基于血红蛋白的过氧化物酶特性测定其在血浆中游离态含量

基于血红蛋白 (Hb)的过氧化物酶特性 ,研究了以铬黑T(EBT)作为其氢供体底物时的酶动力学行为。实验测定了Hb作为辣根过氧化物酶 (HRP)的替代物的类酶催化米氏常数和米氏速率。对Hb催化H2 O2 氧化铬黑T的机理作了探讨。建立了测定Hb的催化动力学光度法 ,方法的线性范围为 2× 10 - 8mol/L～ 2× 10 - 6mol/L ,检出限为 3.6× 10 - 9mol/L。用于血浆中游离Hb的测定 ,结果满意。     

血红蛋白模拟过氧化物酶催化反应体系的极谱分析

用极谱分析法研究了血红蛋白催化H2O2氧化邻苯二胺(OPD)的反应体系.血红蛋白具有类似过氧化物酶的功能,它能够催化OPD-H2O2的反应生成一种具有电化学活性的产物,该产物在滴汞电极上-0.64V(vs.SCE)产生一个峰形良好的极谱还原峰.优化了血红蛋白的催化反应条件和催化反应产物的极谱测定条件 在最佳条件下,该体系可用于血红蛋白含量的测定,线性范围为2.0×10-9～2.0×10-7mol/L,检测限为1.0×10-9mol/L;也可用于痕量H2O2的测定,线性范围为1.0×10-6～2.0×10-4mol/L,检测限为1.0×10-6mol/L.     

血红蛋白模拟过氧化物酶催化H2O2氧化邻氨基酚的固体电极伏安法研究

探讨了用血红蛋白作为辣根过氧化物酶的替代物,用于催化H2O2氧化邻氨基酚的反应体系.其催化反应生成一种具有电化学活性的产物,该产物在玻碳电极上于-0.370 V(vs.Ag/AgCl)产生一个峰形良好的还原峰.还原峰电流随着血红蛋白浓度的增大而增大.同时用微分脉冲伏安法对血红蛋白的催化反应条件进行了优化,选择了催化反应产物的伏安测定的最佳条件.在该条件下,该体系可用于血红蛋白的测定,线性范围为4.0×10-8～8.0×10-7mol/L,检出限为3.4 × 10-8 mol/L.用循环伏安法研究了该产物在不同pH B-R缓冲溶液中于玻碳电极上的电化学性质.     

血红蛋白与葡萄糖氧化酶偶联荧光法测定葡萄糖

利用血红蛋白(Hb)作为辣根过氧化物酶(HRP)的模拟酶,催化H2O2与对甲基酚的荧光反应.并将该反应与葡萄糖氧化酶(GOD)催化氧化葡萄糖的反应偶联,建立了测定葡萄糖的荧光分析法.方法的线性范围为0.0～5.0×10-5mol/L葡萄糖.检测限为6.5×10-8mol/L.用于测定人血清中葡萄糖的含量,获得了满意的结果.     

四磺基锰酞菁作为过氧化物模拟酶在过氧化氢化学发光测定中的应用

以四磺基锰酞菁 (MnTSPc)作为过氧化物模拟酶催化H2 O2 与鲁米诺的化学发光反应 ,建立了测定环境样品中H2 O2 的化学发光分析新方法。该法的线性范围为 4 .0× 10 - 8～ 2 .0× 10 - 5mol L ;检出限为 6 .8×10 - 9mol L ;对 1.0× 10 - 6 mol L的H2 O2 进行连续 10次平行测定 ,相对标准偏差为 2 .4 %。用本法对天然雨水进行了分析测定 ,结果良好。     

血红蛋白作为过氧化物模拟酶催化测定过氧化氢

研究了牛血红蛋白 (Hemoglobin ,Hb)作为过氧化物模拟酶催化H2 O2 氧化隐性亮绿 (RecessiveBrilliantGreen ,RBG)显色反应的催化特性及反应条件。该体系在pH 5 .73的条件下形成的酶催化产物在 640nm处有最大吸收。体系测定H2 O2 时表观摩尔吸光系数为 7.1 5× 1 0 3L·mol-1·cm-1,测定H2 O2 检测限为 2 .8× 1 0 -6mol L。方法可用于天然水中H2 O2 的测定。     

辣根过氧化物酶催化过氧化氢氧化隐性亮绿显色反应的研究

以隐性亮绿 (RBG)为氢供体底物 ,研究了辣根过氧化物酶 -H2 O2 -RBG显色反应体系的酶催化特性。在 p H 5.0～ 6.0的条件下反应形成的酶催化产物亮绿 (BG)于 63 0 .6nm处有最大吸收 ,该显色反应测定 H2 O2 的表观摩尔吸光系数为 5.64×1 0 4 L·mol- 1·cm- 1,线性范围为 3 .55× 1 0 - 8～ 6.0× 1 0 - 6 mol/ L,检出限为 3 .55×1 0 - 8mol/ L。方法用于雨水中痕量 H2 O2 的测定 ,结果满意     

酶催化动力学光度法测定H2O2

H2O2能够氧化偶氮染料刚果红使之褪色,而模拟酶—血红蛋白对其具有催化作用。据此建立了一种以刚果红为指示剂的H2O2-刚果红-血红蛋白酶催化反应体系测定痕量H2O2的新方法。确定了反应的最佳条件,体系的酸度为pH10.7的NH3-NH4Cl缓冲溶液,最大吸收波长为497 nm。该法的线性范围为8.0×10^-8-8.0×10^-5mol/L,检出限为1.97×10^-9mol/L,表观摩尔吸光系数为4.6×10^4L.mol-1.cm^-1。该方法可用于雨水及消毒水中H2O2的测定。     

一种高灵敏度测定血红蛋白的荧光分析法

建立了以双水杨醛邻苯二亚胺为酶催化氧化底物,血红蛋白(Hb)作为过氧化物模拟酶,在Tween80介质中的酶催化反应测定血红蛋白的方法,并探讨了反应机理。讨论了利用本体系测定Hb的最佳条件,结果表明:在优化的条件下,Hb浓度在 5. 0×10-10 ~5. 0×10-8 mol/L范围内呈良好的线性关系,方法的检出限为 2. 6×10-11 mol/L。本方法与其它测定Hb方法相比具有更高的灵敏度。     

流通式化学发光植物组织传感器测定过氧化氢

基于土豆组织中过氧化物酶对H2 O2 Luminol体系的催化作用 ,设计出一种简便、快速、灵敏度高的流通式化学发光植物组织传感器。该传感器的线性响应范围为 1.0× 10 - 6～ 1.0× 10 - 3 mol L ;检出限为 4× 10 - 7mol L ;对 1.0× 10 - 6mol L的过氧化氢进行 11次连续测定 ,相对标准偏差为 2 .4%。从取样到测定的全部分析过程只需 1.5min。作为分子识别的组织柱 ,可连续使用 40 0次以上 ,保存期为 3周。方法已成功地应用于水样中过氧化氢的测定。     

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.