甲基蓝与硫酸阿米卡星相互作用的电化学研究及分析应用

在pH 4.5的Britton-Robinson(B-R)缓冲溶液中,甲基蓝在静汞电极上分别于-0.04 V-、0.275 V和-0.675 V(vs.SCE)处产生三个还原峰。加入硫酸阿米卡星后,阿米卡星与甲基蓝反应并形成离子缔合物,使甲基蓝在-0.275 V(vs.SCE)处的还原峰峰电流下降,其下降值与阿米卡星的浓度在1.0~60.0 mg/L范围内呈良好的线性关系,其线性方程为ΔIp(nA)=-8.48 102.36c(mg/L),相关系数r=0.997,检出限为1.0 mg/L。将该方法应用于药物中阿米卡星含量的测定,回收率在97.0%~105.0%之间,RSD≤4%,结果满意。     

线性扫描极谱法测定人血清白蛋白

以线性扫描极谱法研究了在pH=6．5的Britton-Robinson缓冲溶液中灿烂甲酚蓝与人血清白蛋白的相互作用。灿烂甲酚蓝在-0．18V(vs．SCE)有一个良好的极谱还原峰,加入人血清白蛋白后,其峰电位负移而峰电流下降,峰电流的下降值同人血清白蛋白的浓度在2．0～60．0mg／L内呈线性关系,线性回归方程为Δip=18．05c 123．65,r=0．9970。     

蛋白质与钍试剂I作用的电化学行为的研究

在pH4.8的NaAc HAc缓冲液中,钍试剂Ⅰ与蛋白质能够相互作用形成超分子复合物,使钍试剂Ⅰ在-0.58V(SCE)处的极谱还原峰峰电流下降,在最佳条件下,峰电流的下降值同牛血清白蛋白(BSA)的质量浓度在1.5～25mg/L范围内呈线性关系,其线性回归方程为Δip=-265.4+181.2ρBSA,相关系数r=0 998(n=7),检出限为1mg/L。可应用于血清样品的测定。     

示波极谱法烟丝中尼古丁含量测定及电极反应机理

研究了用示波极谱法直接测定烟丝中的尼古丁含量的新方法.在0.2mol/L草酸底液中(pH=4.0),于-1.22V处得到尼古丁的灵敏还原峰,峰电流与尼古丁浓度在1.5～31.5mg/L范围内呈良好的线性关系,检测下限达0.37mg/L.该方法用于烟丝中尼古丁含量的测定,简单快速,测定回收率在91%左右.     

单扫示波极谱法测定食品包装材料中双酚A的研究

研究发现，在0.12mol/L Na2HPO4-KH2PO4(pH7.5)底液中，双酚A于峰电位（Ep)-1.0V(vs.SCE)处产生灵敏的极谱还原波，该波的二阶导数峰电流（ip)与双酚A浓度在2.0-10.0mg/L范围内呈良好的线性关系，检出限为1.0mg/L，萃取后测定，检出限为0.1mg/L。本法操作简便、快速、准确。用于食品包装材料中双酚A含量的测定，结果令人满意。     

防晒剂2，2’，4，4＇-四羟基二苯甲酮在B—R缓冲体系中的极谱行为

用线性扫描极谱法系统研究了2,2′,4,4′-四羟基二苯甲酮(简称BP-2)在不同缓冲体系中的极谱行为.实验表明,在pH=2.25的B-R缓冲溶液中,BP-2的一阶导数峰电位为-1.12 V,其峰电流与浓度在5.0×10-6～9.0×10-5mol/L范围内的对数值有良好的线性关系,线性方程为ip′(nA/s)=11 457 2 133×lgc(mol/L),相关系数为0.9998.BP-2的微分循环伏安研究表明,该极谱波为不可逆还原波;初步讨论了电极反应机理.     

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     

以茜素兰S为电化学探针测定DNA的研究

在pH 4.5的0.2 mol/L Britton-Robinson(B-R)缓冲溶液中,茜素兰S(ABS)于-0.51 V(vs.SCE)产生一个灵敏的线性扫描二阶导数极谱还原峰。当在上述溶液中加入DNA后,茜素兰S在-0.51 V处还原峰的峰电流降低并且峰电位正移,说明两者之间可以通过嵌插作用而结合。结合反应的发生使溶液中游离的茜素兰S浓度降低,相应的还原峰电流降低。实验优化了结合反应条件和电化学测定条件。在最佳条件下,峰电流的降低值同DNA的浓度在1.0~60.0 mg/L范围内呈线性关系,线性回归方程为△ip″(nA)=18.13c(mg/L)-7.61(n=9,r=0.998)。方法应用于合成样品中DNA的测定,结果令人满意。     

靛玉红在碳糊电极上的阴极吸附伏安法研究

在0.10 mol/L的K2HPO4-NaH2PO4（pH8.5）缓冲液中,使用JP-303极谱分析仪,靛玉红在碳糊电极（CPE）上有一灵敏的吸附伏安还原峰,峰电位为-0.60 V（vs.SCE）。该还原峰的二阶导数峰电流与靛玉红的浓度在8.0×10^-9-8.0×10^-7mol/L（富集90 s）范围内呈良好的线性关系,相关系数为0.9976,检出限为4.0×10^-9mol/L（S/N=3,富集110 s）。探讨了靛玉红在碳糊电极上的伏安性质和电极反应机理,并应用于中草药大青叶中靛玉红含量的测定。     

单扫描示波极谱法测定扑热息痛

扑热息痛与NaNO2在中性介质中发生反应，其亚硝化衍生物具有良好的电活性。在pH9．37的Britton-Robinson缓冲溶液中，于-0．56V(vs．SCE)产生灵敏的极谱还原峰，峰电流与扑热息痛质量浓度在0．007-0．4mg/L范围有良好的线性关系，检测下限为5μg/L。此法已用于测定小儿速效感冒灵。     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.