冷原子荧光法间接测定水中氰化物

本文详细研究了氰化物蒸馏条件及其稳定性问题，建立了一个冷原子荧光法间接测定水中氰化物的方法，并用于海水及氰化液中痕量ＣＮ－的测定，结果令人满意。ＣＮ－检出限为０．０２μｇ／ｍＬ，回收率９５％～９８％，变异系数７．３％～８．９％。     

CN-与异烟酸-硫代巴比妥酸显色反应的研究及应用

在弱酸性介质中,于氯胺T存在条件下,CN-可与异烟酸-硫代巴比妥酸形成一蓝色染料,该染料最大吸收波长位于642 nm,且其吸光度A与氰化物含量在一定的范围内呈良好的线性关系,据此建立了测定生活饮用水中微量氰化物的异烟酸-硫代巴比妥酸分光光度法。本法氰化物含量在0~4.0μg/10 mL范围内符合比耳定律。方法用于生活饮用水中微量氰化物的测定,结果令人满意。     

次甲基蓝萃取分光光度测定铝中微量硼

1957年Ducret首次利用次甲基蓝萃取分光光度法测定了硅中微量硼。十余年来,此法得到了愈来愈多的应用和发展。它比常用的姜黄素比色法具有操作简单、颜色稳定及共存离子干扰较少等优点。本工作将此法应用于铝及其合金中微量硼的测定,获得了较满意的结果。方法的精密度可达±4％,硼的回收率为92％。     

鲁米诺-氰化物化学发光反应的研究——环境水样中氰化物的测定

本文提出了利用鲁米诺-氰化物化学发光体系测定氰化物的新方法。方法的检出限是1.2ng/ml,校正曲线在2～100ng/ml CN~-范围内具有良好的线性。相对标准偏差小于4％。此方法已用于自来水和工业废水中氰化物的测定。文中对鲁米诺与氰化物化学发光反应的可能机理作了初步探讨。     

微量氰化物的测定 Ⅰ.利用铜-铬天青S-氯化十六烷基吡啶络合物间接吸收光度法测定微量的氰

近年来研究金属Hg(Ⅱ)、Pt(Ⅳ)、Cu(Ⅱ)与有机试剂形成的络合物间接吸收光度法测定微量的氰化物的工作曾有报导。利用三元络合物间接吸收光度法测定微量氰化物的研究也得到重视。然而,迄今尚未见到利用三元胶束络合物间接法测定微量氰化物的报导。本文根据铜(Ⅱ)与铬天青S(CAS)在有过量的氯化十六烷基吡啶(CPC)存在下,在pH10溶液中可形成水溶性的红色络合物的特性,又基于氰离子与铜     

ICP-AES法同时测定精对苯二甲酸中微量金属元素

采用等离子体原子发射光谱法(ICP-AES)测定精对苯二甲酸(PTA)中微量金属元素。讨论了影响因素，优化了操作参数。钠、铁、钴、锰、镍、铬六种元素回收率在94．0％～104．0%之间。此法对其它有机体中的金属元素测定有参考价值。     

流动注射光度法测定水中氰化物

基于氯化氰与1,3 二甲基巴比妥酸和吡啶 4碳酸在缓冲条件下反应,产生红色络合物的原理,提出了用流动注射光度法(CFA)测定自来水中氰化物。该方法线性范围为0～40.0μg·L-1,精密度和准确度高,检出限为0.002mg·L-1,适用于自来水中微量氰化物的检测。分析频率为30个样品·h-1,特别适合大批样品的测定。     

金属镍和钴中微量锌的测定-PAN 法

金属镍、钴中微量锌之测定过去多采用乙酸乙酯萃取分离双硫腙比色法,此法需时较长,操作不便;目前国内一般应用氰化物掩蔽主体元素或者高分子胺萃取分离等手段以改善此法。但前法需用剧毒试剂,而后法需用胺类不仅味嗅且萃取剂的再生使用比较麻烦,同时这类方法均离不了用双硫腙显色,干扰元素较多。在批林批孔运动的推动下,我们重温了伟大领袖毛主席的教导:“……人类总得不断地总结经验,有所发现,有所发明,有所创造,有所前进。”在参阅了有关资     

荧光光度法测定水中痕量的氰化物

测定微量氰化物的方法很多,就目前来说,普遍使用的仍是吡啶联苯胺(吡唑啉酮,巴比妥酸)或异烟酸-吡唑啉酮比色法。但它使用的试剂毒性大、有臭味,测定痕量氰化物灵敏度尚欠佳。荧光法是测定痕量氰化物的一种高灵敏度分析方法,本文在前人的基础上,研究了在铜离子和氰化物存在下,无色荧光素被氧化生成荧光素的条件及应用。拟定了一个不经蒸馏分离直接测定饮用水、地面水中痕量氰化物的方法。本法操作简单快速,灵敏度高,检出下限为0.8ppb。     

CN--异烟酸-硫代巴比妥酸-CTMAB显色体系的研究及应用

在弱酸性介质中,有溴化十六烷基三甲铵(CTMAB)存在条件下,CN-与异烟酸-硫代巴比妥酸形成一蓝色化合物,其最大吸收波长(λmax)位于646 nm,表观摩尔吸光系数6ε46=4.67×104L.mol-1.cm-1,且其吸光度A与氰化物含量在一定的范围内呈良好的线性关系。据此,建立了测定生活饮用水中微量氰化物的CTMAB-异烟酸-硫代巴比妥酸显色光度法。本法氰化物含量在0~4.0μg/10.0 mL范围内符合比耳定律,用于生活饮用水中微量氰化物的测定,结果令人满意。     

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.     

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.     

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.     

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.