流动注射在线阴离子树脂预富集火焰原子吸收测定痕量铜

研究了以阴离子交换树脂作吸附剂的流动注射在线微柱预富集火焰原子吸收测定铜的新方法。在最佳条件下富集１５０ｓ，富集２３倍，检出限０．２μｇ／Ｌ，ＲＳＤ为１．６％，分析速度２０次／ｈ。天然水样中可能存在的离子不干扰铜的测定。所建立的方法已用于水样中痕量铜的测定。     

催化荧光光度法测定痕量亚硝酸根

亚硝酸根广泛存在于环境、水体、食品等物质中，它可与胺类及酰胺类化合物反应生成致癌物亚硝胺，因此，它是水质、环境、食品等检测的重要项目之一。催化动力学光度法测定亚硝酸根已有不少报道，而催化荧光法测定亚硝酸根的报道不多。吡啰红B是一种生物染色剂，在水溶液中发射红色荧光。试验发现，稀磷酸介质中，溴酸钾氧化吡哕比B使荧光猝灭，亚硝酸根对此氧化还原褪色反应具有灵敏催化作用，据此建立了测定亚硝酸根的催化荧光光度法。本法灵敏度较高，选择性好，简便快速，用于水及蔬菜中痕量亚硝酸根的测定，结果满意。     

大孔球形纤维素吸附剂的制备及性能研究

本课题以天然棉纤维为原料，通过碱化、老化、碳化以及溶解，制得纤维素粘胶，按一定比例加入Ca-CO3，然后，采用反相悬浮再生法，制备纤维素球，在HCl-NaCl-CaCl2。混合溶液中除去CaCO3后，得大孔球形纤维素经SEM对整体结构和表面结构进行了表征。这种大孔球经环氧化后，制备了一种开链氮杂冠醚化大孔球形纤维素吸附剂（PSC-OCAC），测定了PSC-OCAC对几种常见金属离子的吸附性能，并应用到江河水体中几种金属的分离、富集，建立起PSC-OCAC-分离富集-火焰原子吸收分光光度法，测定水体中痕量重金属总量的方法，测定了南充境内两河、嘉陵江水体中的几种常见重金属含量。     

催化光度法测定超痕量亚硝酸根

迄今为止,有关动力学法测定亚硝酸根的报道甚少,笔者实验发现,在磷酸介质中,以溴酸钾氧化中性红,亚硝酸根具有高催化活性,据此,我们研究了适宜的催化反应条件,以及共存离子的影响,从而建立了测定超痕量亚硝酸根的新催化光度法,本法测定亚硝酸根     

在线螯合树脂富集火焰原子吸收光谱法测定天然水体中铜和锌

对螯合树脂富集——火焰原子吸收光谱法测定天然水体中痕量铜和锌的在线富集条件、干扰因素等进行研究,在线富集倍数达到两个数量级,在灵敏度与石墨炉原子吸收光谱法相当情况下,提高了测定准确度。     

催化溴酸钾氧化萘酚绿B褪色紫外光度法测定亚硝酸根

亚硝酸根广泛存在于环境、水体、食品中,它可与胺类及酰胺类化合物反应生成致癌物质亚硝胺,因此,痕量亚硝酸根的测定方法研究一直受到重视。目前国内外主要利用偶氮染料的分光光度法。催化动力学光度法[1]测定亚硝酸根等也有报道[2~6],而紫外催化光度法测定亚硝酸根的报道不多。在稀磷酸介质中,溴酸钾氧化萘酚绿B,亚硝酸根对此氧化还原反应具有灵敏催化作用。据此建立了测定硝酸根的催化紫外光度方法。方法灵敏度为1.58×10-6g·L-1,线性范围为0.1~2.0μg/25 mL。1试验部分1.1主要仪器与试剂UV-265型紫外光度计亚硝酸根标准溶液:1.0 g·L…     

溴酸钾氧化吡罗红G催化动力学光度法测定痕量NO2^—

研究了在磷酸介质中亚硝酸根催化溴酸钾氧化吡罗红Ｇ而使褪色，建立了催化动力学光度法测定痕量亚硝酸根的新方法，测定范围为０．２－２０μｇ／ｍＬ，检出限为０．２ｎｇ／ｍｌ，用于食品和水样中的亚硝酸根测定获得满意结果。     

溴酸钾氧化吡口罗红G催化动力学光度法测定痕量NO-2

研究了在磷酸介质中亚硝酸根催化溴酸钾氧化吡口罗红Ｇ而使其褪色，建立了催化动力学光度法测定痕量亚硝酸根的新方法，测定范围为０．２～２０μｇ／ｍＬ，检出限为０．２ｎｇ／ｍＬ，用于食品和水样中的亚硝酸根测定获得满意结果     

流动注射-火焰原子吸收法测定天然水体中的铬(Ⅲ)和铬(Ⅵ)

采用流动注射—火焰原子吸收法则定天然水体中的微量铬(Ⅲ)和铬(Ⅵ)。用螯合树脂在线富集浓缩样品中的铬(Ⅲ)，结合流动注射技术，将洗脱液直接导入火焰原子吸收分光光度仪中进行测定。加入盐酸羟胺使水体中的铬(Ⅵ)转化成铬(Ⅲ)，然后间接测定。对在线富集测试条件、干扰物质的影响等进行了探讨。该方法检出限为0．84μg/mL，加标回收率为94．4％～103％。     

药物中亚硝酸根的流动注射催化光度法分析

以亚硝酸根催化溴酸钾在磷酸介质中氧化维多利亚天蓝Ｂ褪色为指示反应，建立了反相流动注射催化光度法测定痕量亚硝酸根的新方法。本法操作简单、快速，灵敏度高，测定亚酸根的线性范围为２￣８０μｇ／Ｌ，直接用于含硝酸内服药和针剂中亚硝酸根的测定，与α－萘胺比色法对照结果一致。     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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%).