基于Mn掺杂ZnS量子点室温磷光法测定生物体液中的磺胺嘧啶钠

利用水相合成法合成了MPA(3-巯基丙酸)包覆的Mn掺杂Zn S量子点,基于该掺杂型量子点的室温磷光性质,建立了一种检测磺胺嘧啶钠(SDS)的新方法。该方法可以有效避免生物体液的自体荧光和散射光,且在水溶液检测时不需要添加任何诱导剂和除氧剂。在p H 7.4磷酸盐缓冲介质中,通过静电作用,SDS可以猝灭Mn掺杂Zn S量子点在590 nm处的磷光,其猝灭的磷光强度与SDS浓度呈良好的线性关系。其线性范围4~400μmol/L,相关系数R=0.99,检出限为0.78μmol/L,相对标准偏差(RSD)为2.6%。     

基于Mn掺杂ZnS量子点室温磷光法检测环丙沙星

建立了基于3-巯基丙酸包裹的Mn掺杂Zn S量子点室温磷光性质定量检测环丙沙星的方法。方法不需要脱氧剂和诱导剂,并且能够有效的避免生物体液的自体荧光和散色光的干扰。在最优化实验条件下,随着环丙沙星浓度的增大,Mn掺杂Zn S量子点室温磷光强度在590 nm处呈现出非常有规律的猝灭,其线性范围为1.2~60μmol/L,检出限(3σ)为0.3μmol/L。在人体血液中的加标回收率为93%~106%。     

基于Mn掺杂ZnS量子点室温磷光法检测盐酸巴马汀

本文以3-巯基丙酸(3-Mercaptopropionic Acid,MPA)为稳定剂,采用水相合成法制备了Mn掺杂ZnS量子点(Mn∶ZnS QDs),基于Mn∶ZnS QDs的室温磷光性质,盐酸巴马汀(Palmatine Hydrochloride,PaH)可与Mn∶ZnS QDs发生静电作用,使得Mn∶ZnS QDs发生室温磷光猝灭效应,从而发展了一种高效、快速检测人体体液中痕量PaH的新方法。实验结果表明,当PaH的浓度在0.75~30μmol/L范围时,其浓度与室温磷光猝灭强度(ΔIRTP)呈良好的线性关系,相关系数为0.996,检出限为0.35μmol/L,加标回收率为94.0%~103.3%。     

量子点室温磷光法检测生物体液中尿酸

在水相中合成了3-巯基丙酸包覆的Mn掺杂ZnS量子点,基于Mn掺杂ZnS量子点的室温磷光特性,利用尿酸中的强吸电子基羰基通过电子转移能够有效猝灭量子点磷光,构建了一种检测尿酸的方法,该法无需预处理过程。结果表明,在pH 7.4的磷酸盐缓冲溶液中,尿酸对Mn掺杂ZnS量子点的猝灭程度呈线性变化,线性范围为2~70μmol/L,相关系数为0.99,检出限为0.31μmol/L。用于尿样中加标回收,加标回收率为97.5%~100.3%。方法适用于人体液中痕量尿酸的检测。     

基于Mn掺杂ZnS量子点室温磷光法测定水样中百草枯

利用水相合成法制备了3-巯基丙酸(3-Mercaptopropionic Acid,MPA)包裹的Mn掺杂ZnS量子点(Quantum Dots,QDs),基于该量子点的室温磷光性质,构建了一种快速、灵敏检测水样中百草枯(Paraquat,PQ)含量的新方法。方法无需添加任何除氧剂和诱导剂等复杂的预处理过程。在pH=7.4的磷酸盐缓冲溶液中,PQ通过静电作用可以猝灭Mn掺杂ZnS QDs在波长590nm处的磷光,且在一定范围内PQ的浓度与磷光猝灭强度(P0/P)呈良好的线性关系,线性范围为2.5~50μg/L,相关系数为0.994,方法检出限为0.769μg/L。该方法适用于不同水样中百草枯的痕量检测。     

分子印迹Mn掺杂ZnS量子点磷光法检测烟酸转化液中的6-羟基烟酸

以6-羟基烟酸(6-HNA)为模板,采用分子印迹溶胶-凝胶法合成了具有良好光学性质的印迹Mn掺杂Zn S量子点磷光传感器(MIP-QDs)。红外光谱(FT-IR)和扫描电镜(SEM)测试表明,印迹聚合物成功接枝在纳米传感器表面。吸附试验显示,MIP-QDs对6-HNA的亲和性与选择性显著高于其结构类似物阔马酸和烟酸,具备作为检测探针的潜力。在最优条件下,基于6-HNA可选择性猝灭MIP-QDs磷光而建立了灵敏、简便的检测微量6-HNA的光学新方法。当6-HNA浓度在3.4~67.0μmol/L范围内,MIP-QDs的磷光猝灭率P_0/P随浓度变化的关系符合Stern-Volmer方程(r~2=0.996 5),检出限为1.03μmol/L。实际样品测定显示,6-HNA的回收率为91.0%~103.9%,相对标准偏差不超过4.5%,检测结果与HPLC法相一致(P0.05),方法具有良好的准确性和可行性。     

基于室温磷光量子点/硼酸基联吡啶盐纳米复合材料检测果糖

以Mn掺杂的ZnS(Mn-ZnS)室温磷光(RTP)量子点的磷光为信号,以2-溴甲基苯硼酸与4,4ˊ-联吡啶为原料合成的硼酸基联吡啶盐(BBV)为受体,带负电的量子点与带正电BBV通过静电作用形成Mn-ZnS/BBV纳米复合材料,Mn-ZnS量子点磷光猝灭,加入果糖,BBV与果糖形成阴离子硼酸酯,降低了对量子点猝灭效率,RTP恢复.考察了时间、pH值对Mn掺杂的ZnS QDs/BBV纳米复合材料磷光强度的影响,在最优条件下,此传感器检测果糖的线性范围为0.05~1.00 mmol/L,检出限为0.01 mmol/L,相关系数r为0.99.本磷光分析法简便快速、灵敏度高,有望应用于食品、医药行业中果糖含量的检测分析.     

基于Mn掺杂ZnS量子点的室温磷光猝灭法测定H2O2

以N-乙酰基-L-半胱氨酸为稳定剂,合成了具有独特光学性质的水溶性Mn掺杂ZnS量子点(QDs)。该量子点在室温不除氧的条件下即可发射较强的磷光信号,最大发射波长位于592nm处。在pH=7.0的磷酸盐缓冲溶液中,H2O2对量子点有显著的磷光猝灭作用,且在一定的范围内H2O2的浓度与磷光猝灭值(P0/P)呈现良好的线性关系,以此建立了测定H2O2的新方法。在最佳的实验条件下,该方法的检出限为1.0×10-6 mol/L,线性范围为1.0×10-5～2.5×10-2 mol/L,相关系数为0.9978。通过测定猝灭过程的时间分辨磷光光谱,推断猝灭机理为动态猝灭。     

黄芩素室温磷光传感器的构建及应用

黄芩素可通过电子转移效应猝灭聚乙烯亚胺(PEI)包覆的锰(Mn)掺杂硫化锌(Zn S)量子点(PEIMn/Zn S QDs)的室温磷光。基于上述原理,建立了一种简单、快速测定黄芩素含量的室温磷光检测方法,PEI-Mn/Zn S QDs以水相共沉淀法获得。结果表明:当pH=8.0,反应时间为10 min时,量子点的磷光猝灭程度与黄芩素浓度呈良好的线性关系,线性范围为0.07~0.60 mg·L~(-1),方法检出限为0.039 mg·L~(-1),相关系数(r)为0.997,相对标准偏差为4.1%,实际样品的检测回收率为96.0%~100.7%。所建立的方法可有效避免常见离子和氨基酸等的干扰,适用于黄芩饮片及血清中黄芩素含量的快速测定,有望应用于医药行业中黄芩素含量的测定分析,也为其他药物基于量子点电子转移机制的检测提供了技术依据。     

锰掺杂硫化锌量子点室温磷光检测铅离子

采用锰掺杂硫化锌量子点室温磷光（RTP）探针,基于Pb^{2 1}对其磷光的猝灭现象进行选择性测定,考察了量子点溶液浓度、缓冲液体系及浓度、反应时间、干扰物质等多种因素影响,在最优条件下,即25μmol/L量子点溶液在Tris-HCl（10 mmol/L,pH 7.4）缓冲液中,反应时间为2 min时,检测Pb^2--的线性范围为0 25～1000μmol/L,检出限为0.04μmol/L,方法的精密度和准确度良好。本方法简单、快速、灵敏度和选择性较好,线性范围较宽,可用于96孔板进行高通量检测,并成功应用于生物样品中Pb^2-的选择性检测,在稀释5倍人血浆中检测Pb^2-的线性范围为5～1000μmol/L,检出限为0.48μmol/L。     

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性;均苯四甲酸二酐;联苯四羧酸二酐;二羟基联苯胺;聚酰亚胺;聚苯并噁唑;耐热性     

Studies on the Formation of Catalytically Active PGM Nanoparticles from Model Solutions as a Basis for the Recycling of Spent Catalysts

The paper presents basic studies on the precipitation of platinum, palladium, rhodium, and ruthenium nanoparticles from model acidic solutions using sodium borohydride, ascorbic acid, and sodium formate as reducing agents and polyvinylpyrrolidone as a stabilizing agent. The size of the obtained PGM particles after precipitation with NaBH₄ solution does not exceed 55 nm. NaBH₄ is an efficient reducer; the precipitation yields for Pt, Pd, Ru, Rh are 75, 90, 65 and 85%, respectively. By precipitation with ascorbic acid, it is possible to efficiently separate Pt, Rh, and Ru from Pd from the two-component mixtures. The obtained Pt, Pd, and Rh precipitates have the catalytic ability of the catalytic reaction of p-nitrophenol to p-aminophenol. The morphological characteristic of the PGM precipitates was analyzed by AFM, SEM-EDS, and TEM.     

Synthesis of Some Novel Class of Bis(isoxazoline) and Bis(aziridine) Derivatives

Synthesis of some new bis(isoxazoline) derivatives has been described from terepthaldehyde derived bis(nitrones) using microwave irradiation via 1,3‐dipolar cycloaddition reaction. Bis(isoxazoline) derivatives in turn successfully converted into new bis(aziridine) derivatives via Baldwin rearrangement. Simple reaction methodology, non involvement of catalysts, and good to excellent yields are the important features noticed in this synthesis.     

柴油加氢精制催化剂制备技术

柴油加氢精制催化剂制备技术的发展大致经历了3个阶段,由此形成了三代柴油加氢催化剂:单层分散的负载型金属硫化物催化剂,多层分散的负载型金属硫化物催化剂和非负载型金属硫化物催化剂。本文对金属硫化钼基柴油加氢精制催化剂的应用背景、制备思想及催化剂研究开发现状进行了系统的总结,对柴油加氢催化剂的发展方向进行了展望。     

Direct Quantitation of Phytocannabinoids by One-Dimensional 1H qNMR and Two-Dimensional 1H-1H COSY qNMR in Complex Natural Mixtures

The widespread use of phytocannabinoids or cannabis extracts as ingredients in numerous types of products, in combination with the legal restrictions on THC content, has created a need for the development of new, rapid, and universal analytical methods for their quantitation that ideally could be applied without separation and standards. Based on previously described qNMR studies, we developed an expanded ¹H qNMR method and a novel 2D-COSY qNMR method for the rapid quantitation of ten major phytocannabinoids in cannabis plant extracts and cannabis-based products. The ¹H qNMR method was successfully developed for the quantitation of cannabidiol (CBD), cannabidiolic acid (CBDA), cannabinol (CBN), cannabichromene (CBC), cannabichromenic acid (CBCA), cannabigerol (CBG), cannabigerolic acid (CBGA), Δ9-tetrahydrocannabinol (Δ9-THC), Δ9-tetrahydrocannabinolic acid (Δ9-THCA), Δ8-tetrahydrocannabinol (Δ8-THC), cannabielsoin (CBE), and cannabidivarin (CBDV). Moreover, cannabidivarinic acid (CBDVA) and Δ9-tetrahydrocannabivarinic acid (Δ9-THCVA) can be distinguished from CBDA and Δ9-THCA respectively, while cannabigerovarin (CBGV) and Δ8-tetrahydrocannabivarin (Δ8-THCV) present the same ¹H-spectra as CBG and Δ8-THC, respectively. The COSY qNMR method was applied for the quantitation of CBD, CBDA, CBN, CBG/CBGA, and THC/THCA. The two methods were applied for the analysis of hemp plants; cannabis extracts; edible cannabis medium-chain triglycerides (MCT); and hemp seed oils and cosmetic products with cannabinoids. The ¹H-NMR method does not require the use of reference compounds, and it requires only a short time for analysis. However, complex extracts in ¹H-NMR may have a lot of signals, and quantitation with this method is often hampered by peak overlap, with 2D NMR providing a solution to this obstacle. The most important advantage of the COSY NMR quantitation method was the determination of the legality of cannabis plants, extracts, and edible oils based on their THC/THCA content, particularly in the cases of some samples for which the determination of THC/THCA content by ¹H qNMR was not feasible.     

Magnetism of metal-nitroxide compounds involving bis-chelating imidazole and benzimidazole substituted nitronyl nitroxide free radicals

Coordination compounds based on imidazole and benzimidazole substituted nitronyl nitroxide radicals with transition metal ions and trivalent lanthanide ions are described from the perspective of their magnetic properties.For the transition metal compounds the crystal structures show various metal-nitroxide dimensionalities including mononuclear (0D), one-dimensional (1D) and two-dimensional (2D) complexes. The mononuclear complexes were isolated with most metal ions of the first transition series. One copper(II) complex shows a copper(II)-radical ferromagnetic coupling (J = +75 cm⁻¹) while for the other mononuclear compounds, mainly with manganese(II), the metal-radical interactions are antiferromagnetic. The one-dimensional and two-dimensional complexes are manganese(II) compounds which show canting effects leading to weak ferromagnetism.For the trivalent lanthanide ions [La(III), Gd(III) and Eu(III)], three series of mononuclear complexes were obtained in which the metal center is bound to four, two or one nitroxide radicals depending on the counter ions and ancillary ligands. Unexpectedly, in most gadolinium(III) complexes, the Gd(III)-radical interactions were found to be antiferromagnetic in contradiction with other foundings and previous theoretical models. In support to the magnetic studies, the optical properties of the lantanide complexes have also been investigated and are briefly described.     

Transition metal complexes of the tripodal ligand 4-(2′-pyridylmethyl)-4-azaheptane-1,7-diamine. Crystal structures of [CuLCl]ClO4 and [NiL(MeCN)2](ClO4)2

The tripodal ligand 4-(2′-pyridylmthyl)-4-azaheptane-1,7-diamine has been prepared by reaction of 2-aminemethyl pyridine with acrylonitrile, followed by the reduction of the nitrile groups. Copper(II), nickel(II), zinc(II), cobalt(III) and chromium(III) complexes of the ligand have been prepared and characterized and the crystal structures of the complexes [CuLCl]ClO₄ and [NiL(MeCN)₂](ClO₄)₂ determined. The copper complex is five coordinate with approximate square pyramidal stereochemistry with the apical position occupied by a primary amine donor. The nickel complex is octahedral with the pyridine nitrogen donor lying trans to an acetonitrile ligand.     

Simple,Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel（Ⅱ）, Copper （Ⅱ）, Cobalt （Ⅱ）, and Iron （Ⅲ） with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.     

The development and application of guidance on equipment qualification of analytical instruments

 This paper describes the development of guidance for the equipment qualification (EQ) of analytical instruments. EQ is a formal process that provides documented evidence that an instrument is fit for its intended purpose and kept in a state of maintenance and calibration consistent with its use.     

Electrochemically selective determination of dopamine in the presence of ascorbic and uric acids on the surface of the modified Nafion/single wall carbon nanotube/poly(3-methylthiophene) glassy carbon electrodes

A voltammetric method based on a combination of incorporated Nafion, single-walled carbon nanotubes and poly(3-methylthiophene) film-modified glassy carbon electrode (NF/SWCNT/PMT/GCE) has been successfully developed for selective determination of dopamine (DA) in the ternary mixture of dopamine, ascorbic acid (AA) and uric acid (UA) in 0.1M phosphate buffer solution (PBS) pH 4. It was shown that to detect DA from binary DA-AA mixture, the use of NF/PMT/GCE was sufficient, but to detect DA from ternary DA-AA-UA mixture NF/SWCNT/PMT/GCE was required. The later modified electrode exhibits superior electrocatalytic activity towards AA, DA and UA thanks to synergic effect of NF/SWCNT (combining unique properties of SWCNT such as high specific surface area, electrocatalytic and adsorptive properties, with the cation selectivity of NF). On the surface of NF/SWCNT/PMT/GCE AA, DA, UA were oxidized respectively at distinguishable potentials of 0.15, 0.37 and 0.53 V (vs. Ag/AgCl), to form well-defined and sharp peaks, making possible simultaneous determination of each compound. Also, it has several advantages, such as simple preparation method, high sensitivity, low detection limit and excellent reproducibility. Thus, the proposed NF/SWCNT/PMT/GCE could be advantageously employed for the determination of DA in real pharmaceutical formulations.