罗丹明6G-高碘酸钾体系催化荧光光度法测定氟化物

建立了测定水中微量氟化物的催化动力学光度方法。在硫酸介质中,微量氟化钠对高碘酸钾氧化罗丹明6G具有催化作用,使罗丹明6G的荧光强度减弱。结果表明:溶液的荧光激发波长和发射波长分别为535nm、556nm,氟化钠浓度在0.04~2.8μg·m L-1时与荧光强度ΔF呈良好的线性关系。其线性回归方程与相关系数为△F=26.94C+45.135,R2=0.9909,检出限为0.023μg·m L-1。回收率为98.8%~101%,RSD为0.02~0.85,该方法简便,快速,灵敏度好,准确度高,可用于水中微量氟化物的测定。     

催化动力学荧光法测定水中氟

在酸性条件下,游离的F-对高碘酸钾氧化罗丹明B的反应具有催化作用,可使罗丹明B的荧光减弱.基于此,建立了测定微量F的催化动力学荧光光度分析新方法.结果表明:溶液的荧光激发波长和发射波长分别为562 nm、582 nm,测定的线性范围是0.04～2.6 μg/mL,检出限是0.032 μg/mL,并已用于水中微量F-的测定.     

罗丹明6G荧光猝灭法测定痕量肝素

在pH 8.0的缓冲体系中,肝素使得罗丹明6G的荧光发生明显猝灭,罗丹明6G的荧光猝灭程度在一定范围内与肝素的浓度成正比,据此建立了荧光猝灭法测定痕量肝素的方法,并对体系的荧光猝灭机理进行了讨论。体系的激发波长为482 nm,发射波长为560 nm,线性范围为0.05~3.0 mg/L,检出限为6.1μg/L。方法已应用于肝素钠注射液中肝素含量的测定。     

恒波长同步荧光猝灭法测定饮用水中微量溴酸根

在HCl介质中,Δλ=20nm,溴酸根对罗丹明123的恒波长同步荧光有猝灭作用,且猝灭程度与溴酸根的含量呈线性关系,据此建立了恒波长同步荧光猝灭测定饮用水中的微量测定溴酸根的新方法。该方法的线性范围为0～200μg/L,检出限为3.0ng/mL。该方法可用于化学试剂和各种饮用水中溴酸盐含量的测定。     

罗丹明类染料荧光猝灭法测定异烟肼

在HAc-NaAc缓冲溶液中,罗丹明类染料罗丹明6G(Rh6G)、罗丹明B(RhB)和丁基罗丹明(b-RhB)分别在553,582和589 nm处产生一个较强的荧光峰。加入异烟肼(INH)后,由于异烟肼分别与Rh6G,RhB和b-RhB发生作用,从而使得3种体系的荧光均发生猝灭。在最佳实验条件下,异烟肼浓度分别在0. 10～20μg/mL,0. 10～25μg/mL和0. 50～22μg/mL范围内与各体系的荧光强度改变值(!F)之间呈良好的线性关系,且3种体系的检出限分别为9. 04,21. 7和20. 4 ng/mL。据此,建立了一种荧光猝灭法测定药物中异烟肼含量的分析方法。     

吖啶橙-罗丹明6G能量转移荧光法测定痕量磷

在λex/λem=450/556nm,十二烷基苯磺酸钠(DBS)存在下,吖啶橙-罗丹明6G能够能有效能量转移,使罗丹明6G荧光大大增强,酸性条件下,正酸根与钼酸钼反应生成磷钼酸,磷钼酸与R6G形成离子缔合物,使R6G的光猝来利用吖淀橙-罗丹明6G能量转变荧光法测定痕量磷,提高了测定磷的灵敏度和选择性,磷含量的0.05~0.70μg/L 范围内与罗丹明6G的荧光猝程度呈良好的线性关系.最低检出限为5ng/L,回收率为95%~110%,测定0.50μg/L,磷溶液,相对标偏差为6%,该法用于水样及土壤中的活性磷的测量,结果满意.     

桑色素荧光猝灭法测定水中微量锑

在B-R缓冲液中,微量Sb(III)对桑色素的荧光具有明显的猝灭作用,据此建立了测定微量Sb(III)的新方法。当最大激发波长与发射波长分别为417 nm和496 nm时,Sb(III)的质量浓度在0.004~0.06μg/mL范围内与桑色素荧光强度的猝灭值ΔF呈线性关系,其检出限为9.80×10-4μg/mL。对0.02μg/mL Sb(III)进行12次平行测定,相对标准偏差为0.31%。方法可用于不同环境水样中微量Sb(III)的测定,回收率在98.4%~103.6%之间。     

SAF-Tween80-β-CD荧光熄灭法测定微量钼的研究

在HCl介质中,吐温80(Tween80)和β-环糊精(β-CD)存在下,钼与水杨基荧光酮(SAF)形成复杂配合物使荧光熄灭,由此建立了测定微量钼的荧光熄灭新方法。该体系的最大激发波长λex=455 nm,最大发射波长λem=522 nm。Mo(Ⅵ)量在0~0.12μg/mL范围荧光熄灭程度(ΔF)与Mo(Ⅵ)质量浓度呈线性关系,线性回归方程为ΔF=31.839ρ(μg/mL) 29.726,相关系数R2=0.9996,检出限为1.53μg/L。该方法灵敏度高,选择性好,用于测定水样中的微量钼,回收率在99.4%~100.8%之间。     

荧光光度法测定面粉中的过氧化苯甲酰

在中性或弱酸性中,氨存在条件下亚硫酸盐与邻苯二甲醛生成强荧光物质,而过氧化苯甲酰对该荧光物质具有抑制作用。基于该原理建立了一种简单、灵敏测定面粉中微量过氧化苯甲酰的荧光光度法。荧光物质的最大激发波长和发射波长分别为326、389 nm。方法检出限为0.23μg/mL,线性范围为0.8~8.0μg/mL,线性回归方程为ΔF=20.589c 2.8805,相关系数r=0.999 0。该法用于测定面粉中微量过氧化苯甲酰含量的相对标准偏差为1.34%~2.32%,回收率为95.4%~101.1%。     

水杨基荧光酮-乳化剂-羟丙基-β-环糊精荧光猝灭法测定微量铜

建立了在羟丙基-β-环糊精(HP-β-CD)和乳化剂(OP)存在下,在NaAc-HAc介质中,以水杨基荧光酮(SAF)作为荧光试剂,用荧光猝灭法测定微量铜的新方法;最大激发波长和发射波长分别为365 nm和539 nm,Cu2+含量在0~0.20μg/mL范围内符合线性关系,方法检出限为1.0μg/L。已用于人发和茶叶中铜含量的测定。     

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.     

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.