斯巴沙星-三辛基氧化膦-溴化十六烷基三甲基铵吸光光度法测定混合稀土中钕

研究了钕 斯巴沙星 (SPLX) 三辛基氧化膦 (TOPO) 溴化十六烷基三甲基铵 (CTMAB)体系的光度特性 ,确定了测定混合稀土中钕的最佳条件 ,提出了一种灵敏度较高、选择性好的测定钕的方法。在最佳试验条件下 ,钕的线性范围为 0 .4～ 5 .0× 10 -4 mol·L-1,检出限为 1.0× 10 -6mol·L-1(S N =3)。采用标准曲线法测定混合稀土中钕 ,结果满意     

单扫描示波极谱法测定磷酸氯喹

建立了极谱测定磷酸氯喹的方法。在4.0×10-2mol LNH3·H2O NH4Cl(pH9.5)支持电解质中,磷酸氯喹极谱还原波的峰电位Ep为-1.61V(vs.SCE),其二阶导数峰峰电流ip″与磷酸氯喹浓度在1.0×10-8mol L～1.0×10-6mol L和1.0×10-6mol L～1.0×10-4mol L范围内呈线性关系。10次测量1.0×10-6mol L磷酸氯喹还原波二阶导数峰峰电流,相对标准偏差RSD为0.92%。该方法用于片剂中磷酸氯喹的测定。     

Zr(Ⅳ)-桑色素络合物在碳糊电极上的二次导数吸附伏安法测定Zr的研究

研究了Zr(Ⅱ)-桑色素络合物在碳糊电极正电位区的吸附伏安行为,并利用其在0.74V处的二次导数吸附氧化峰电流与Zr(Ⅳ)浓度为6.0×10-9～2.0×10-6 mol/L呈线性而测定Zr;检出限为3.0×10-9 mol/L(S/N=3).最佳测定条件为2.0 mol/L HCl、1.0×10-5 mol/L桑色素;富集电位为0V(vs.SCE);扫描速度为250 mV/s.该法不需萃取分离,可直接用于岩石样品中Zr的测定,结果满意.     

钼(Ⅵ)-7-(1-苯偶氮)-8-羟基喹啉-5-磺酸钠络合吸附波研究及应用

在pH4.8的0.013mol/L的HAc-NaAc介质中,钥(Ⅵ)-7-(1-苯偶氮)-8-羟基喹啉-5-磺酸钠体系在滴汞电极上,于-0.46V(vs.SCE)电位处得到良好的吸附还原波,其二阶导数峰电流I_p与Mo(Ⅵ)在2.5×10~(-8)～4.5×10~(-7)mol/L浓度范围内呈良好的线性关系,检测限为1.25×10~(-8)mol/L Mo(Ⅵ),方法用于钢样中微量钼的测定,结果较好.对电极机理进行了研究.     

锡(Ⅳ)-3,4-二羟基苯甲酸-钒(Ⅳ) 体系极谱吸附催化波的研究

在含有 3.6×10-3mol/L 的 VOSO4、6.0×10-5mol/L 的 3,4-二羟基苯甲酸(DHBA)、 0.1mol/L 的甲酸盐缓冲溶液(pH3.3)体系中,Sn(Ⅳ)-DHBA 络合物产生一灵敏的吸附平行催化波,峰电位在 -0.52 V(vs.SCE).二次导数波高与锡浓度在 3.4×10-10～5.1×10-7mol/L 范围内呈良好线性关系.检出限达浓度 2×10-10mol/L .研究了催化波的性质和电极反应机理.方法已应用于罐头食品中微量锡的测定.     

铅-N-(8-喹啉基)-N′-苯甲酸基硫脲络合吸附波的研究

在8×10~(-3)mol/L NaOH-0.2mol/L KClO_3底液中,Pb(Ⅱ)-QBTU体系产生灵敏的阴极化二阶导数波,峰电流与铅浓度在4.0×10~(-8)～4.5×10~(-6)mol/L范围内有良好的线性关系。本文对电极过程,反应机理,极谱波的性质进行了详细的探讨。     

极谱催化波法测定马蔺子素

报道了在Na2 B4 O7 KH2 PO4 K2 S2 O8体系中马蔺子素的极谱催化波。拟定了测定马蔺子素的新方法。在 8.0× 10 - 3mol/LNa2 B4 O7 1.6× 10 - 2 mol/LKH2 PO4 (pH =7.7) 5 .0× 10 - 3mol/LK2 S2 O8底液中 ,极谱催化波峰电位Ep=-1.2 3V(vs .SCE) ;二阶导数峰峰电流i″p 与马蔺子素浓度在 2 .0× 10 - 9～ 2 .0× 10 - 6 mol/L范围内呈良好线性关系 ,检出限为 1.0× 10 - 9mol/L。催化波灵敏度比相应马蔺子素还原波高 75倍。采用该法测定了胶囊中马蔺子素的含量     

铽(Ⅲ)-1,4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4]体系荧光性质的研究及应用

本文研究了Tb(Ⅲ)-1,4-双(′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4](BPMPBD)-溴化十六烷基三甲胺(CTMAB)体系的荧光性质,探讨了响影体系荧光性质的诸因素,确定了最佳实验条件。该体系中Tb(Ⅲ)浓度以2.0×10~(-5)～1.0×10~(-10)mol/L范围内与其荧光强度呈线性关系,检测限可达到5.0×10~(-11)mol/L。应用于合成样品中微量Tb(Ⅲ)的分析,结果令人满意。     

铑（Ⅲ）与2—（3,5—二氯—2—吡啶偶氮）—5—二甲氨基苯胺络合物的催化氢波

本文提出一种新的测定铑的催化氢波体系.先使Rh(Ⅲ)与3,5-diCl-PADMA在HAc-NaAc缓冲溶液中生成稳定的络合物,再以适量HclO_4将溶液酸化后进行极谱测定。利用正交试验法确定体系的最佳分析条件为:0.05 mol/L pH5.0的HAc-NaAc,1.6×10~(-5)mol/L3,5-diCl-PADMA,沸水浴加热15min.,4.4 mol/L HCIO4酸化。在此条件下的线性范围为1.9×10~(-11)～3.9×10~(-9)mol/L,检出限达5.8×10~(-12)mol/L。大量Cu(Ⅱ)、Ni(Ⅱ)、Fe(Ⅲ)及Co(Ⅱ)对体系的干扰可用EDTA消除。研究了催化波的性质,表明该波为Rh(Ⅲ)与3,5-diClPADMA络合物的催化氢波。     

2,6-二溴-4-甲基偶氮磺分光光度法测定钕铁硼合金中的钕

研究2,6-二溴-4-甲基偶氮磺(DBM-SA)与钕(Ⅲ)的显色反应,建立了测定钕铁硼合金中钕的分光光度分析方法。在2mol/L磷酸介质中,钕(Ⅲ)与DBM-SA发生灵敏的显色反应,生成配合比为1:2的蓝色配合物,其最大吸收波长为634nm,表观摩尔吸光系数为1.0×10~5L/(mol·cm)。钕(Ⅲ)的浓度在0～1.0μg/mL内符合比耳定律。该方法用于实际样品分析,加标回收率为97.6％～99.8％,测定结果的相对标准偏差为0.65％～0.82％。     

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.