见共存离子的选择性系数为 1 0 - 5～ 1 0 - 4。电极性能稳定 ,重现性好 ,使用寿命可长达 6 0多天 ,特别适合于高酸度溶液中 H+ 的测定。     

用碘离子选择性电极测定砷(Ⅲ)

砷是自然界中普遍存在而且对人体有毒的化学元素之一 ,目前分析砷的方法很多[1,2 ] ,本文用碘离子选择性电极间接测定砷 (Ⅲ )的含量 ,方法操作简单 ,结果可靠 ,检出限可达到 6.2 5× 1 0 -7ｍｏｌ·Ｌ-1。1　试验部分1 .1　主要仪器与试剂ｐＸＳ 2 1 5离子活度计(上海精科雷磁公司 )79 1型磁力加热搅拌器碘离子选择性电极 (江苏电分析仪器厂 )离子强度调节剂 :0 .5ｍｏｌ·Ｌ-1ＫＮＯ3 +0 1ｍｏｌ·Ｌ-1氯乙酸水为二次蒸馏水1 .2　试验方法取 5 0ｍｌ容量瓶若干个 ,分别加入 0 .5ｍｏｌ·Ｌ-1ＫＮＯ3 溶液 5ｍｌ,0 .1ｍｏｌ·Ｌ-1氯乙酸 2…     

乙二胺四乙酸二钠/碳糊修饰电极测定银离子

报道EDTA/碳糊修饰电极的制备及对银离子的测定。该电极在硝酸介质中 - 0 .6 0V(vs .Ag/AgCl)电位下富集Ag+ ,在 +0 .0 8V处得到一个灵敏的阳极溶出峰 ,峰电流与Ag+ 浓度在 1.0× 10 -9～ 1.0× 10 -6mol/L范围呈良好线性关系 ,检出限为 6 .8× 10 -10 mol/L。     

利用扫描电化学显微镜研究过氧化氢检测中电化学消除抗坏血酸

利用扫描电化学显微镜 (SECM)将微探针定位于宏观金盘基底电极的扩散层内 .通过向基底电极施加适当电位以氧化消除电活性干扰物质 (如抗坏血酸 ) ,提高探针电极检测过氧化氢的选择性 .基于此方法 ,系统研究了探针 -金基底电极间距和电极电位对铂微探针检测过氧化氢选择性的影响 .结果表明 ,当探针 -基底电极间距为 2 2 .6μm ,金基底电极和铂探针电极电位分别为 0 4V和 0 5V时 ,探针电极检测过氧化氢不受抗坏血酸 ( 0 0 5mmol·L-1)的干扰 .此时 ,过氧化氢检测的线性范围为 :4× 10 -5～ 1× 10 -3 mol·L-1.基于实验结果 ,提出了在微型化电化学器件制备过程中设计互相靠近的双工作电极 ,利用电化学法消除电活性干扰物以提高检测选择性的新方法 .     

纳米金修饰玻碳电极在抗坏血酸共存下选择性测定多巴胺

利用电沉积的方式制备了纳米金 ( Nano- gold,NG)修饰玻碳电极 ( GCE)。该电极对多巴胺 ( DA)和抗坏血酸 ( AA)均有催化作用 ,且多巴胺在纳米金修饰玻碳电极上有较强的吸附作用。同时研究了磷酸缓冲溶液的 p H值和离子强度对 DA的电化学行为的影响。纳米金修饰玻碳电极在 DA和 AA的混合溶液中的循环伏安图上可观察到两个明显分开的氧化峰 ,峰电位差达到 1 5 0 m V。据此 ,提出了两种利用该电极在抗坏血酸共存下选择性测定多巴胺的方法 ,线性范围分别为 3.0× 1 0 - 6 ～1 .0× 1 0 - 4mol/ L和 1 .2 5× 1 0 - 6 ～ 1 .0× 1 0 - 4mol/ L。     

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.