以碘为受体的荷移络合物的荧光光谱研究及应用

采用荧光光谱法研究了诺氟沙星与碘形成荷移络合物的荧光性质,发现碘对诺氟沙星有强烈的荧光增敏效应。据此,建立了一种高灵敏的测定诺氟沙星的荷移荧光光谱新方法。优化了影响反应的不同变量和参数,在最佳实验条件下,方法线性范围为0.04~1.5μg/mL,检出限为0.01μg/mL。该方法用于药物制剂中诺氟沙星含量的测定,其回收率为98.09%~99.97%。     

浊点萃取-同步荧光法测定痕量荧光增白剂VBL

根据表面活性剂和荧光增白剂之间的相互作用,提出了浊点萃取-同步荧光法测定纸制样品中痕量荧光增白剂VBL的新方法。研究发现,相比于传统荧光发射光谱,当最佳波长差为30 nm时,VBL在402 nm处有一强度高、峰型窄的同步荧光峰。体系的相对荧光峰强度与VBL的浓度在0.001~0.053μg/mL范围内呈良好的线性关系,相关系数0.9993,线性方程为IF=10729.48ρ(μg/mL)+42.36,检测限(3S/K)为8.415×10-4μg/mL。方法用于样品测定,回收率在90.6%~102%之间,相对标准偏差在1.3%~5.2%之间。     

动物源性食品中五种氟喹诺酮类药物残留量的同时测定

建立了一种测定动物源性食品中5种氟喹诺酮类药物残留量的高效液相色谱法。样品经酸性乙腈提取,正己烷液-液分配净化,0.01 mol/L四丁基溴化铵溶液溶解残渣,过微孔滤膜,采用高效液相色谱附荧光检测器检测,外标法定量。氧氟沙星、环丙沙星、恩诺沙星线性范围为0.002~0.200μg/mL;诺氟沙星、达氟杀星线性范围为0.001~0.100μg/mL,5种氟喹诺酮类药物的相关系数为0.99901~0.99917。在0.002~0.040 mg/kg范围内,样品加标平均回收率在79.6%~97.5%之间,相对标准偏差为2.8%~15.3%。方法的检出限氧氟沙星、环丙沙星、恩诺沙星为0.004 mg/kg,诺氟沙星、达氟沙星为0.002 mg/kg。     

诺氟沙星-Tb3+-牛血清白蛋白相互作用的荧光光谱研究

采用诺氟沙星-Tb3 体系,在pH 9.0的Tris-HCl缓冲溶液中,利用牛血清白蛋白(BSA)能增强诺氟沙星的特征荧光的特性,建立了BSA的定量分析方法。结果表明:当诺氟沙星浓度/[Tb3 ]在1/8~1/12范围内时,BSA的加入量与体系的荧光增强(ΔF)有良好的线性关系,线性范围为0~25μg/mL,相关系数r=0.998。并初步探讨了BSA的存在对诺氟沙星-Tb3 体系荧光增强的作用机理。     

火焰原子吸收光谱法测定铼产品中的痕量钠

建立了火焰原子吸收光谱法测定高铼酸、高铼酸铵、铼粉中痕量钠的方法,对样品的预处理和测定钠的条件进行了研究。结果表明:水溶解法、硝酸溶解法或硝酸-硫酸溶解法溶解样品完全,测得钠的结果吻合;于选定条件下,钠的测定浓度在0.020 0~0.500 0μg/mL范围内线性良好;测定高铼酸、高铼酸铵和铼粉样品中0.27~0.47mg/L、0.000047%~0.00048%和0.000040%~0.00049%的钠含量,检出限、相对标准偏差(RSD,n=7)、加标回收率分别为高铼酸3×10-4μg/mL、6%~10%、98%~102%,高铼酸铵3×10-4μg/mL、8%~9%、96%~102%和铼粉3×10-4μg/mL、5%~9%、96%~103%。方法结果准确、分析快速、操作简便,应用于实际的样品分析,结果满意。     

微波消解-端视ICP-AES测定茶叶中微量重金属元素

采用微波消解-端视等离子体原子发射光谱(ICP-AES)测定茶叶中微量重金属元素Pb、As、Cd、Cu、Fe,并对ICP-AES工作参数及条件进行了优化和选择。Pb、As、Cd、Cu、Fe的检出限分别为2.9×10-3μg/mL、5.2×10-3μg/mL、0.056×10-3μg/mL、0.55×10-3μg/mL、0.59×10-3μg/mL,线性范围为0~10000μg/L,相对标准偏差为1.7%~8.5%;回收率为90%~104%。该方法与国标法比较,结果无显著性差异。本法能用于茶叶测定。     

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%。     

同步荧光光谱法直接测定尿液中卡那霉素

基于卡那霉素对CdTe量子点荧光的增强效应,建立一种直接测定尿液中卡那霉素含量的同步荧光光谱法。研究发现采用同步荧光光谱法,能够有效避免尿液中复杂基质的荧光干扰。在优化实验条件下,卡那霉素浓度在0.2~20.0μg/mL范围内与体系相对同步荧光强度呈良好的线性关系,相关系数为0.9996,检出限为0.005μg/mL。该方法用于尿液样品中卡那霉素含量的直接测定,回收率为96.3%~104.4%。     

荧光分析法测定维生素C

维生素C经Cu2 氧化为脱氢抗坏血酸,与苯甲酸及十六烷基三甲基溴化铵产生荧光协同增敏作用。提出一种新的测定维生素C的高灵敏荧光分析法,建立了测定维生素C的适合条件。该方法的的线性范围为0.02~8.0μg/mL,检出限为0.006 5μg/mL。对3.0μg/mL的维生素C测定6次,测定结果的相对标准偏差为0.12%。将该法用于西红柿、果珍以及维生素C药片中维生素C含量的测定,加标回收率为96.7%~100.5%。     

Cu(Ⅱ)-头孢羟氨苄的荧光光谱性质及应用

采用不同的表面活性剂对Cu(Ⅱ)与头孢羟氨苄生成的配合物在胶束体系中的荧光性质进行了研究,发现在pH6.2的Tris缓冲溶液中阴离子表面活性剂十二烷基硫酸钠对其配合物的荧光有显著的增敏作用,据此建立了胶束增敏荧光光谱法测定头孢羟氨苄的新方法。在最佳实验条件下其线性范围为0.03~1.14μg/mL,检出限为0.03μg/mL,经实际样品测定,其平均回收率为97.3%~101.4%,相对标准偏差为1.1%~1.3%。     

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.