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.     

射频电场幅值对高场非对称波形离子迁移谱检测对二甲苯的影响

高场非对称波形离子迁移谱(FAIMS)是一种利用非对称电场对气相分子进行分离检测的高灵敏度快速检测技术,超高的非对称波形电场是其迁移区的核心,非对称射频电场的幅值显著影响FAIMS的检测性能.实验以对二甲苯为样品,分析了非对称射频电场幅值对FAIMS检测性能的影响,实验表明随着射频电场幅值增大,检测灵敏度降低而分辨率增...     

利用芯片式高场非对称波形离子迁移谱技术快速检测苯丙氨酸

采用金属扩散管-芯片式高场非对称波形离子迁移谱(FAIMS)技术对苯丙氨酸进行了快速检测,设定测试压强为250 kPa,金属扩散管温度为190℃,在优化的最佳分析条件下,即:载气流速为2000 mL/min,分离电压为152.8 V时,在正模式下获得了苯丙氨酸的离子特征谱图和补偿电压特征值-0.62 V.另外,利用FAIMS对不同浓度的苯丙氨酸样品气进行了检测,确定了FAIMS检测的定量线性范围为6～20 mg/L和检出限为5.9 mg/L.本实验为FAIMS应用于苯丙氨酸的快速检测提供了重要参考.     

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。     

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。     

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。     

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.     

载气流速对高场不对称波形离子迁移谱的影响

载气流速是影响高场不对称波形离子迁移谱(FAIMS)的重要参数.以自制的高场不对称波形离子迁移谱仪为实验平台,在射频电场幅值3 kV/cm,频率500 kHz,占空比0.36的条件下,研究了载气流速对苯离子迁移谱谱峰强度和半峰宽的影响.实验结果表明: 载气流速为3.7 L/min时,苯样品的谱峰强度最大,仪器的灵敏度最高.随着载气流速的增加,谱峰半峰宽变宽,仪器的分辨率下降.载气流速为3 .0～3.7 L/min时仪器综合性能最佳.此结果对于控制迁移谱仪载气流速有重要的参考意义.     

一种用于高场非对称波形离子迁移谱系统的新型敞开式化学离子源

根据高场非对称波形离子迁移谱(FAIMS)系统的要求, 本文提出了一种新型敞开式直流电晕放电化学离子源. 该离子源主要由内线电极、外筒电极和牵引电极组成, 内、外电极半径分别是0.08、2 mm. 筒壁电极上开有对称的4个槽, 用于通入样品和牵引离子. 质谱实验结果表明, 该离子源能够在敞开环境下很好地离子化丙酮、乙醇、苯胺、N,N-二甲基甲酰胺、甲基磷酸二甲酯(DMMP)、乙酸乙酯、甲酸、乙酸、苯酚等正、负电性物质. 静电计测试实验结果说明该离子源能够稳定地产生离子电流. 通过分析不同时刻的谱图发现, 在不同时间点上产生的主要离子相同, 具有很好的稳定性. 利用感应耦合等离子体(ICP)工艺在硅片上加工了该离子源, 从而验证了该结构可以由微机电系统(MEMS)加工技术实现. 该离子源具有体积小、结构简单、无辐射、工作稳定等特点, 不仅可以满足FAIMS系统的要求, 还可用于敞开式质谱、微型质谱仪、离子迁移谱(IMS)等仪器.     

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。     

Ion conductivity studies of blends of poly(methyl methacrylate)-g-poly(ethylene glycol) and poly(ethylene glycol) complexed with LiCF3 SO3

Polymer electrolytes which are adhesive, transparent, and stable to atmospheric moisture have been prepared by blending poly(methyl methacrylate)-g-poly(ethylene glycol) with poly(ethylene glycol)/LiCF₃ SO₃ complexes. The maximum ionic conductivities at room temperature were measured to be in the range of 10⁻⁴ to 10⁻⁵ s cm⁻¹. The clarity of the sample was improved as the graft degree increased for all the samples studied. The graft degree of poly(methyl methacrylate)-g-poly(ethylene glycol) was found to be important for the compatibility between the poly(methyl methacrylate) segments in poly(methyl methacrylate)-g-poly(ethylene glycol) and the added poly(ethylene glycol), and consequently, for the ion conductivity of the polymer electrolyte. These properties make them promising candidates for polymer electrolytes in electrochromic devices. © 1996 John Wiley & Sons, Inc.     

Simultaneous concentration enrichment and electrophoretic separation of weak acids on a microchip, using in situ photopolymerized carboxylate-type polyacrylamide gels as the permselective preconcentrator

A method for the simultaneous concentration and separation of weak acids using an acidic polyacrylamide gel, fabricated in the microfluidic channel of a commercial poly(methyl methacrylate)-made microchip, is reported. This approach is based on simple photochemical copolymerization for the fabrication of a permselective preconcentrator. The intersection of the poly(methyl methacrylate)-made microchip was filled with a gel solution comprising acrylamide, N,N'-methylene-bis-acrylamide, and 2-acrylamidoglycolic acid, with riboflavin as a photocatalytic initiator. In situ polymerization, near the cross of the sample outlet channel, was performed by irradiation with an argon ion laser beam that is also used as the light source for fluorimetric detection. The electrokinetic properties, combined with electrostatic repulsion between sample components and the anionic groups on the polyacrylamide gel, enable the entrapment and concentration of weak acids at the interface of the cathodic side of the gel plug. This method displays concentration factors of up to 10(5) within 3 min. The effectiveness of the ionic preconcentrator was demonstrated by the sensitive analysis of fluorescein isothiocyanate-labeled amino acids.     

Investigation of the detection limit for the determination,by pyrolysis-capillary GC,of the thickness of ultra thin PMMA layers coated on to PET film

The determination of nanometer thick layers of poly(methyl methacrylate) coated on to the surface of poly(ethylene terephthalate) film has been investigated by high resolution pyrolysis gas chromatography without sample pretreatment or modification of the instrumentation used. A good linear relationship was observed between the quantity of the characteristic pyrolysate and the thickness of the poly(methyl methacrylate) layer; the detection limit was sufficient to enable the quantitation of poly(methyl methacrylate)-to-poly(ethylene terephthalate) film thickness ratios of 1:20000 in composite materials.     

Polymerization of methyl methacrylate with cupric laurate–benzoin system as initiator

The polymerization of methyl methacrylate initiated by cupric laurate in combination with benzoin has been investigated in carbon tetrachloride medium at 60°C. The rate of polymerization was found to be proportional to the square root of both cupric ion and benzoin concentrations, and to the 1.5th power of the monomer concentration. Spectral studies indicated that there is a complex formation between cupric ion and the monomer methyl methacrylate. A reaction scheme, based on initial formation of the complex and its subsequent reaction with benzoin to produce the free radicals responsible for initiation has been postulated to explain the observed results.     

The Nature of the Active Centers of Methyl Methacrylate Anionic Electrochemical Polymerization

By the methods of classical and oscillographic polarography, electrolysis with controlled potential and spectrophotometry, the mechanism of electrochemical generation and the active centers nature of anionic polymerization of methyl methacrylate in dimethylformamide was investigated. It was shown that in dimethylformamide in the presence of tetraalkylammonium cations, methyl methacrylate carbanions exist as solvately divided ion pairs in which the electrostatic interaction is determined by the radius of the cation. It affects the chemical stages rate of the electrochemical generation of carbanions and appears by the anomalous shift of ζ 1/2 of polarographic reduction with the increasing of the cation radius of the supporting electrolyte. The replacement of the lithium cation with tetraalkylammonium changes the interaction type of methyl methacrylate carbanion with the counterion.     

Identification of a stereoblock poly(methyl methacrylate) sample with a stereocomplex

Acid hydrolysis of a stereoblock poly(methyl methacrylate) sample leads to a mixture of isotactic and syndiotactic poly(methacrylic acid) which can be separated by electrophoresis. The experiment confirms the stereochemical identity between the so-called “stereoblock” poly(methyl methacrylate) and the stereocomplex which syndiotactic and isotactic poly(methyl methacrylate) form in the ratio 2:1. A possible mechanism of replica polymerization is suggested to account for this effect.     

Grafting to Vinylpyrrolidone Polymers and Copolymers by the Ceric lon Method

Polymers and copolymers of vinylpyrrolidone were investigated as grafting substrates for methyl methacrylate using the ceric ion method. Ceric ion readily initiates methyl methacrylate grafting to commercial poly (vinylpyrrolidone) (PVP) of 360,000 nominal molecular weight. The resulting graft copolymer was surprisingly found to be an ABA triblock system with PVP in the center block. This conclusion is supported by three key pieces of evidence: first, selective degradation of the PVP/MMA graft copolymer showed two PMMA grafts per PVP chain: second, blocking of what are apparently hydroxylic or glycolic PVP end groups by reaction with phenyl isocyanate rendered the PVP unreactive to ceric ion grafting; third, if the PVP is prepared by methods which preclude formation of hydroxylic end groups, the PVP is unreactive to ceric ion grafting.

Vinylpyrrolidone polymers can be made graftable via ceric ion if N-methacryloyl-D-glucosamine (NMAG) is incorporated as a comonomer in the PVP backbone. Regardless of the method of preparation, incorporation of NMAG provides grafting sites which are highly reactive to ceric ion. At copolymer compositions up to 10 mole % NMAG, the methyl methacrylate graft copolymers are soluble in organic solvents. Above 10 mole % NMAG, the grafting reaction leads to cross-linking and formation of intractable gels.     

Polymerization of vinyl monomers in the water–1,4-dioxane system containing peroxide and water-soluble polymer

Water-solube polymer (PST) containing triethylenetetramine side chain was prepared by the amination of chloromethylated polystyrene with triethylenetetramine in 1,4-dioxane. The polymerization of vinyl monomers was carried out in the water–organic solvent system containing PST and a very small amount of peroxide. The polymerization of methyl methacrylate proceeded smoothly in the presence of both peroxide and PST. It was found that the polymerization was initiated with the radicals generated by the interaction between hydroperoxide and amino groups of PST. 1,4-Dioxane hydroperoxide showed a high activity for the polymerization of methyl methacrylate. The maximum rate of the polymerization was observed at 60°C and in an approximately neutral solution. The addition of suitable amount of Cu(II) accelerated the polymerization of methyl methacrylate. The selective polymerization of vinyl monomers was observed in this system.     

Polymerization of methyl methacrylate with cupric laurate-N,N-dimethyl formamide as initiator system

The polymerization of methyl methacrylate with cupric laurate in combination with N,N-dimethyl formamide as initiator was studied in carbon tetrachloride medium at 60°C. The rate of polymerization was found to be proportional to the 3/2th power of the monomer concentrations and to the square root of both cupric laurate and DMF concentrations. Spectroscopic investigations indicated a ternary complex formation involving cupric ion, methyl methacrylate, and DMF. A reaction scheme is suggested on the basis of these results and various kinetic constants have been evaluated.     

Cationic and polymeric radicals of vinyl monomers in halogenated matrices: An ESR and SCF MO study

The vinyl monomers methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, and β-methylstyrene were dissolved in CF₃CCl₃, x-irradiated at 4 or 77 K, and investigated by ESR spectroscopy. The molecular cation of methyl acrylate has no resolved hyperfine structure, indicating that the unpaired electron is localized on the carbonyl oxygen. Evidence that a two-stage photoinduced reaction gives rise to a propagating radical was obtained. Propagating radicals were observed also with methyl methacrylate, acrylic acid, and methacrylic acid as solutes. The positive ion of β-methylstyrene has been prepared and characterized. The experimental data have been compared with molecular orbital calculations at different levels of approximation.