甲基橙褪色动力学光度法测定槲皮素的研究

基于稀H2SO4介质中,槲皮素对KBrO3氧化甲基橙褪色反应的明显催化作用,建立了测定痕量槲皮素的动力学光度法。在选定的条件下,方法的线性范围为0~0.05 mg/L,表观摩尔吸光系数为4.52×106L.mol-1.cm-1,检出限为0.0012 mg/L。利用此法测定了银杏叶和中药制剂慢严舒柠中的槲皮素,加标回收率为95%~106.7%,相对标准偏差小于3.3%。     

催化动力学光度法测定维脑路通片及槐米中维生素P4

在HAc存在下,少量维生素P4可催化KBrO3氧化丙基红的反应,导致丙基红在521 nm处吸光度显著减小,据此建立了测定维生素P4含量的催化动力学新体系.其线性范围为0.01～0.9 mg/L,检出限为8.9×10-3 mg/L,催化反应总速率常数为9.90×10-4/s.该方法可用于维脑路通片剂和槐米中维生素P4含量...     

甲基绿-钒(Ⅴ)-溴酸钾催化体系测定超痕量钒的研究

在H3PO4介质中,抗坏血酸存在下,超痕量钒能灵敏地催化KBrO3氧化甲基绿褪色。研究了该催化褪色反应的最佳条件及动力学参数,建立了一种测定超痕量钒的新方法。该法的线性范围为0~1.00 ng/mL,检出限为5.20×10-12g/mL。方法可用于芹菜和小麦中钒的测定。     

氯酸钾体系催化动力学光度法测定痕量钒(Ⅱ)

研究了在0.1 mol/L H3PO4介质中,活化剂抗坏血酸的作用下,V(Ⅴ)催化KClO3氧化甲基红褪色的指示反应,由此建立了一种测定痕量V(Ⅱ)的催化动力学光度新方法。研究了影响该催化褪色反应的因素。方法的线性范围为0.09～7.0 ng/mL,检出限为2.9×10-2 ng/mL。方法用于实际样品的测定。     

溴酸钾氧化孔雀石绿和甲基橙褪色光度法测定水中亚硝酸根

在H3PO4介质中,利用痕量NO2-催化KBrO3氧化孔雀石绿和甲基橙褪色的反应,建立了双波长双指示剂催化动力学光度法测定痕量NO2-的新方法。该反应在最大吸收峰505nm和615nm处,催化和非催化体系吸光度的变化与NO2-浓度呈线性关系,线性范围为0.01～0.80μg/mL,检出限为1.3×10-3μg/mL,该方法用于环境水样(自来水、雨水、延安卷烟厂废水)中痕量NO2-的测定,加标回收率为97%～110.2%.     

甲基紫动力学催化光度法测定火腿肠中痕量亚硝酸根

基于在稀H3PO4介质中,亚硝酸根对KBrO3氧化甲基紫的褪色反应具有催化作用,建立了一种测定痕量亚硝酸根的催化光度法。该方法在室温下进行,操作方便,大多数离子不干扰。在选择的实验条件下,检出限为2 89×10-3μg/mL,线性范围为0.003～0.28μg/mL,可用于火腿肠样品中亚硝酸根的测定。     

停流-催化动力学光度法测定药物中的溴

研究了H3PO4介质中,溴离子催化KBrO3氧化丁基罗丹明B的褪色反应特性,测定了反应级数和表观活化能,拟定了反应的最佳条件,建立了停流-催化动力学光度法测定微量溴的新方法。在(27±0.05)℃反应4min测定的检出限为1.51×10-4g/L,线性范围为0~10.0mg/L。该方法用于药物中溴离子的测定,相对标准偏差为2.2%~2.3%,回收率为98%~102%。     

KBrO3氧化甲基紫褪色动力学光度法测定食品中痕量钒

基于0.004 mol/L的柠檬酸介质中,痕量V(Ⅴ)催化KBrO3氧化甲基紫的褪色反应,建立了测定痕量V(Ⅴ)的动力学光度法。方法的检出限为1.23μg/L,线性范围为0～0.16μg/mL。讨论了酸度、反应物浓度、温度、反应时间、干扰离子等因素的影响,确定了该体系反应的最佳条件。在25 mL溶液中,测定2.0μg V(Ⅴ)的RSD为1.9%(n=11)。方法可用于测定小麦和苹果中的痕量V(Ⅴ),RSD为1.1%～2.7%,标准加入回收率为97.6%～99.0%。     

邻苯二酚紫体系催化动力学光度法测定痕量锡(Ⅱ)

基于痕量锡在0.5 mol/L的H2SO4介质中对溴酸钾氧化邻苯二酚紫的褪色反应具有催化作用,建立了一种新的测定痕量锡的催化动力学光度法.确定了该褪色反应的最佳条件:0.5 mol/L H2SO4 1.5 mL;0.1 mol/L KBrO3 1.3 mL;2.0×10-4 mol/L邻苯二酚紫3.5 mL;反应时间为7 min;反应温度为100℃.方法的检出限为4.51×10-3 μg/mL,线性范围为0～3 μg/25 mL.对该方法进行了精密度测定,其相对标准偏差为1.9%.研究了反应的动力学参数,确定了催化反应的的速率方程和表现活化能(Ea=34.10 kJ/mol).该方法可用于水样、人发中痕量锡的测定,相对标准偏差分别为0.32%和1.2%,标准加入回收率分别为99.2%和99.1%.     

胶束增敏阻抑动力学光度法测定痕量水杨酸

基于在H2SO4介质中,溴化十六烷基吡啶(CPB)对于KBrO3氧化曙红Y褪色反应的增敏作用和水杨酸对此反应的阻抑作用。建立了阻抑动力学光度法测定痕量水杨酸的新方法。研究了该反应的最适宜的条件和动力学参数。方法的表观摩尔吸光系数为3.79×105L.mol-1.cm-1,线性范围为:0.040~0.50mg/L,检出限为0.020 mg/L。方法用于复方苯甲酸搽剂中水杨酸的测定。对阻抑褪色反应的机理进行了探讨。     

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.     

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.     

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.     

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.