IMS-oaTOF-MS对选定的挥发性有机化合物（VOC）进行大气压化学电离研究
atmospheric pressure chemical ionisation study of selected volatile organic compounds (vocs) by ion mobility spectrometry
coupled with orthogonal accelerated time of flight mass spectrometry
离子迁移谱(ims)和正交加速飞行时间质谱(oatof-ms)法对选定的挥发性有机化合物（voc）进行大气压化学电离研究
1bartosz michalczuk, 1ladislav moravský, 1jana hrdá and 1,2štefan matej?ík
1comenius university in bratislava, faculty of mathematics, physics and informatics,
department of experimental physics, mlynská dolina f2 842 48, bratislava, slovakia
2national research nuclear university mephi, kashirskoe sh 31, moscow 115409, russia
abstract
in this work, we present an atmospheric pressure chemical ionisation (apci) study of several organic solvents relevant to thin layer chromatography (tlc) (methanol, ethanol, propan-2-ol, acetone, ethyl acetate, diethylamine). the solvents were investigated using an ion mobility spectrometry (ims) combined with orthogonal acceleration time of flight mass spectrometry (ims-oatof ms). the solvents were iononised by reactant ions (ri – h+.(h2o)3,4 m/z 55 and 73). the ions were analysed using ims and ims-oatof technique was used to assign the ion mobility peaks to ions according to their m/z. ims spectra of methanol, ethanol, propan-2-ol and diethylamine exhibited only one peak (reduced ion mobilities of 2.19, 2.07, 1.98, 2.06 cm2.s-1.v-1 respectively) whereas acetone and ethyl acetate were characterised by two peaks (2.15, 1.85 and 1.94, 1.53 cm2.s-1.v-1 respectively). the ims-oatof spectrometry assigned ims peaks of vocs to m.h+(h2o)n.n=0,1,2 or m2 .h+ ions, where m represents the solvent molecule.
本文对几种与薄层色谱(tlc)有关的有机溶剂(甲醇、乙醇、丙醇、丙酮、乙酸乙酯、二乙胺)进行了常压化学电离(apci)研究。采用离子迁移谱法(ims)和正交加速飞行时间质谱法(ims-oatof-ms)对溶剂进行了研究。溶剂被反应离子(ri–h+(h2o)3,4 m/z 55和73)离子化。利用ims和ims-oatof技术对离子进行了分析，并根据离子的m/z来确定离子迁移率峰，甲醇、乙醇、丙醇和二乙胺的ims光谱仅显示了一个峰(离子迁移率分别降低了2.19、2.07、1.98、2.06 cm~2.s-1.v-1)，而丙酮和乙酸乙酯的ims光谱则显示了一个有两个峰(分别为2.15、1.85和1.94、1.53 cm~2.s-1.v-1)。ims-oatof光谱法将vocs的ims峰分配给m.h+(h2o)n. n=0,1,2或m2.h+离子，其中m表示溶剂分子。
introduction
vocs are widely used in the chemical synthesis and chemical industry. in analytical chemistry, vocs solvents are used in the processes of sample preparation and in different chromatographic techniques. traces of the vocs are thus very often present in the laboratory environment and in the analytical samples. in the case of hyphenated technique, such as thin layer chromatography (tlc) with ims (tlc-ims), we deal with the problem of the presence of the solvents vocs contaminants in the ims spectra. for this reason, we have carried out a study focused on the identification of the solvents present in the tlc samples. in addition,
we have tried to understand the processes of ion formation from vocs in ims as they may interact with the analytes and influence the response of the system1,2,3. in present study we have selected six vocs – solvents (methanol, ethanol, propan-2-ol, acetone, diethylamine and ethyl acetate) and we have recorded their ims spectra in positive polarity atmospheric pressure chemical ionisation ion mobility spectrometry (apci-ims) and by the ion mobility spectrometry-orthogonal acceleration time of flight mass spectrometry technique (ims – oatof ms). to the selected solvents belong monohydric alcohols - methanol, ethanol, propan-2-ol, which
are widely used not only as a solvent but also in other applications, e.g., as a fuel additives (methanol, ethanol) or substrates for the synthesis of other compounds (methanol is used to produce formaldehyde)2,4,5,6. alcohols due to their ubiquity were investigated by ims with many different ionization sources i.e. uv, 63ni or corona discharge. depending on their concentration one or two peaks were observed in ims spectra corresponding to monomer and dimer formation. from available literature ions like m·h+·(h2o)m or m2·h+·(h2o)m formed in the reaction region of ims7,8,9. another important and widespread solvent is acetone, also known as 2-propanone or dimethyl ketone with chemical formula ch3coch3. it is volatile, flammable, colourless compound miscible in water. acetone is mainly used as a solvent and as an intermediate in many syntheses of organic compounds1,10 . regarding acetone’s high volatility and high proton affinity, it is possible to detect it at very low concentration. in most cases, even trace level in a range of ppb is enough to detect acetone by ims. vautz et al. has observed in positive polarity and radioactive ion source two peaks in the ims spectrum and assigned them to mh+ and m2h+11.
vocs广泛应用于化学合成和化工行业。在分析化学中，挥发性有机物溶剂用于样品制备过程和不同的色谱技术。因此，在实验室环境和分析样品中，挥发性有机化合物的痕迹经常存在。在联用技术的情况下，如薄层色谱(tlc)和ims(tlc-ims)，我们处理的是ims光谱中溶剂vocs污染物的存在问题。为此，我们开展了一项研究，重点是鉴别薄层色谱样品中的溶剂。此外，我们试图了解ims中vocs的离子形成过程，因为它们可能与分析物相互作用并影响系统1、2、3的响应。在本研究中，我们选择了六种挥发性有机化合物-溶剂(甲醇、乙醇、丙醇、丙酮、二乙胺和乙酸乙酯)，并在正极性大气压化学电离离子迁移谱(apci-ims)和离子迁移谱正交加速飞行时间质谱中记录了它们的ims谱光谱分析技术(ims-oatof ms)。所选溶剂为一元醇-甲醇、乙醇、丙烷-2-醇，其中不仅广泛用作溶剂，也广泛用于其他用途，例如用作燃料添加剂(甲醇、乙醇)或用于合成其他化合物(甲醇用于生产甲醛)2,4,5,6的基质。利用ims研究了不同电离源(uv、63ni或电晕放电)对醇类化合物的影响。根据它们的浓度，在ims光谱中观察到一个或两个对应于单体和二聚体形成的峰。从现有文献来看，ims7,8,9反应区形成的离子有m·h+·(h2o)m或m2·h+·(h2o)m。另一种重要且广泛使用的溶剂是丙酮，也称为2-丙酮或二甲酮，化学式为ch3coch3。它是易挥发、易燃、无色的化合物，可混溶于水。丙酮在许多有机化合物1，10的合成中主要用作溶剂和中间体。由于丙酮的高挥发性和高质子亲和力，可以在很低的浓度下进行检测。在大多数情况下，即使在ppb范围内的微量水平也足以通过ims检测丙酮。vautz等人。在正极性和放射性离子源中观察到ims光谱中的两个峰值，并将它们分配给mh+和m2h+11。
amines are a widespread contaminant in the environment due to their industrial applications or their use as intermediates in chemical and pharmaceutical syntheses12,13,14. the amines are unique as they can form several types of isomers: linear, positional isomers, primary, secondary, and tertiary amines, branched, and cyclic structures and finally, also aromatic isomers15. due to their odorous and toxic characteristics, these compounds have received much attention as environmental pollutants 16. some of them are sensitizers and irritants to the skin, mucous membrane and respiratory tract17. the most frequently used techniques for the determination of amines in air and liquid samples are gas chromatography (gc) coupled with different detectors, high-performance liquid chromatography (hplc) 18 , 19 ion chromatography20, spectrophotometry21 and capillary electrophoresis22. in some cases, for detection of amines in gas and liquid phase ion mobility spectrometry (ims) has been used23. due to their high proton affinities, amines protonate readily in the ims source, and there is usually little doubt about the site of protonation, as the nitrogen electron lone pair is the favoured site. in most cases, the major ionic product is the protonated molecule, although in some cases protonated dimers or molecular or fragment ions are also formed14. one of the most important amines is a secondary amine named diethylamine - (dea) (chemical formula - c4h11n) which is a strong base compound miscible with most solvents. it is used as an anti-corrosion agent, as well as in rubber, synthetic resin, paint and drug manufacturing. it is used in the production of certain agrochemicals, such as rice herbicides or insecticides pharmaceuticals, radical scavengers and insect repellents24. in some cases, dea is frequently used as a chemical reducer25,26.
胺是一种广泛存在于环境中的污染物，由于其工业应用或在化学和药物合成中用作中间体12、13、14。胺是*的，因为它们可以形成几种异构体：线性、位置异构体、一级、二级和三级胺、支链和环状结构，后还有芳香异构体15。由于它们的气味和毒性特征，这些化合物作为环境污染物16受到了广泛关注。其中一些是皮肤、粘膜和呼吸道的致敏剂和刺激物17。用于测定空气和液体样品中技术是气相色谱(gc)与不同检测器的耦合、高效液相色谱(hplc)18、19离子色谱20、分光光度计21和毛细管电泳22。在某些情况下，气相和液相离子迁移率光谱法(ims)已用于检测胺类化合物23。由于胺具有很高的质子亲和力，因此在ims源中很容易发生质子化，而且通常对质子化的位置几乎没有疑问，因为氮-电子孤对是利的位置。在大多数情况下，主要的离子产物是质子化分子，尽管在某些情况下，质子化二聚体或分子或片段离子也形成14。重要的胺之一是二乙胺(dea)(化学式-c4h11n)，它是一种强碱性化合物，可与大多数溶剂混溶。用于橡胶、合成树脂、涂料和药品制造等领域。它用于生产某些农用化学品，如水稻除草剂或杀虫剂药物、自由基清除剂和驱虫剂24。在某些情况下，dea经常被用作化学还原剂25，26。
ethyl acetate is the organic compound (chemical formula c4h8o2) synthesized in the industry from ethanol and acetic acid. it is widely used as a solvent in the production of pharmaceuticals, essential ingredients in many products and materials, in variety of coating formulations such as epoxies, urethanes, cellulosic, acrylics and vinyls, fragrances in food production and precursors of important chemicals being favoured because of its low cost, low toxicity and agreeable odour27. in high purity, it can be used as a viscosity reducer for resins used in photoresist formulations in the electronics industry. ethyl acetate is rarely selected as a reactant due to its tendency to hydrolysis and transesterification28,29. mixtures containing ethyl acetate are commonly used in column-liquid chromatography and extractions. because of its high polarity index (4.4) ethyl acetate can be used very frequently as a polar-solvent to run tlc (thin layer chromatography)30,31,32,33,34.
乙酸乙酯是工业上由乙醇和乙酸合成的有机化合物(化学式c4h8o2)。它被广泛用作药物生产中的溶剂，在许多产品和材料中的基本成分，在各种涂料配方中，如环氧树脂、聚氨酯、纤维素、丙烯酸和乙烯基酯、食品生产中的香料和重要化学品的前体由于其低成本而受到青睐。毒性低，气味适中。在高纯度的情况下，它可以用作电子工业中用于光刻胶配方的树脂的降粘剂。乙酸乙酯很少被选作反应物，因为它倾向于水解和酯交换28,29。含有乙酸乙酯的混合物通常用于柱液相色谱和萃取。乙酸乙酯由于其极性指数高(4.4)，可以非常频繁地用作极性溶剂来运行tlc(薄层色谱法)30、31、32、33、34。
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IMS-oaTOF-MS对选定的挥发性有机化合物（VOC）进行大气压化学电离研究
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65型填充改性PS加碳酸钙塑料抽粒机
coupled with orthogonal accelerated time of flight mass spectrometry
离子迁移谱(ims)和正交加速飞行时间质谱(oatof-ms)法对选定的挥发性有机化合物（voc）进行大气压化学电离研究
1bartosz michalczuk, 1ladislav moravský, 1jana hrdá and 1,2štefan matej?ík
1comenius university in bratislava, faculty of mathematics, physics and informatics,
department of experimental physics, mlynská dolina f2 842 48, bratislava, slovakia
2national research nuclear university mephi, kashirskoe sh 31, moscow 115409, russia
abstract
in this work, we present an atmospheric pressure chemical ionisation (apci) study of several organic solvents relevant to thin layer chromatography (tlc) (methanol, ethanol, propan-2-ol, acetone, ethyl acetate, diethylamine). the solvents were investigated using an ion mobility spectrometry (ims) combined with orthogonal acceleration time of flight mass spectrometry (ims-oatof ms). the solvents were iononised by reactant ions (ri – h+.(h2o)3,4 m/z 55 and 73). the ions were analysed using ims and ims-oatof technique was used to assign the ion mobility peaks to ions according to their m/z. ims spectra of methanol, ethanol, propan-2-ol and diethylamine exhibited only one peak (reduced ion mobilities of 2.19, 2.07, 1.98, 2.06 cm2.s-1.v-1 respectively) whereas acetone and ethyl acetate were characterised by two peaks (2.15, 1.85 and 1.94, 1.53 cm2.s-1.v-1 respectively). the ims-oatof spectrometry assigned ims peaks of vocs to m.h+(h2o)n.n=0,1,2 or m2 .h+ ions, where m represents the solvent molecule.
本文对几种与薄层色谱(tlc)有关的有机溶剂(甲醇、乙醇、丙醇、丙酮、乙酸乙酯、二乙胺)进行了常压化学电离(apci)研究。采用离子迁移谱法(ims)和正交加速飞行时间质谱法(ims-oatof-ms)对溶剂进行了研究。溶剂被反应离子(ri–h+(h2o)3,4 m/z 55和73)离子化。利用ims和ims-oatof技术对离子进行了分析，并根据离子的m/z来确定离子迁移率峰，甲醇、乙醇、丙醇和二乙胺的ims光谱仅显示了一个峰(离子迁移率分别降低了2.19、2.07、1.98、2.06 cm~2.s-1.v-1)，而丙酮和乙酸乙酯的ims光谱则显示了一个有两个峰(分别为2.15、1.85和1.94、1.53 cm~2.s-1.v-1)。ims-oatof光谱法将vocs的ims峰分配给m.h+(h2o)n. n=0,1,2或m2.h+离子，其中m表示溶剂分子。
introduction
vocs are widely used in the chemical synthesis and chemical industry. in analytical chemistry, vocs solvents are used in the processes of sample preparation and in different chromatographic techniques. traces of the vocs are thus very often present in the laboratory environment and in the analytical samples. in the case of hyphenated technique, such as thin layer chromatography (tlc) with ims (tlc-ims), we deal with the problem of the presence of the solvents vocs contaminants in the ims spectra. for this reason, we have carried out a study focused on the identification of the solvents present in the tlc samples. in addition,
we have tried to understand the processes of ion formation from vocs in ims as they may interact with the analytes and influence the response of the system1,2,3. in present study we have selected six vocs – solvents (methanol, ethanol, propan-2-ol, acetone, diethylamine and ethyl acetate) and we have recorded their ims spectra in positive polarity atmospheric pressure chemical ionisation ion mobility spectrometry (apci-ims) and by the ion mobility spectrometry-orthogonal acceleration time of flight mass spectrometry technique (ims – oatof ms). to the selected solvents belong monohydric alcohols - methanol, ethanol, propan-2-ol, which
are widely used not only as a solvent but also in other applications, e.g., as a fuel additives (methanol, ethanol) or substrates for the synthesis of other compounds (methanol is used to produce formaldehyde)2,4,5,6. alcohols due to their ubiquity were investigated by ims with many different ionization sources i.e. uv, 63ni or corona discharge. depending on their concentration one or two peaks were observed in ims spectra corresponding to monomer and dimer formation. from available literature ions like m·h+·(h2o)m or m2·h+·(h2o)m formed in the reaction region of ims7,8,9. another important and widespread solvent is acetone, also known as 2-propanone or dimethyl ketone with chemical formula ch3coch3. it is volatile, flammable, colourless compound miscible in water. acetone is mainly used as a solvent and as an intermediate in many syntheses of organic compounds1,10 . regarding acetone’s high volatility and high proton affinity, it is possible to detect it at very low concentration. in most cases, even trace level in a range of ppb is enough to detect acetone by ims. vautz et al. has observed in positive polarity and radioactive ion source two peaks in the ims spectrum and assigned them to mh+ and m2h+11.
vocs广泛应用于化学合成和化工行业。在分析化学中，挥发性有机物溶剂用于样品制备过程和不同的色谱技术。因此，在实验室环境和分析样品中，挥发性有机化合物的痕迹经常存在。在联用技术的情况下，如薄层色谱(tlc)和ims(tlc-ims)，我们处理的是ims光谱中溶剂vocs污染物的存在问题。为此，我们开展了一项研究，重点是鉴别薄层色谱样品中的溶剂。此外，我们试图了解ims中vocs的离子形成过程，因为它们可能与分析物相互作用并影响系统1、2、3的响应。在本研究中，我们选择了六种挥发性有机化合物-溶剂(甲醇、乙醇、丙醇、丙酮、二乙胺和乙酸乙酯)，并在正极性大气压化学电离离子迁移谱(apci-ims)和离子迁移谱正交加速飞行时间质谱中记录了它们的ims谱光谱分析技术(ims-oatof ms)。所选溶剂为一元醇-甲醇、乙醇、丙烷-2-醇，其中不仅广泛用作溶剂，也广泛用于其他用途，例如用作燃料添加剂(甲醇、乙醇)或用于合成其他化合物(甲醇用于生产甲醛)2,4,5,6的基质。利用ims研究了不同电离源(uv、63ni或电晕放电)对醇类化合物的影响。根据它们的浓度，在ims光谱中观察到一个或两个对应于单体和二聚体形成的峰。从现有文献来看，ims7,8,9反应区形成的离子有m·h+·(h2o)m或m2·h+·(h2o)m。另一种重要且广泛使用的溶剂是丙酮，也称为2-丙酮或二甲酮，化学式为ch3coch3。它是易挥发、易燃、无色的化合物，可混溶于水。丙酮在许多有机化合物1，10的合成中主要用作溶剂和中间体。由于丙酮的高挥发性和高质子亲和力，可以在很低的浓度下进行检测。在大多数情况下，即使在ppb范围内的微量水平也足以通过ims检测丙酮。vautz等人。在正极性和放射性离子源中观察到ims光谱中的两个峰值，并将它们分配给mh+和m2h+11。
amines are a widespread contaminant in the environment due to their industrial applications or their use as intermediates in chemical and pharmaceutical syntheses12,13,14. the amines are unique as they can form several types of isomers: linear, positional isomers, primary, secondary, and tertiary amines, branched, and cyclic structures and finally, also aromatic isomers15. due to their odorous and toxic characteristics, these compounds have received much attention as environmental pollutants 16. some of them are sensitizers and irritants to the skin, mucous membrane and respiratory tract17. the most frequently used techniques for the determination of amines in air and liquid samples are gas chromatography (gc) coupled with different detectors, high-performance liquid chromatography (hplc) 18 , 19 ion chromatography20, spectrophotometry21 and capillary electrophoresis22. in some cases, for detection of amines in gas and liquid phase ion mobility spectrometry (ims) has been used23. due to their high proton affinities, amines protonate readily in the ims source, and there is usually little doubt about the site of protonation, as the nitrogen electron lone pair is the favoured site. in most cases, the major ionic product is the protonated molecule, although in some cases protonated dimers or molecular or fragment ions are also formed14. one of the most important amines is a secondary amine named diethylamine - (dea) (chemical formula - c4h11n) which is a strong base compound miscible with most solvents. it is used as an anti-corrosion agent, as well as in rubber, synthetic resin, paint and drug manufacturing. it is used in the production of certain agrochemicals, such as rice herbicides or insecticides pharmaceuticals, radical scavengers and insect repellents24. in some cases, dea is frequently used as a chemical reducer25,26.
胺是一种广泛存在于环境中的污染物，由于其工业应用或在化学和药物合成中用作中间体12、13、14。胺是*的，因为它们可以形成几种异构体：线性、位置异构体、一级、二级和三级胺、支链和环状结构，后还有芳香异构体15。由于它们的气味和毒性特征，这些化合物作为环境污染物16受到了广泛关注。其中一些是皮肤、粘膜和呼吸道的致敏剂和刺激物17。用于测定空气和液体样品中技术是气相色谱(gc)与不同检测器的耦合、高效液相色谱(hplc)18、19离子色谱20、分光光度计21和毛细管电泳22。在某些情况下，气相和液相离子迁移率光谱法(ims)已用于检测胺类化合物23。由于胺具有很高的质子亲和力，因此在ims源中很容易发生质子化，而且通常对质子化的位置几乎没有疑问，因为氮-电子孤对是利的位置。在大多数情况下，主要的离子产物是质子化分子，尽管在某些情况下，质子化二聚体或分子或片段离子也形成14。重要的胺之一是二乙胺(dea)(化学式-c4h11n)，它是一种强碱性化合物，可与大多数溶剂混溶。用于橡胶、合成树脂、涂料和药品制造等领域。它用于生产某些农用化学品，如水稻除草剂或杀虫剂药物、自由基清除剂和驱虫剂24。在某些情况下，dea经常被用作化学还原剂25，26。
ethyl acetate is the organic compound (chemical formula c4h8o2) synthesized in the industry from ethanol and acetic acid. it is widely used as a solvent in the production of pharmaceuticals, essential ingredients in many products and materials, in variety of coating formulations such as epoxies, urethanes, cellulosic, acrylics and vinyls, fragrances in food production and precursors of important chemicals being favoured because of its low cost, low toxicity and agreeable odour27. in high purity, it can be used as a viscosity reducer for resins used in photoresist formulations in the electronics industry. ethyl acetate is rarely selected as a reactant due to its tendency to hydrolysis and transesterification28,29. mixtures containing ethyl acetate are commonly used in column-liquid chromatography and extractions. because of its high polarity index (4.4) ethyl acetate can be used very frequently as a polar-solvent to run tlc (thin layer chromatography)30,31,32,33,34.
乙酸乙酯是工业上由乙醇和乙酸合成的有机化合物(化学式c4h8o2)。它被广泛用作药物生产中的溶剂，在许多产品和材料中的基本成分，在各种涂料配方中，如环氧树脂、聚氨酯、纤维素、丙烯酸和乙烯基酯、食品生产中的香料和重要化学品的前体由于其低成本而受到青睐。毒性低，气味适中。在高纯度的情况下，它可以用作电子工业中用于光刻胶配方的树脂的降粘剂。乙酸乙酯很少被选作反应物，因为它倾向于水解和酯交换28,29。含有乙酸乙酯的混合物通常用于柱液相色谱和萃取。乙酸乙酯由于其极性指数高(4.4)，可以非常频繁地用作极性溶剂来运行tlc(薄层色谱法)30、31、32、33、34。
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