热解析-高场非对称波形离子迁移谱(FAIMS)技术快速检测合成色素

采用热解析-高场非对称波形离子迁移谱(FAIMS)技术快速检测柯衣定、 孔雀石绿、 罗丹明B和甲基红4种合成色素. 通过对热解析温度和载气流量进行优化, 确定了不同色素的离子特征信号. 在最佳分析条件下, 热解析温度为160 ℃, 载气流量为1.6 L/min, 采用不同模式下补偿电压(CV)值定性, 以FAIMS在正模式下检测柯衣定(CV=0.41 V)和罗丹明B(CV=-0.89 V), 在负模式下检测甲基红(CV=-0.67 V)和孔雀石绿(CV=0.02 V); 用外标法定量检测了样品中的4种合成色素, 线性关系R²≥0.9967, 检出限为2.5~10 μg/L, 定量限为5~20 μg/L, 加标回收率≥78.2%, 相对标准偏差RSD≤8%. 本文为FAIMS技术快速检测合成色素提供了一定的技术基础.     

用高场非对称波形离子迁移谱技术快速检测二乙醇胺

采用高场非对称波形离子迁移谱(FAIMS)对二乙醇胺(DEA)进行快速检测分析, 以热解析法进样, 确定了二乙醇胺的离子特征信号, 并与气相色谱-质谱联用仪的检测结果进行了比较. 用聚四氟乙烯(PTFE)扩散管进样, 控制二乙醇胺样品气(DEA与空气的混合气)浓度, 利用FAIMS对不同浓度的二乙醇胺样品气进行检测. 通过对离子特征信号进行量化和重复性分析, 确定了二乙醇胺样品气的检出限为0.02 μg/L, 并建立了FAIMS检测二乙醇胺样品气的离子电流强度积分面积与样品气浓度关系曲线. 为FAIMS应用于现场快速检测二乙醇胺提供了一定的依据.     

一种微型FAIMS传感器芯片的研制

基于微机电系统(MEMS)技术,研制了一种微型高场非对称波形离子迁移谱(FAIMS)传感器芯片.芯片尺寸为18.8mm×12.4mm×1.2mm,由离子化区、迁移区、离子检测区组成.采用真空紫外灯离子源在大气压环境下对样品进行离子化,经过离子化区中聚焦电极的电场作用,实现离子在进入迁移区之前的聚焦,提高离子信号的强度.通过在上下玻璃上溅射Au/Cr(300nm/30nm)金属,并与厚度为200μm、采用感应耦合等离子体(ICP)工艺刻蚀的硅片键合,形成迁移区的矩形通道,尺寸为10mm×5mm×0.2mm.离子检测区为三排直径200μm、间距100μm交错排列的圆柱阵列式微法拉第筒,能同时检测正负离子.采用频率为2MHz,最大电压为364V,占空比为30%的高场非对称方波电压进行FAIMS芯片实验.以丙酮和甲苯为实验样品,载气流速80L·h-1,补偿电压从-10V到3V以0.1V的步长进行扫描,得到了丙酮和甲苯的FAIMS谱图,验证了FAIMS芯片的性能.丙酮和甲苯的FAIMS-MS实验进一步表明FAIMS系统实现了离子分离和过滤功能.     

芯片级高场非对称波形离子迁移谱技术检测危险品

建立了吸气法-芯片级高场非对称波形离子迁移谱(FAIMS)技术,设置进样温度为50℃,载气与样品气流量分别为1500和100 mL/min时,测定了10种国家交通部门规定严禁携带的易燃易爆危险品。实验结果表明,利用FAIMS技术可以有效检测多种危险品。实验得到了10种危险品的FAIMS图谱,并对其进行了指纹识别。利用扩散管辅助技术得到10种物质的检测浓度范围约为0.1～20 mg/L。此方法方便快速,灵敏度高,具有很好的应用前景。     

高场不对称波形离子迁移谱快速检测水样中苯含量

建立了高场不对称波形离子迁移谱(FAIMS)检测水中苯含量的分析方法。研究了不同分离电压(Dispersion voltage,DV)下的苯标准谱图,获得用于苯识别的非线性函数二阶α2及四阶α4系数值分别为-3.8×10-5Td-2和5.1×10-8Td-4;通过平衡灵敏度与分离度,得到用于苯识别的最佳分离电压为800 V;通过不同质量浓度(0.08~0.64 mg/L)的苯样品与苯离子信号强度的关系,确定高场不对称波形离子迁移谱(FAIMS)对水中苯的检出限为0.89μg/L,远优于国家饮用水中苯浓度的限值10μg/L。本研究为水中苯检测提供了一种快速、高灵敏的方法。     

基于水分掺杂的高场非对称波形离子迁移谱检测硫化氢的研究

高场非对称波形离子迁移谱(FAIMS)是一种芯片级高灵敏度快速分析检测技术,其在大气压环境下工作的特点使之受环境影响明显,其中气体的湿度是显著影响因素,湿度的变化可引起迁移区离子反应机理以及迁移过程的变化。该文研究了干燥条件下痕量硫化氢的定量检测方法,确定了DF=33%时的检测线性范围与回归方程。利用PTFE管渗透作用,设定水浴温度为40～90℃,考察了不同含量水分对FAIMS检测硫化氢的影响。通过考察不同湿度下硫化氢的FAIMS特征谱图以及特征离子峰,研究了掺杂水分对于硫化氢谱峰峰值、补偿电压以及检测分辨率的影响。结果表明,FAIMS对于硫化氢的检测谱图清晰可见,能够准确定位其特征离子峰。随着气体中水分增多,不同分离电场下的产物离子峰峰值增大,说明湿度增大在一定程度上提高了灵敏度,DF=35%时的检出限为1.43×10~(-3) mg/m~3。     

基于两维扫描高场不对称离子迁移谱技术检测挥发酚

要采用自制高场不对称波形离子迁移谱(FAIMS)仪对苯酚、2-甲酚、3-甲酚、4-甲酚以及2,4-二氯酚进行检测,通过结合补偿电压以及射频高压的二维扫描优化了对检测物的分辨.射频高场强度为1.6×104 V/cm时,2-甲酚与4-甲酚有最佳分辨效果,其余物质在高场强度大于1.8×104 V/cm时可以得到最佳分辨.研究...     

芯片级非对称场离子迁移谱技术检测爆炸物和毒品

本研究使用蒸气法-芯片级非对称场离子迁移谱技术(FAIMS)检测部分爆炸物和毒品。通过14～21d的连续测试得到目标物的扩散速率。在设定条件下,实现了对爆炸物和毒品的良好分析。同时针对FAIMS检测技术开发出了新的数据识别方法,使FAIMS技术以超高的灵敏度完成了对部分爆炸物和毒品的有效分辨,检测浓度范围约为33～100ng/L。该方法无需前处理、方便、快捷,灵敏度高,具有很好的应用前景。     

紫外光离子源-高场不对称波形离子迁移谱检测环境中挥发性有机物

本研究采用紫外光离子源-高场不对称波形离子迁移谱(UV-FAIMS)快速检测环境中挥发性有机物.选取苯和对二甲苯为研究对象,并分析了分离电压、流速等因素对其分离识别的影响.实验结果表明:当分离电压值为0～1200 V时,苯和对二甲苯信号强度逐渐降低,而特征补偿电压值却逐渐增加.实验选取分离电压值为900 V,当载气流速为0～240 L/h时,苯和对二甲苯的特征离子峰信号强度逐渐增加,当载气流速为0～120 L/h时,苯和对二甲苯团簇峰信号强度增加,当载气流速为120～240 L/h时,苯的团簇峰信号强度增加,而对二甲苯的团簇峰信号强度降低.此外,对样品浓度、信号强度与噪声的比值进行探讨,获得UV-FAIMS检测苯的检测限为0.011mg/m3.     

基于高场非对称离子迁移谱(FAIMS)技术快速检测水基食品模拟物中乙酸乙酯

基于高场非对称离子迁移谱(FAIMS)技术建立了水基食品模拟物中乙酸乙酯的测定方法,并与顶空气相色谱质谱法(GC-MS)的检测结果进行了比较。考察了样品扫描次数、加热温度、加热时间、取样体积、溶剂掺杂等因素对检测的影响。结果表明在最佳的实验条件下乙酸乙酯的检出限为0.4 mg/L,其单体离子峰强度在低浓度(0~1.4 mg/L)范围与其浓度呈线性关系。与顶空GC-MS法相比,本方法操作更便捷、快速,但抗干扰能力较差。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.