碳纳米管化学修饰电极测定土壤沉积物中的铜

本文研究了在碳纳米管(CNT)修饰的玻碳电极上,用微分脉冲溶出伏安法(DPSV)对土壤沉积物中铜的测定方法,在1.0mol/L的HCl介质中,于-0.6V电位处富集240s,静置10s,在阳极扫描过程中,被富集于修饰电极表面的铜在约-0.25V电位处出现特定的溶出峰,据此实现铜离子的测定。该方法的线性范围为8.0×10-7～1.2×10-5mol/L,检出限为2.0×10-7mol/L,结果令人满意     

血红蛋白在L-半胱氨酸微银修饰电极上的电化学行为

L-半胱氨酸通过化学键结合到微银电极表面成化学修饰电极,研究表明此修饰电极对血红蛋白的氧化还原有促进作用.并用预富集和示差脉冲溶出伏安法检测血红蛋白的浓度,检测限为1.0×10~(-8)mol/L,8次测定2.0×10~(-7)mol/L血红蛋白的相对标准偏差是6.3%.     

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。     

邻苯三酚红修饰碳糊电级阳极溶出伏安法测定痕量锡的研究

研制了邻苯三酚红 ( PR)修饰碳糊电极 ,研究了采用该电极测定痕量锡的阳极溶出伏安法。在 0 .1 5 mol/L乙酸盐缓冲溶液 ( p H 4.5 )中 ,通过开路富集 ,Sn( )与修饰电极表面的邻苯三酚红生成络合物而富集于电极表面 ,然后介质交换至 4.0mol/L盐酸中 ,于 - 0 .80 V还原后再进行阳极化扫描 ,于 - 0 .69V左右获得一灵敏的 Sn的溶出峰 ,二次导数峰电流与 Sn( )浓度在 1 .68× 1 0 - 8～ 1 .68× 1 0 - 6mol/L范围内呈现良好的线性关系 ,检出限达 8× 1 0 - 9mol/L。对电极反应机理进行了讨论 ,方法已应用于罐头食品中锡的测定     

槲皮素修饰碳糊电极吸附溶出伏安法测定人血清中铜

制作了用槲皮素作修饰剂的修饰碳糊电极 ,利用此电极为工作电极 ,建立了测定痕量铜的新方法。在甲酸钠 -盐酸缓冲溶液 ( p H4.7)中 ,于 0 .2 0 V( vs.SCE下同 )处搅拌富集 ,铜 ( )与碳糊修饰电极表面的槲皮素形成电活性络合物而吸附富集于电极表面 ,于 - 0 .40 V静止还原后 ,阳极化线性扫描 ,在 - 0 .0 3V左右获得一灵敏的二次导数溶出峰。在不同富集时间下 ,其二次导数峰电流与铜 ( )浓度分别在1 .5× 1 0 - 9～ 8.0× 1 0 - 8mol/ L和 1 .5× 1 0 - 8～ 9.0× 1 0 - 7mol/ L两个范围内成良好的线性关系 ,检出限可达 8.0× 1 0 - 10 mol/ L。同时探讨了电极反应机理。方法应用于人血清中痕量铜的测定 ,获得了令人满意的结果     

双硫腙修饰玻碳电极阳极溶出伏安法测定痕量镉和铅

报道了双硫腙修饰玻碳电极同时测定痕量镉和铅的电分析方法。镉和铅离子通过与电极表面的双硫腙发生螯合作用而富集在电极表面 ,同时在 -1 .2 0V(vs.SCE)还原成零价镉和铅 ,当电极电势从 -1 .2 0V向 -0 .3 0V扫描时 ,被还原的镉和铅从电极表面溶出 ,分别于 -0 .78V和 -0 .4 8V左右形成灵敏的阳极溶出峰。优化了支持电解质及pH值、双硫腙用量、富集电位及时间等实验参数。利用该修饰电极测定镉、铅的线性范围分别为 1 .0×1 0 - 8～ 2 .5× 1 0 - 6 mol L和 5 .0× 1 0 - 9～ 2 .5× 1 0 - 6 mol L。检测限分别为 5 .0× 1 0 - 9mol L和7.0× 1 0 - 1 0 mol L。该法用于实际水样中镉和铅的测定 ,平均回收率分别为 99.3 0 %和 99.5 4 %。     

2-羟基-3-(三乙胺基)丙基正癸基硫醚修饰碳糊电极测定痕量金

制备了2＿羟基＿3＿(三乙胺基)丙基正癸基硫醚修饰碳糊电极,用于痕量金的测定。研究了电极的伏安特性及分析条件。在0.2mo／LKCl-HCl缓冲溶液中(pH1),Au(Ⅲ)被富集到电极表面,然后介质交换到0.2mol／LKCl-HCl空白溶液中(pH1)进行阳极溶出伏安测定,对于5min富集,Au(Ⅲ)浓度在2×10-8～1×10-6mol／L范围内呈线性关系,检出限为1×10-8mol／L,相对标准偏差5.2%,一般常见离子不干扰。     

铜膜差分脉冲阳极溶出伏安法测定药物中铋的含量

研究了铜膜电极代替汞膜电极测定重金属铋的差分脉冲溶出伏安法。实验了同位镀膜法测定铋的条件。在最佳实验条件下,Bi3+浓度在5×10-8~2×10-5mol/L范围内,其溶出峰峰高与浓度呈线性关系,检出限达到1×10-8mol/L。测定了一些药物中铋的含量,结果准确。     

就地镀铜旋转圆盘玻碳电极上阳极溶出测定砷(Ⅳ)

在铜或硒存在下利用悬汞电极阴极溶出测定砷已见报道,但使用玻碳电极进行砷的测定尚属少见。砷的阳极溶出法因汞电极中汞的氧化干扰而无法进行。本实验采用就地镀铜玻碳电极作工作电极成功地进行砷的阳极溶出法测定。 (一)操作步骤加入适量的砷、铜及硫酸溶液到50ml容量瓶中使砷的最终浓度为1.0×10~(-7)mol/L-9.0×10~(-6)mol/L,铜(Ⅱ)为4.0×10~(-6)mol/L,硫酸为0.6mol/L。将溶液转入石英电解池中,通氮除氧5min,在-0.60V沉     

碳糊电极吸附溶出伏安法测定游离钙

基于Ca(Ⅱ)-茜素红S(ARS)络合物在碳糊电极上的还原波,建立了吸附溶出伏安测定游离钙的新方法。在1.5×10-2mol/LKOH-2.0×10-5mol/LARS介质中,Ca(Ⅱ)-ARS络合物在碳糊电极上于-0.89V处产生一吸附还原波。当富集电位为.0.1V,富集时间90s,扫描速度为100mV/s时,该络合物单扫描阴极溶出峰的二阶导数峰电流与游离钙离子浓度在3.0×10-8~2.0×10-6mol/L范围内呈线性关系;检出限为9.4×10-9mol/L。在0.2mol/LHCl中清洗2min,该电极重现性良好。该方法可用于血清、牛奶和自来水中游离钙的测定。     

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%.     

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.