二甲酚橙催化光度法测定亚硝酸根的研究

基于硫酸介质中亚硝酸根催化溴酸钾氧化二甲酚橙的褪色反应 ,建立了测定痕量亚硝酸根的新方法 ,并探讨了动力学条件 ,测定了反应的表观速率常数( k=1 .32× 1 0 -3 S-1)和表观活化能 ( Ea=35 .0 2 k J/mol)。方法的测定范围为 0～ 0 .1 8μg/m L,检出限为 1 .1 ng/m L。方法已用于水中及水基产品中亚硝酸根的测定     

新体系催化动力学光度法测定痕量亚硝酸根

基于增敏剂吐温 - 80存在下亚硝酸根催化过氧化氢氧化中性红的反应 ,建立了测定痕量亚硝酸根的新催化动力学光度法。方法的灵敏度较常规方法提高了 2 .2倍 ,测定的线性范围为 2～ 1 0 μg/L,检出限为 2 .7× 1 0 - 10 g/m L。已用于测定水样中 NO2 - 的含量     

光化学反应在流动注射分析中的应用研究V.硝酸根-鲁米诺光化学反应体系化学发光法测定痕量硝酸根

基于紫外光照射下硝酸根能够转化生成过氧化亚硝酸酯及过氧化亚硝酸酯氧化鲁米诺而产生化学发光,建立了流动注射光化学反应测定痕量硝酸根的新方法。测定硝酸根的线性范围是5×10(-8)～1×10(-4)mol/L,进样频率为60～80次/h.     

四波长负吸收催化光度法测定痕量亚硝酸根

采用负吸收光谱校正技术 ,研究了在磷酸介质中亚硝酸根催化溴酸钾氧化灿烂绿的褪色反应 ,根据四波长处负吸光度加和值与亚硝酸根的含量成线性关系 ,提出并建立了四波长负吸收催化光度法测定痕量亚硝酸根含量的新方法。线性范围 5 .0× 1 0 -7～ 1 .0× 1 0 -5mol/L。用于环境水样中亚硝酸根含量的测定获得满意结果。基于四波长处负吸光度加和值与时间成良好的线性关系 ,亚硝酸根物质的量浓度与灿烂绿物质的量浓度没有固定的比例。提出了亚硝酸根催化溴酸钾氧化灿烂绿的反应机理     

催化光度法测定水中的痕量NO2-

基于磷酸介质中亚硝酸根催化溴酸钾氧化靛蓝胭脂红的褪色反应,建立了测定水中痕量亚硝酸根的催化光度法,并利用正交试验对测定方法进行了优化,亚硝酸根的检测限为1.36×10~(-6)g/L,线性范围为0.3～2.0 μg/25mL。该法用于蔬菜及环境水样中痕量亚硝酸根的测定,结果准确。     

甲基紫电极催化动力学电位法测定亚硝酸根

基于在稀磷酸介质中亚硝酸根对溴酸钾氧化甲基紫的反应具有明显的催化作用 ,应用自制的甲基紫选择性电极跟踪反应液中甲基紫浓度的变化 ,建立了一种测定亚硝酸根的催化电位新方法。该方法在室温下进行 ,操作方便 ,样品溶液不受颜色限制。在选择的最佳条件下 ,检出限为 7 6× 1 0 -7g/L ,线性范围为8 0× 1 0 -7～ 8.0× 1 0 -5g/L。用于肉制品中亚硝酸根含量的测定 ,结果满意     

NO_2-Ni~(2+)-SCN配合物极谱吸附波的研究及痕量NO_2的测定

本文提出了极谱法测定痕量亚硝酸根的一个新体系。在含有Ni~(2+)和SCN~-的稀硫酸底液中,在单扫示波极谱仪上,有一灵敏的亚硝酸根配合物吸附波,峰电位为-0.57V(vs SCE)。一阶导数峰高与亚硝酸根浓度在2×10~(-8)～2×10~(-6)mol/L之间成线性关系。检测限达8×10~(-9)mol/L。回归方程为:Y=0.47x+0.096,相关系数为0.998,相对标准偏差为1.6％。该法具有良好的选择性,尤其是大量硝酸根不干扰测定。成功地应用于实际样品中痕量亚硝酸根的分析。     

以酸性铬蓝K作为氢供体的酶催化光度法测定过氧化氢

研究了以酸性铬蓝 K作为氢供体底物的过氧化氢酶 -过氧化氢催化反应体系 ,拟定了测定痕量过氧化氢的新的酶催化光度法。测得该体系的最大反应速率 Vmax值为 6.2 5× 1 0 -3 mol· L-1·S-1,米氏常数 Km值为 2 .78× 1 0 -5mol/L。测定过氧化氢的线性范围为 0 .0 3～ 0 .6mg/L。检出限为 4.6× 1 0 -4 mol/L。方法可应用于雨水中过氧化氢的测定     

甲基橙亚硝化极谱法测定亚硝酸根

研究了甲基橙亚硝化产物的极谱波行为 ,提出了亚硝化极谱法测定亚硝酸根的灵敏极谱波新体系。在 0 .6mol/L 盐酸中 ,甲基橙与 NO-2 的亚硝化反应产物在极谱仪上于 - 0 .31 V( vs.SCE)可获得灵敏的极谱波。导数波高与亚硝酸根浓度在 1 .0 9× 1 0 -7～ 1 .0 9× 1 0 -5mol/L范围内成正比 ,检出限为 6.52× 1 0 -8mol/L。研究了极谱波行为及反应机理。并利用该法测定了水样中的亚硝酸根     

新催化动力学光度法测定痕量亚硝酸根

在磷酸介质中,痕量亚硝酸根对溴酸钾氧化酰胺黑10B的催化褪色作用,建立了催化动力学光度法测定痕量亚硝酸根的新方法。并探讨了动力学反应条件,方法的线性范围为0.05～1.2μg/10ml,检出限为4.88×10-9·ml-1,用于地面水及雨水中亚硝酸根的测定,结果满意。     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

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.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.