CdTe:Mn/ZnS量子点的合成及其磷光法检测水体中超痕量汞离子的研究

以3-巯基丙酸为稳定剂水相合成了新型CdTe:Mn/ZnS量子点,用原子力显微镜、紫外-可见光谱、荧光光谱等技术对其进行了表征.以CdTe:Mn/ZnS量子点为磷光探针,建立了基于汞离子对该量子点的磷光猝灭定量检测汞离子的新方法.文中考察了pH值、缓冲介质、反应时间、量子点浓度等因素的影响.在最佳实验条件下,可测定5.0×10-8～1.0×10-5mo1/L的汞离子,检出限为43×10～mol/L.方法成功地应用于实际样品中超痕量汞离子的测定.文中就其作用机理作了初步探讨.     

基于CdTe量子点内滤效应同步荧光猝灭法测定四环素

以巯基丙酸作为稳定剂制备CdTe量子点,发现CdTe量子点的激发光谱与四环素的吸收光谱有较好重叠,满足发生内滤效应的条件。据此以四环素为吸光体、CdTe量子点为荧光体构建内滤效应荧光传感体系,从而建立一种测定四环素含量的同步荧光猝灭法。实验结果表明,当固定波长差为220 nm时,CdTe量子点的同步荧光最大发射波长为297 nm。在最佳实验条件下,四环素浓度在1.0×10-6~1.0×10-5mol·L-1范围内与体系同步荧光强度呈良好的线性关系,相关系数和检出限分别为0.999和2.5×10-8mol·L-1。该方法灵敏度高、选择性好,应用于牛奶样品中四环素的检测,加标回收率为97.0%~104.3%。     

3-巯基丙酸修饰的CdTe量子点荧光探针用于碘酸根离子的检测

以3-巯基丙酸(MPA)为稳定剂,采用水相合成法制备了CdTe量子点(QDs)。基于IO-3可使CdTe QDs荧光显著猝灭的特性,建立了一种检测IO-3的荧光分析新方法。优化了实验条件,在pH=6.0、三酸缓冲溶液浓度为30mmol/L、QDs溶液浓度为8.66×10-6 mol/L、反应时间为24min最佳实验条件下,检测IO-3的线性范围为6.0×10-8~7.2×10-6 mol/L,检出限为4.92×10-8 mol/L,方法相对标准偏差为2.37%。实验表明,IO-3对CdTe QDs的荧光猝灭有较好的选择性。方法用于自来水中IO-3的回收率实验,回收率为92.17%~103.29%。对可能的机理进行了探讨。     

水溶性量子点碲化镉测定同型半胱氨酸的研究

以巯基丙酸为稳定剂,在水溶液中一步合成了CdTe量子点,以该量子点为荧光探针,基于荧光增敏法对同型半胱氨酸(Hcy)进行选择性测定,考察了缓冲体系、缓冲液浓度、缓冲液pH值、反应时间、量子点浓度等多种因素的影响.在0.05 mol/L、pH 8.8的磷酸二氢钠-磷酸氢二钠缓冲液中,当量子点浓度为1.2 mmol/L、反应时间为10 min时,该方法的线性区间为0.1 ～60 μmol/L,检出限为8×10-8 mol/L.     

以碲化镉量子点为荧光探针测定西红柿中残留吗啉胍

利用吗啉胍使CdTe量子点荧光增强的特性,建立了西红柿中吗啉胍残留量的检测新方法。研究了影响量子点荧光探针行为的因素,确定最佳工作条件:量子点浓度为1×10-4mol/L,pH=5.6,反应温度为20℃,反应时间为20 min。在最佳测定条件下,CdTe量子点荧光探针对吗啉胍响应的线性范围为1.0×10-12~5.0×10-10mol/L,检出限为5.2×10-13mol/L,线性相关系数R=0.9981,方法的回收率97%~106%,常见共存离子、抗生素、维生素等共存物质对吗啉胍的测定不产生干扰。本方法用于西红柿中吗啉胍残留量的测定,结果令人满意。     

谷胱甘肽稳定的CdTe量子点荧光猝灭法测定痕量过氧化氢

以谷胱甘肽稳定的CdTe量子点作为荧光探针,基于荧光猝灭法对过氧化氢进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响。实验结果表明,在pH=7.2的Na2HPO4-NaH2PO4缓冲液中,反应时间为15min,过氧化氢浓度为1.0×10-6～3.0×10-5 mol/L范围时,其线性回归方程为△F=9.78+7.56c(10-6 mol/L),线性相关系数和检测限分别为0.9992和1.27×10-8 mol/L。谷胱甘肽稳定的CdTe量子点荧光猝灭法已用于水样的测定,回收率在96%～103%之间,相对标准偏差RSD不大于3.3%,结果令人满意。     

基于L-半胱氨酸/CdTe量子点修饰电极的电化学传感器的制备及其对Pb~(2+)的检测

成功制备了由L-半胱氨酸和CdTe量子点作为修饰材料的电化学传感器并用于水体中Pb~(2+)的检测。巯基丙酸修饰的CdTe量子点通过水相合成,表面含有大量羧基,与L-半胱氨酸表面的氨基形成酰胺键,修饰于金电极表面。通过荧光分光光度计、透射电子显微镜、红外光谱、X射线衍射对L-Cys/CdTe QDs复合材料进行表征。采用循环伏安法(CV)研究了L-Cys/CdTe QDs修饰成分在金电极上的电化学性能及CdTe量子点的最佳自组装时间。采用差分脉冲溶出伏安法(DPSV)研究了铅离子在修饰电极上的电化学行为。在优化实验条件下,Pb~(2+)浓度在1.0×10~(-6)~1.0×10~(-2) mol/L范围内与其峰电流呈良好的线性关系,相关系数(r2)为0.993 8,检出限(3σ,n=5)为4.0×10~(-7) mol/L。该传感器具有良好的重现性和稳定性,有望用于实际水样中铅离子的检测。     

抑制荧光动力学法测定痕量抗坏血酸

在Na2HPO4-NaH2PO4弱碱性介质中,痕量抗坏血酸对氮氧自由基使CdTe量子点荧光猝灭具有抑制作用,由此建立了动力学荧光法测定痕量抗坏血酸的新方法。考察了不同pH、CdTe量子点和氮氧自由基的用量、反应时间等条件对抑制反应的影响。在最佳实验条件下,方法线性范围为2×10-7～1.5×10-5mol/L,检出限为5×10-8mol/L。该方法用于饮料等实际样品中抗坏血酸的测定,回收率为98%～103%。     

3-巯基丙酸修饰的CdSe/ZnS量子点的合成及测定牛血清白蛋白的研究

以3-巯基丙酸作为修饰剂,在水溶液中合成了稳定的CdSe/ZnS量子点(QDs),透射电镜观察所合成量子点的形貌近似球形,粒径约为25 nm.吸收光谱与荧光光谱的研究表明,CdSe QDs在410 nm处有最大吸收峰,而CdSe/ZnS QDs的最大吸收峰在470 nm处,CdSe/ZnS QDs的荧光强度是CdSe QDs的11倍.考察了缓冲溶液的体积、pH值、反应温度、反应时间对体系荧光的影响.在最佳实验条件下,体系的荧光强度与BSA的浓度呈线性关系,线性响应范围为0.746×10-7～4.48×10-7 mol/L,检出限为3.846×10-10 mol/L.并且CdSe/ZnS QDs荧光强度基本保持稳定,可达两个多月.该方法应用于合成样品的测定,结果满意.     

新型量子点“开关”测定痕量诺氟沙星

研究并构建了一种新型CdTe量子点“开关”,利用量子点荧光强度的变化进行痕量诺氟沙星的检测.考察了不同缓冲溶液,pH值,C02+浓度等因素对体系的影响.结果表明,在pH=10的硼砂缓冲液中,C02+能猝灭CdTe的荧光;体系中加入诺氟沙星后,CdTe的荧光得到恢复,并且量子点荧光的恢复强度与诺氟沙星的浓度与呈良好的线性关系.基于量子点“开关”技术,通过检测CdTe荧光恢复强度,建立了一种测定诺氟沙星的方法.方法的线性范围为0.8×10-8～4.4×10-7 mol/L;检出限为2.3×10-9 mol/L.应用于实际样品的检测,RSD≤2.2％(n=6),回收率为98.4％～102.1％,结果令人满意.     

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.