双波长双指示剂催化光度法测定铜的研究

研究了在pH 4.0的HAc～NaAc缓冲介质中,利用痕量铜(Ⅱ)催化过氧化氢氧化罗丹明B和亚甲基蓝褪色的指示反应,通过测量540 nm和660 nm下,催化体系和非催化体系吸光度的变化,建立了双波长双指示剂催化动力学光度法测定痕量铜的新方法.方法的线性范围为0.00080～0.048μg/mL,检出限为4.0×10~(-11) g/mL.方法可用于水中铜的测定.     

双波长双指示剂催化动力学光度法测定食品中的痕量铜

在pH=9.65的NH3-NH4Cl缓冲溶液中,利用Cu2+对H2O2氧化中性红和溴甲酚紫褪色反应具有较强的催化作用,通过测量460nm和590nm波长下催化体系和非催化体系的吸光度,建立了双指示剂、双波长催化动力学光度法测定痕量Cu2+的新方法。方法的线性范围为0.0060～0.072μg/mL,检出限为8.0×10-12g/mL。对Cu2+进行11次平行测定的相对标准偏差为2.9%。方法用于面粉和大米中痕量铜的测定,结果令人满意。     

双波长双指示剂-催化动力学光度法测定奶粉中的锌

研究发现在HCl介质中,痕量锌对H2O2氧化甲基紫和亚甲基蓝褪色具有强烈的催化作用,通过测量580 nm和668 nm处催化反应体系和非催化反应体系吸光度的变化,建立了双波长双指示剂催化动力学光度法测定痕量锌的新方法。在最佳实验条件下,线性范围为1.5~60μg/L,线性方程为ΔA=0.0169ρZn2+(μg/mL)+0.0019,r=0.9982,方法检出限为0.84μg/L。该方法可用于奶粉痕量锌的测定。     

双波长双指示物催化光度法测定水中痕量铜

研究了在pH5.5的Na2HPO4-NaH2PO4缓冲溶液介质中，痕量Cu（Ⅱ）催化过氧化氢氧化吖啶黄和酸性品红褪色的指示反应。通过测量450nm和540nm处，催化反应体系和非催化反应体系吸光度的变化，利用铜离子浓度与两波长处吸光度差值的和呈线性关系，建立了双波长双指示物催化光度法测定痕量铜的新方法。在最佳实验条件下，测定铜的线性范围为0．60～32μg/L，检出限为0．24μg/L。该方法操作简单，灵敏度高，选择性好，用于水样中痕量铜的测定，获得满意结果。     

甲基橙-亮绿体系动力学光度法测定茶叶中痕量铁

在硫酸介质中,Fe(Ⅲ)对过氧化氢氧化甲基橙和亮绿褪色反应具有强烈的催化作用,通过测定510 nm和640 nm波长下催化体系和非催化体系的吸光度,建立了双波长双指示剂催化动力学光度法测定痕量Fe(Ⅲ)的新方法。最佳实验条件下,测定的线性范围为8.0~200μg/L,检出限为1.12×10-10g/L。对20.0μg/L Fe(Ⅲ)进行12次平行测定的相对标准偏差为0.067%。该方法灵敏度高,体系稳定,具有较好的选择性,用于茶叶中痕量铁的测定,结果满意。     

双波长双指示剂催化光度法同时测定Fe和Cu

研究了在Na2SO4介质中,痕量Fe(Ⅲ)和Cu(Ⅱ)催化H2O2氧化次甲基蓝和甲基橙褪色的指示反应,通过测量440和664 nm波长下,催化反应体系和非催化反应体系的吸光度,建立了双波长、双指示剂催化动力学光度法同时测定痕量Fe(Ⅲ)和Cu(Ⅱ)的新方法.同时测定Fe(Ⅲ)和Cu(Ⅱ)的线性范围分别为0.0050～0.50 μg/25 mL和0.0025～0.75 μg/25 mL,检出限分别为6.9×10-8 g/L和8.7×10-8 g/L.用于水样中痕量Fe(Ⅲ)和Cu(Ⅱ)的测定.     

双波长双指示剂催化光度法测定痕量Mn(Ⅱ)

在硫酸介质中,以氨三乙酸为活化剂,利用痕量Mn(Ⅱ)催化高碘酸钾氧化灿烂绿和酸性铬蓝K褪色的指示反应,分别在430nm和630nm波长下测量催化体系和非催化体系的吸光度,建立了双指示剂双波长催化动力学光度法测定痕量Mn(Ⅱ)的新方法。在优化条件下,测定Mn(Ⅱ)的线性范围为0.00200～0.0300μg/mL,检出限为1.2×10-11 g/mL。方法可用于茶叶和废水中痕量锰的测定。     

高碘酸钾氧化刚果红和萘酚绿B褪色催化动力学光度法测定茶叶中的微量锰

在NH3-NH4Cl缓冲溶液介质中,以氨三乙酸为活化剂,利用微量Mn(Ⅱ)对KIO4氧化刚果红和萘酚绿B的褪色反应具有催化作用,通过测量480nm和720nm波长处催化和非催化体系吸光度的变化,建立了双波长双指示剂催化动力学光度法测定微量Mn(Ⅱ)的新方法。方法的线性范围为2.4～40μg/L,检出限为0.301μg/L。用于茶叶中锰的测定,加标回收率为96.2%～101.4%。     

双波长分光光度法测定矿石中的锡

研究了用双波长光度法在锡-苯芴酮-动物胶体系测定矿石中锡,在测定波长为505 nm和为540 nm时测定锡以消除钼的干扰,锡在5~50μg/50 mL范围内符合郎伯-比耳定律,小于30μg/50 mL钼不干扰锡的测定。     

双波长双指示剂催化动力学光度法测定痕量Fe(Ⅲ)

研究了在HCl介质中,Fe(Ⅲ)催化H2O2氧化甲基橙和亚甲基蓝褪色的指示反应。通过测量510nm和660nm波长处催化和非催化体系吸光度的变化,基于Fe(Ⅲ)的浓度与两波长处吸光度差值的加和呈线性关系,建立了双波长双指示剂催化动力学光度法测定Fe(Ⅲ)含量的新方法。方法的线性范围为0.008~0.24μg/mL,用该法测定菠菜、紫菜、蛋黄中Fe(Ⅲ)含量,相对标准偏差为1.0%~4.6%,加标回收率为98.9%~104.6%。     

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.