四-（对甲氧基苯基）-卟啉柱前衍生，固相萃取高效液相色谱法测定痕量铁、钴、铜、锌和锰

研究了用固相萃取富集，高效液相色谱法测定环境水样中痕量Fe、Co、Cu，Zn和Mn的方法。环境水样中的Fe、Co、Cu、Zn和Mn用四-(对甲氧基苯基)-卟啉(T4MPP)柱前衍生，用Waters Sep—Pak—C18固相萃取小柱萃取富集Fe、Co、Cu、Zn和Mn的T4MPP络合物，富集倍数达50倍；然后用甲醇和四氢呋喃梯度洗脱为流动相，Waters Xterra^TM RP18色谱柱为固定相分离，用二极管矩阵检测器检测。Fe、Co、Cu、Zn和Mn的检测限分别为：3．2、1．8、2．0、2．0和4．5ng/L。方法相对标准偏差为2．1％～3．7％，标准回收率为94％～107％。该方法用于环境水样分析，结果令人满意。     

偏最小二乘法辅助分光光度法同时测定痕量锰、铁、铜和锌

痕量Mn（Ⅱ）、Fe（Ⅲ）、Cu（Ⅱ）和Zn（Ⅱ）与2－（5－溴－2－吡啶偶氮）－5－二乙氨基苯酚和聚乙二醇辛基本基醚在pH8．8发生高灵敏的显色反应，所形成的三元胶束络合物的吸收光谱严重重叠，用偏最小二乘法（PLS）辅助分光光度法成功地同时测定了模拟试样及铝合金和饲料添加剂中上述四种痕量组分。结果表明，PLS法是化学计量学法中一种可适用于基体较复杂的实际试样中痕量组分同时分光光度测定的优良的多元计算方法。     

等离子体发射光谱法测定茶水中无机元素的含量

采用电感耦合等离子体发射光谱法对茶水中的无机元素进行分析,对其中的Cu、Zn、Mn、P、Fe5种元素进行定量,讨论了等离子体发射光谱法最佳实验条件及影响茶叶中无机元素浸出量的因素。Cu、Zn、Mn、P、Fe的回收率为92．5％～103．5％,测定结果的相对标准偏差为1．34％-4．5％（n=5）。     

FAAS测定十味平性活血化淤中药中Fe、Cu、Zn、Mn的含量

为揭示中药药性本质,用FAAS测定并比较了十味平性活血化淤中药中微量元素Fe、Cu、Zn和Mn的含量。结果表明,十味活血化淤中药均含有Fe、Cu、Zn、Mn等4种元素,其中Fe、Cu、Zn、Mn的含量范围分别为0．0416～1．2977,0．0025—0．0297,0．2100～0．1501,0．0071～0．7380μg·g^-1。方法加标回收率为98．7％～100．5％,RSD≤2．45％（n=6）。实验方法简便可行,测定结果准确可靠,为后续研究提供了基础数据。     

微波消解火焰原子吸收光谱法连续测定金银花中铁、锌、铜和锰

采用微波消化技术,以氘灯背景校正方式,在HNO3介质中,直接用火焰原子吸收法在同一体系中连续测定了金银花中微量元素Fe、Zn、Cu、Mn,并优化了最佳实验条件.在选定条件下,检出限为Fe 0.0047 μg/mL,Zn 0.0032μg/mL,Cu 0.0052μg/mL,Mn 0.0028μg/mL,相对标准偏差为1.5%～3.2%,回收率为96.4%～103.4%.适用于金银花中微量Fe、Zn、Cu、Mn的测定.     

Nafion化学修饰圆盘预富集-石墨炉 原子吸收联用法对牛血超氧化物歧化酶中铜、锌分布状态的研究

本文研究了Nafion化学修饰钨丝圆盘预富集-石墨炉原子吸收(GFAAS)方法测定牛血超氧化物歧化酶(SOD)中游离态Cu～(2+)及Zn～(2+)的方法,并用GFAAS法直接测定SOD中铜、锌的总量,证实了牛血SOD中金属辅基铜、锌原子个数比为1:1,初步探讨了一定浓度的牛血SOD中Cu～(2+)、Zn～(2+)的表观离解平衡常数。为提高SOD的活性和稳定性的研究,提供了一种有效的方法。     

应用石墨炉-电感耦合等离子体光谱分析法直接测定生物试样中的痕量元素

本文提出了以石墨炉为蒸发装置,以ICP为激发光源直接测定生物试样中痕量元素的新方法。该法以高纯石墨粉为稀释剂,按一定比例(通常为1:1)与试样混合,采用标准加入法进行测定。方法简便、灵敏、进样效率高,分析前试样无需进行化学处理。方法测定As、Cd、Co、Cr、Cu、Fe、Mn、Ni、Pb、Se和Zn的检出限达ppm至ppb级,并成功地用于某些生物试样中上述痕量元素的直接测定,分析结果同NBS的参考值相吻合。     

黄芪及其水煎液中Cu、Mn、Zn、Fe、Se的测定和浸出率研究

用原子吸收法对黄芪及其水煎液中的Cu、Mn、Zn、Fe进行了测定 ,用紫外分光光度法测定了其中的Se ,从而得出各元素的浸出率。结果表明五种元素的浸出率为 :Cu >Zn >Mn >Se >Fe。     

以8-羟基喹啉为化学改进剂石墨炉原子吸收光谱测定水和空气尘粒物中铬的研究

研究了8－羟基喹啉在石墨炉原子吸收光谱法（GFAAS）测定痕量铬中的化学改进作用及其主要影响因素。在优化实验条件下，8－羟基喹啉的存在能显著提高石墨炉原子吸收法测定铬的灵敏度。方法的检出限为0．20ng/mL，精密度为RSD＝2．6％（n＝8，c＝5ng/mL），本法已用于天然水和大气尘粒物中痕量铬的测定。     

FAAS法测定新疆两种不同产地沙枣中的6种微量元素

目的建立沙枣中Ca、Mg、Cu、Zn、Fe、Mn等6种微量元素的火焰原子吸收光谱法。方法在确定的火焰原子吸收光谱法检测条件下,使用马弗炉处理样品,对新疆两种不同产地的沙枣中Ca、Mg、Cu、Zn、Fe、Mn等6种微量元素的含量进行了测定。结果各元素的回收率（／Z=5）在97．50％～104．60％之间,RSD（n=5）在1．61％～3．51％之间。结论该法简单、快速,具有很好的精密度和灵敏度,适用于沙枣中6种微量元素的测定。     

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%.     

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.     

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.     

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.     

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.