Breath-by-breath measurement of exhaled ammonia by acetonemodifier positive photoionization ion mobility spectrometry via online dilution and purging sampling

Exhaled ammonia(NH_(3))is an essential noninvasive biomarker for disease diagnosis.In this study,an acetone-modifier positive photoionization ion mobility spectrometry(AM-PIMS)method was developed for accurate qualitative and quantitative analysis of exhaled NH_(3)with high selectivity and sensitivity.Acetone was introduced into the drift tube along with the drift gas as a modifier,and the characteristic NH_(3)product ion peak of(C_(3)H_(6)O)_(4)NH_(4)^(+)(K_(0)=1.45 cm^(2)/V·s)was obtained through the ion-molecule reaction with acetone reactant ions(C_(3)H_(6)O)_(2)H^(+)(K_(0)=1.87 cm^(2)/V·s),which significantly increased the peak-to-peak resolution and improved the accuracy of exhaled NH_(3)qualitative identification.Moreover,the interference of high humidity and the memory effect of NH_(3)molecules were significantly reduced via online dilution and purging sampling,thus realizing breath-by-breath measurement.As a result,a wide quantitative range of 5.87-140.92μmol/L with a response time of 40 ms was achieved,and the exhaled NH_(3)profile could be synchronized with the concentration curve of exhaled CO_(2).Finally,the analytical capacity of AM-PIMS was demonstrated by measuring the exhaled NH_(3)of healthy subjects,demonstrating its great potential for clinical disease diagnosis.

Volatile Compounds Fingerprints for White Duck down and White Goose down Determined by Gas Chromatography-Ion Mobility Spectrometry

This work first describes a simple approach for the untargeted profiling of volatile compounds for distinguishing between white duck down (WDD) and white goose down (WGD) based on resolution-optimized GC-IMS combined with optimized chemometric techniques, namely PCA. The detection method for down samples was established by using GC-IMS. Meanwhile, the reason of unpleasant odors caused by WDD was explained on the basis of the characteristic volatile compounds identification. GC-IMS fingerprinting can be considered a revolutionary approach for a truly fully automatable, cost-efficient, and in particular highly sensitive method. A total of 22 compounds were successfully separated and identified through GC-IMS method, and the significant differences in volatile compounds were observed in three parts of WDD and WGD samples. The most characteristic volatile compounds of WGD belong to aldehydes, whereas carboxylic acids from WDD were detected generated by autoxidation reaction. Meanwhile, the main reason of unpleasant odor generation was possibly attributed to the high concentration of volatile carboxylic acids of WDD. Therefore, the constructed model presents a simple and efficient method of analysis and serves as a basis for down processing and quality control.

Separation of Ions from Volatile Organic Compounds Using High-Field Asymmetric Waveform Ion Mobility Spectrometry-Mass Spectrometer

A combination of high-field asymmetric waveform ion mobility spectrometry （FAIMS） with mass spectrometer （MS） was analyzed. FAIMS separates ions from the volatile organic compounds in the gas-phase as an ion-filter for MS. The sample ions were created at ambient pressure by ion source, which was equipped with a 10.6 eV UV discharge lamp （A=116.5 nm）. The drift tube of FAIMS is composed of two parallel planar electrodes and the dimension is 10 mm×8 mm×0.5 mm. FAIMS was investigated when driven by the high-filed rectangular asymmetric waveform with the peak-to-peak voltage of 1.36 kV at the frequency of 1 MHz and the duty cycle of 30%. The acetone, the butanone, and their mixture were adopted to characterize the FAIMS-MS. The mass spectra obtained from MS illustrate that there are ion-molecular reactions between the ions and the sample neutral molecular. And the proton transfer behavior in the mixture of the acetone and the butanone is also observed. With the compensation voltage tuned from -30 V to 10 V with a step size of 0.1 V, the ion pre-separation before MS is realized.

Electron Attachment Studies for CHCl3 Using Ion Mobility Spectrometry

The dissociative electron attachment process for CHCl3 at different electric field have been studied with nitrogen as drift and carrier gas using corona discharge ionization source ion mobility spectrometry （CD-IMS）. The corresponding electron attachment rate constants varied from 1.26×10-8 cm3/（molecules s） to 8.24×10-9 cm3/（molecules s） as the electric field changed from 200 V/cm to 500 V/cm. At a fixed electric field in the drift region, the attachment rate constants are also detected at different sample concentration. The ionmolecule reaction rate constants for the further reaction between Cl^- and CHCl3 are also detected, which indicates that the technique maybe becomes a new method to research the rate constants between ions and neural molecules. And the reaction rate constants between Cl- and CHCl3 are the first time detected using CD-IMS.

Peak Profile Analysis in High Field Asymmetric Wave Ion Mobility Spectrometry

High field asymmetric wave ion mobility spectrometry （FAIMS） is a powerful tool to detect and characterize gas-phase ions, while the unsolvable partial differential equation of ions moving in ion drift tube poses a big challenge to FAIMS spectral peak analysis. In this work, a universal and effective model of FAIMS spectral peak profile has been proposed by introducing ion trajectory and loss height. With this model, the influence of the structure of ion drift tube, dispersion voltages, compensation voltages, and carrier gas flow rate on the FAIMS spectral peak characteristics like peak shape, full width at half maximum and peak height is analyzed and discussed. The results show that the influence of different factors on the FAIMS spectral peak profile can be qualitatively described by the model which agrees with the experimental data.

Determination of alcohol compounds using corona discharge ion mobility spectrometry

Ion mobility spectrometry （IMS） is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions （H2O）nH^＋ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1- propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions （H2O）nH^＋. The mixture of these alcohols, including two isomers, has been detected, and the results showed that they could be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional ^63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.

Dimension-Enhanced Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry Combined with Intelligent Peak Annotation for the Rapid Characterization of the Multiple Components from Seeds of Descurainia sophia

The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a cough and asthma relieving agent.Herein,a dimension-enhanced integral approach,by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(UHPLC/IMQTOF-MS)and intelligent peak annotation,was developed to rapidly characterize the multicomponents from SDS.Good chromatographic separation was achieved within 38 min on a UPLC CSH C18(2.1×100 mm,1.7μm)column which was eluted by 0.1%formic acid in water(water phase)and acetonitrile(organic phase).Collision-induced dissociation-MS^(2)data were acquired by the data-independent high-definition MS^(E)(HDMS^(E))in both the negative and positive electrospray ionization modes.A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume.Moreover,a self-built chemistry library was established,which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS^(E)data.As a result of applying the intelligent peak annotation workflows and further confirmation process,a total of 53 compounds were identified or tentatively characterized from the SDS,including 29 flavonoids,one uridine derivative,four glucosides,one lignin,one phenolic compound,and 17 others.Notably,four-dimensional information related to the structure(e.g.,retention time,collision cross section,MS^(1)and MS^(2)data)was obtained for each component by the developed integral approach,and the results would greatly benefit the quality control of SDS.

Rapid authentication of sesame oil using ion mobility spectrometry and chemometrics

To ensure authenticity of sesame oil,an authentication technology was proposed using ion mobility spectrometry(IMS)and chemometrics.One-class classification(OCC)methods including one-class partial least squares(OCPLS)and one-class support vector machine(OCSVM)were employed to build authentication models for sesame oil.Subsequently,an independent test set was used to validate the constructed models.Validation set of 45 adulterated oils indicated that prediction correction rate of OCPLS model reached 95.6%(43 out of 45).Moreover,the complete set of sesame oils adulterated by sesame oil essence could be identified as counterfeit.Compared with previous studies,OCPLS model could work to identify untargeted adulteration.In conclusion,OCC method could effectively detect adulterated sesame oils containing as little as 10%other vegetable oils.This study provided a rapid screening method for adulterated sesame oil in market surveillance and a reference for developing authentication methods of other edible oils.

Structures of Stoichiometric Sodium Oxide Cluster Cations Studied by Ion Mobility Mass Spectrometry

Structures of stable compositions of sodium oxide cluster cations (NanOm+,n≤11) have been investigated by ion mobility mass spectrometry. Stoichiometric compositions series, Na(Na2O)(n-1)/2^+(n=3, 5, 7, 9, and 11), were observed as stable composition series, and NaO(Na2O)(n-1)/2^+ series (n=5, 7, 9, and 11) were observed as secondary stable series in the mass spectra. To assign the structures of these cluster ion series, collision cross sections between the ions and helium buffer gas were determined experimentally from the ion mobility measurements. Theoretical collision cross sections were also calculated for optimized structures of these compositions. Finally, the structures of Na(Na2O)(n-1)/2^+ and NaO(Na2O)(n-1)/2^+ were assigned to those having similar structural frames for each n except for n=9. All bonds in the assigned structures of Na(Na2O)(n-1)/2^+ were between sodium and oxygen. On the other hand, there was one O-O bond in addition to Na-O bonds in NaO(Na2O)(n-1)/2^+. This result indicates that NaO(Na2O)(n-1)/2^+ have a peroxide ion (O22-) as a substitute for an oxide ion (O2-) of Na(Na2O)(n-1)/2^+. As a result, both stable series, Na(Na2O)(n-1)/2^+ and NaO(Na2O)(n-1)/2^+, are closed-shell compositions. These closed-shell characteristics have a strong influence on the stability of sodium oxide cluster cations.

Effect of Temperature on Separation of Sarin (GB) Ions in Differential Mobility Spectrometry

Different environmental conditions in which, equipment based on differential ion mobility spectrometry must operate, forced designers and engineers to analyze the impact of, among other things, external factors on their performance and efficiency. These devices, thanks to the DMS technology, can identify and characterize the ions contained in the gaseous state. However, many areas of this technique remain undiscovered, which should be examined in more detail. One such aspect is the influence of the temperature of gaseous medium, containing tested analyte. The research presented in this article shows why temperature is an important factor on the distribution of generated peaks. The results are shown for different spectra generated carrier gas temperatures (50°C - 80°C) in which ions were toxic warfare agents. Based on those graphs, it can be stated that increase of the temperature allows for better separation of the peaks from the background. Because of the similar ion mobility of the analyte and background ions for high and low electric field, DMS device can send false alarms, due to the poor interpretations of passing a signal to them. So to be able to accurately assess the level of risk due to the presence of substances BST in air, the test medium was added to isobutanol and isopropanol additives. They help better analyze and separate measured ions.

Measurement of Ion Mobilities of Selected Amines by Ion Mobility Spectrometry

The ion mobilities of selected amines were measured by IMS. The minimum detection limits and linear ranges of selected amines were detected.

Glowing discharge ion source of ion mobility spectrometry

The paper investigated a new method of analyzing perfume odors.The study adopted IMS with glow dischargeas ion source and with positive ion mode.We got the quality characteristics of perfume odors in this way without any collection and concentration process.The quality of perfume odors can be identified by IMS peak characteristics,and the characteristics of different quality of perfume also can be identified.In summary,the IMS is an effective technique in the perfume odor detection,it is also a new way of gas sample analysis.

Screening for Plant Toxins in Honey and Herbal Beverage by Ultrahigh-Performance Liquid Chromatography-Ion Mobility-Quadrupole Time of Flight Mass Spectrometry

The standards of plant toxins were separated by a C18 column with gradient elution with 0.1% formic acid/water (V/V) and 0.1% formic acid/acetonitrile (V/V) as mobile phase and acquired by ion mobility-quadrupole time of flight mass spectrometry (IM-QTOF MS) in positive ion mode. A database of 308 plant toxins including retention time, collision cross-section (CCS) and its fragment ions was established. Honey dissolved in water or herbal beverage was extracted by acetonitrile and purified with PSA sorbent, and then acquired by ultrahigh-performance liquid chromatography IM-QTOFMS. The acquired data were processed by comparing with the database we established to confirm the target compounds. The average recoveries for samples at two levels ranged from 60.6% - 120.1%, with relative standard deviation (n = 6) less than 25%. The limit of quantitation for plant toxins ranged from 1 - 20 μg/kg. The developed screening method was used in determination of honey, herbal beverage and honey flavored tea beverage samples. The results showed that berberine was detected in one honey with 1 μg/kg and caffeine was present in some beverages with the concentration from 200 and 5500 μg/kg. This method could meet the requirement for rapid screening of plant toxins in honey and herbal beverage. It can be used for the quality control of honey and herbal beverage in enterprises or quality inspection departments. It also can be used in the rapid screening of food poisoning.

MALDI coupled with laser-postionization and trapped ion mobility spectrometry contribute to the enhanced detection of lipids in cancer cell spheroids

Cancer cell spheroids(CCS) are a valuable three-dimensional cell model in cancer studies because they could replicate numerous characteristics of solid tumors. Increasing researches have used matrix-assisted laser desorption/ionization mass spectrometry imaging(MALDI-MSI) to investigate the spatial distribution of endogenous compounds(e.g., lipids) in CCS. However, only limited lipid species can be detected owing to a low ion yield by using MALDI. Besides, it is still challenging to fully characterize the structural diversity of lipids due to the existence of isomeric/isobaric species. Here, we carried out the initial application of MALDI coupled with laser-postionization(MALDI-2) and trapped ion mobility spectrometry(TIMS) imaging in HCT116 colon CCS to address these challenges. We demonstrated that MALDI-2 is capable of detecting more number and classes of lipids in HCT116 colon CCS with higher signal intensities than MALDI. TIMS could successfully separate numerous isobaric/isomeric species of lipids in CCS. Interestingly, we found that some isomeric/isobaric species have totally different spatial distributions in colon CCS. Further MS/MS imaging analysis was employed to determine the compositions of fatty acid chains for isomeric species by examining disparities in signal intensities and spatial distributions of product ions. This work stresses the robust ability of TIMS and MALDI-2 imaging in analyzing endogenous lipids in CCS, which could potentially become powerful tools for future cancer studies.

Molecular Structural Characterization and Quantitative Prediction of Reduced Ion Mobility Constants for Diversified Organic Compounds

Based on two-dimensional topological structures, a novel molecular electronegativity interaction vector with hybridization （MEHIV） was developed to describe atomic hybridization state in different molecular environments. Five quantitative models by MEHIV characterization and multiple linear regression modeling were successfully established to predict reduced ion mobility constants （Ko） of alkanes, aromatic hydrocarbons, fatty alcohols, fatty aldehydes and ketones and carboxylic esters. The correlation coefficients Roy by leave-one-out cross-validation are 0.792, 0.787, 0,949, 0.972 and 0.981, respectively, and the standard deviations SDcv are 0.067, 0.086, 0.064, 0.043 and 0.042, respectively. These results suggested that MEHIV is an excellent topological index descriptor with many advantages such as straightforward physicochemical meaning, high characterization competence, convenient expansibility and easy manipulation.

基于GC-IMS和GC-MS技术结合化学计量法分析干燥方式对香椿挥发性成分的影响

为研究干燥方式对香椿挥发性风味物质的影响,利用气相色谱-离子迁移谱技术(gaschromatography-ion mobility spectrometry,GC-IMS)和气相色谱-质谱联用技术(gas chromatography-mass spectrometry,GC-MS)、相对香气活性值(relative odor activity value,ROAV)对真空冷冻干燥、热泵干燥、热风干燥、微波真空干燥的香椿样品进行挥发性成分分析,并进一步结合化学计量方法主成分分析(principal component analysis,PCA)和偏最小二乘判别分析(partial least squares-discriminant analysis,PLS-DA),探究样品间挥发性成分的差异性。结果表明,通过GC-IMS检测到78个峰,鉴定出59种化合物。通过GC-MS鉴定出94种挥发性化合物,主要挥发性成分是硫化物、烯烃类和醛类。经过干燥后总挥发性化合物的含量显著降低。通过ROAV法确定了(E,Z)-二-1-丙烯基二硫化物、2-巯基-3,4-二甲基-2,3-二氢噻吩、正己醛、2-己烯醛、丁香酚等为香椿样品中关键香气化合物。PCA和PLS-DA结果表明,不同干燥方式的样品与新鲜样品有明显的分离,彼此之间也有明显的区别。鲜样和真空冷冻干燥样品为一组,其他3个干燥香椿样品为一组。根据变量投影重要性(variable importance in projection,VIP)得分共筛选出10种(VIP>1)标志挥发性化合物。干燥方式对香椿风味特性影响显著,真空冷冻干燥组与鲜样最为接近,考虑实际应用热泵干燥为香椿最适宜的脱水方式。本研究为热加工过程中风味品质控制提供一定的理论参考。

基于HS-GC-IMS和HS-SPME-GC-MS的蛋白酶对豆粕挥发性风味的影响分析

为研究不同蛋白酶酶解对豆粕挥发性风味成分的影响,选用4种蛋白酶(碱性蛋白酶、中性蛋白酶、木瓜蛋白酶、风味蛋白酶)对豆粕进行酶解,采用顶空-气相色谱-离子迁移谱(Headspace-gas chromatography-ion mobility spectroscopy,HS-GC-IMS)和顶空固相微萃取-气相色谱-质谱(Headspace solid phase microextraction-gas chromatography-mass spectrometry,HS-SPME-GC-MS)联用技术分析不同豆粕酶解物(Soybean meal hydrolysates,SMH)的挥发性风味成分,并结合主成分分析(Principal component analysis,PCA)、热图聚类和正交偏最小二乘判别法(Orthogonal partial least squares-discriminant analysis,OPLS-DA)对不同SMH进行分析。结果表明:碱性蛋白酶、中性蛋白酶、木瓜蛋白酶和风味蛋白酶酶解豆粕的挥发性风味成分存在较大差异。HS-GC-IMS鉴定出84种挥发性成分,筛选得到33种差异风味物质,发现酶解后酮类物质显著降低而醛类、醇类和酯类物质含量明显增加。PCA结果表明不同SMH之间的风味存在显著差异。最终通过OPLS-DA筛选出贡献较大的挥发性化合物,同时构建出可靠的用以鉴别SMH的模型。HS-SPME-GC-MS检测出103种差异风味物质,可用于区分不同SMH,被检出的挥发性组分中醛类、醇类和酮类等化合物为SMH风味的形成做出主要贡献,明晰了部分风味化合物形成的原因。PCA和聚类热图结果表明不同蛋白酶酶解对豆粕的挥发性风味物质的种类和含量有显著影响,其中,风味蛋白酶和木瓜蛋白酶对豆粕的风味改善最为显著。

离子淌度质谱在食品分析中的应用

离子淌度谱是一种以样品离子在电场和气流共同作用下发生迁移时的差异来表征化合物的技术,可根据离子的电荷数、质量、尺寸以及形状对其进行分离,同时还可以通过计算出离子的碰撞横截面积,从而获得化合物的结构信息,在分离物质的同分异构体方面表现出优异的性能。近年来,多种离子淌度技术相继出现,并与质谱技术相联合广泛应用于食品、生物、医药、环境等领域。本文介绍了离子淌度谱技术的种类和工作原理,分析了不同种类技术当前存在的优势和缺陷,综述了离子淌度谱和液相、质谱等多维联用在分析鉴定食品营养活性成分和食品化学危害物中的应用,并对该技术的应用前景和发展趋势进行了展望。

干燥方式对苹果干品质特性及风味的影响

为探究提高静宁苹果干零食品质的加工方式,本研究探讨了5种干燥方式(热风干燥、太阳能干燥、真空冷冻干燥、微波-压差膨化干燥和热泵干燥)对苹果干能耗、抗氧化活性、微观结构和风味的影响。结果表明,和其它4种方式相比,在能耗方面,真空冷冻干燥的单位能耗最高(69.48±1.69 kW·h/kg),而太阳能干燥的单位能耗最低(19.60±1.36 kW·h/kg);在硬脆度方面,热风干燥的苹果干具有最高的硬度、最低的脆度,而真空冷冻干燥的苹果干硬度最低、脆度较高;在色差方面,真空冷冻干燥苹果干的L*值最高(72.91±0.59),ΔE值最接近鲜样(10.48±0.30);此外,真空冷冻干燥能有效降低苹果干中抗氧化物质的损失,与鲜样相比,其抗坏血酸、总酚和总黄酮的含量分别降低了35.22%、39.27%和32.02%。同时,总抗氧化能力、羟自由基清除率和超氧阴离子清除率也分别降低了23.50%、57.24%和10.56%;在微观结构方面,真空冷冻干燥的苹果干细胞层呈较规律的海绵状多孔性结构,质地较好;在风味方面,鉴定出5种干燥方式的苹果干有96种挥发性物质,其中真空冷冻干燥的苹果干更加芳香、口感更加丰富。综合考虑,真空冷冻干燥是提高苹果干零食品质特性和风味的推荐方法,对苹果干制品的工业化生产有现实的指导意义。

基于GC-IMS分析泡椒味万州烤鱼堂食过程的“三层次”风味变化

为分析泡椒味万州烤鱼堂食过程中风味的变化,采用气相色谱-离子迁移谱(GC-IMS)技术结合偏最小二乘判别分析(PLS-DA)探究其堂食过程中3个阶段的整体风味差异性及关键的风味标志物。结果显示:在3个阶段中共筛选出65种差异性风味成分,基于这些成分的PLS-DA模型能够有效区分各阶段的风味,呈现“三层次”风味分明的特点;变量投影重要性分析表明,乙酸异戊酯、乙酸芳樟酯、香茅醛(D)、2-乙基-5-甲基吡嗪、丁酸丁酯、己醇、2,6-二甲基吡啶、2-丁醇、1-辛烯-3-醇、2-庚醇、丁酸异丁酯、乙酸乙酯、2-甲基-2-戊烯醛、3-蒈烯、2,5-二甲基吡嗪共15种风味成分是区分泡椒味万州烤鱼堂食过程中“三层次”风味的潜在风味标志物。该研究深入挖掘万州烤鱼风味特征,为提升万州烤鱼品牌价值和制定万州烤鱼风味标准提供了有力的支持。