用异丙嗪快速检定微量铈的新方法

把医用药物异丙嗪引入分析化学作新无机分析试剂。报道了新显色剂异丙嗪与高价铈显色反应的最佳条件、灵敏度、选择性和界限比,建立了用异丙嗪检定高价铈的新方法。于0.9 mol.L-1H2SO4介质中,异丙嗪与铈(Ⅳ)在室温下反应,溶液显桃红色,色泽稳定3 h以上。检出限为0.01μg,稀释限为1∶5×106。     

快速检定微量铋(Ⅲ)离子的新方法

将医用药物异丙嗪引入分析化学作无机分析试剂.报道了显色剂异丙嗪与铋离子显色反应的最佳条件、灵敏度、选择性和界限比,建立了用异丙嗪检定Bi(Ⅲ)离子的新方法.于5.4 mol/L H2SO4介质中,异丙嗪与Bi(Ⅲ)在室温下反应,溶液显桃红色,络合物稳定3 h以上.检出限量为0.01 μg,界限比为1:5×106.     

曙红B共振光散射法测定微量的盐酸异丙嗪

研究了染料曙红B与盐酸异丙嗪的结合反应.在pH=3.50的Walpole介质中,曙红B本身的共振光散射信号较弱,与盐酸异丙嗪结合形成离子缔合物后,体系的共振光散射明显增强,并且光散射增强强度与盐酸异丙嗪在一定浓度范围内成正比,据此建立了一种高灵敏测定盐酸异丙嗪的方法.在体系的最大散射波长363 nm处,测得盐酸异丙嗪的线性范围为7.5×10-8～4.5×10-6 g/mL,检测限为1.8×10-8 g/mL,用于盐酸异丙嗪片剂、针剂、人血清及尿样中盐酸异丙嗪的测定,结果令人满意.     

超高效液相色谱-质谱对动物源食品中氯丙嗪、异丙嗪及其代谢物的测定

建立了动物源食品中吩噻嗪类药物氯丙嗪、异丙嗪及其代谢物氯丙嗪亚砜和异丙嗪亚砜同时测定的固相萃取超高效液相色谱-电喷雾电离串联四极杆质谱(UPLC-ESI MS/MS)方法.样品用乙酸乙酯和氢氧化钠溶液提取,Oasis HLB柱富集净化,超高效液相色谱-电喷雾串联四极杆质谱仪检测,采用多反应监测正离子模式,可以一次性对动物源性食品中的吩噻嗪类药物氯丙嗪、异丙嗪及其代谢物氯丙嗪亚砜和异丙嗪亚砜进行定性和定量测定.方法在 1 ～100 μg/L范围具有良好的线性,回收率为76% ～96%,定量下限(S/N＞10)为异丙嗪5 μg/kg,氯丙嗪、氯丙嗪亚砜、异丙嗪亚砜1 μg/kg.检出限(S/N=3)为异丙嗪1.5 μg/kg,氯丙嗪、氯丙嗪亚砜、异丙嗪亚砜0.3 μg/kg.     

VOSO_4/活性炭上常压催化氧化乳酸乙酯合成丙酮酸乙酯

以氧化改性活性炭为载体,用浸渍法制备了系列VOSO4/活性炭催化剂(VO/ACO).采用FT-IR、XRD、ICP和比表面及孔结构测定等表征了催化剂组成与结构.考察了VO/ACO催化剂在常压分子氧氧化乳酸乙酯中的催化作用.结果表明,氧化活性炭是氧钒催化剂的有效载体,以pH=3的VOSO4溶液浸渍得到的VO-3/ACO催化剂具有优良的催化性能,在二氯乙烷中常压,80℃反应18 h,乳酸乙酯转化完全,丙酮酸乙酯的选择性达95.2%.催化剂重复使用三次后的性能基本保持不变.     

水热法合成纳米氧化铜及其对盐酸异丙嗪的电化学传感研究

采用简单的水热法一步反应,制备了尺径均一的纳米氧化铜颗粒并构建了纳米氧化铜修饰电极。结果表明,该修饰电极对盐酸异丙嗪的电化学氧化有显著的电催化作用,研究了各种因素包括pH值、修饰剂用量、扫速以及共存离子等对电极响应的影响,优化了各项测试条件。该方法测定盐酸异丙嗪的线性范围为0.5~150μmol/L,检出限为1.3×10-7 mol/L,同时成功测定了药物中盐酸异丙嗪的含量。     

VOSO4/活性炭在常压合成丙酮酸乙酯中的催化作用

以氧化改性活性炭为载体,用浸渍法制备了系列VOSO4/活性炭催化剂(VO/ACO). 采用FT-IR、XRD、ICP和比表面及孔结构测定等表征了催化剂组成与结构. 考察了VO/ACO催化剂在常压分子氧氧化乳酸乙酯中的催化作用. 结果表明, 氧化活性炭是氧钒催化剂的有效载体,以pH=3的VOSO4溶液浸渍得到的VO-3/ACO催化剂具有优良的催化性能, 在二氯乙烷中常压,80 ℃ 反应18 h, 乳酸乙酯转化完全, 丙酮酸乙酯的选择性达95.2%. 催化剂重复使用三次后的性能基本保持不变.     

流动注射化学发光法测定盐酸异丙嗪

在酸性溶液中，高锰酸钾能氧化盐酸异丙嗪产生化学发光反应，乙二醛的存在可使发光强度增强。据此，采用流动注射技术，建立了一种测定盐酸异丙嗪的化学发光分析分析。方法的检出限为３．５×１０＾－８ｇ／ｍＬ，相对标准偏差为２．８％（１．０×１０＾－６ｇ／ｍＬ盐酸异丙嗪，ｎ＝１１），线性范围为１．０×１０＾－７￣６．０×１０＾－５ｇ／ｍＬ。该法已用于盐酸异丙嗪针剂和片剂中盐酸异丙嗪含量的测定，并与药典标准方法进     

金纳米微粒作探针共振瑞利散射光谱法测定盐酸异丙嗪

在pH 1.8～3.0的酸性介质中,质子化的盐酸异丙嗪(PMZ)可与带负电荷的金纳米微粒依靠静电和疏水作用相互结合,导致共振瑞利散射(RRS)强度显著增强,其最大散射峰位于368 nm,并在284,440,498 nm处有明显的散射峰,在选定的测量波长下,盐酸异丙嗪在0.04～0.10μg/mL的浓度范围内与RRS强度成正比,该法具有高的灵敏度,其检出限为1.34 ng/mL。考察了体系的RRS光谱特征,研究了适宜的反应条件、影响因素,研究了共存物质的影响,据此建立了金纳米微粒作探针RRS法测定盐酸异丙嗪的新方法。     

β-环糊精/碳纳米管修饰电极上盐酸异丙嗪的电化学行为研究

研究盐酸异丙嗪在β-环糊精修饰多壁碳纳米管玻碳电极上的电化学行为,建立了一种新的测定盐酸异丙嗪的电化学分析方法.在碳纳米管和β-环糊精的协同作用下,用循环伏安法研究了盐酸异丙嗪在修饰电极上的氧化还原特性,结果表明该修饰电极对盐酸异丙嗪具有显著的催化氧化作用.在pH=5.4的磷酸盐缓冲溶液中,氧化峰电流与盐酸异丙嗪浓度在...     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.