飞行时间质谱峰形分析

报道了在用脉冲355 nm的YAG激光对水/甲醇二元团簇的多光子电离飞行时间质谱研究中,发现在电离激光相对于脉冲分子束的不同延时或是同一延时下不同的激光能量下,测得的离子谱峰除强度变化外,峰值发生漂移.离子峰值漂移的大小与信号强度密切相关.信号强度越大,离子的飞行时间越短,峰值漂移越大.分析认为:这种峰值漂移不是因为新质量数谱峰的出现,而是离子在穿越质谱仪的离子引出区和加速区极板时发生部分离子吸附,引起极板间电压的起伏造成的.离子信号越强,意味着极板对离子吸附的量越大,导致离子峰值的漂移越大.离子在电场起伏下的数值模拟结果与实验中观测到的离子峰值漂移规律一致.     

电离效应对EBCMOS中电子倍增层增益的影响研究

采用蒙特卡罗模拟方法研究了电子轰击互补金属氧化物半导体(EBCMOS)成像器件中高能电子轰击半导体时产生的电离效应对电荷收集效率和电子倍增层增益的影响。分析了入射电子能量、p型衬底层掺杂浓度、电子倍增层和钝化层厚度对电荷收集效率和增益的影响。结果表明,增加入射电子能量(小于4 keV)、减小电子倍增层和钝化层厚度、降低掺杂浓度等是提高电荷收集效率和电子倍增层增益的有利途径,可为获得高增益的EBCMOS器件提供理论支撑。     

基质辅助激光解吸电离飞行时间质谱法检测副溶血性弧菌

目的 建立基质辅助激光解吸电离飞行时间质谱法(matrix assisted laser desorption ionization time of flight mass spectrometry, MALDI-TOF-MS)检测副溶血性弧菌的方法。方法 从样品预处理方法、分析菌量、培养基、培养时间方面分析各因素对MALDI-TOF-MS方法重复性、鉴定结果准确性的影响。将从市售420份水产品中分离并用全自动微生物鉴定及药敏分析系统生化鉴定为副溶血性弧菌的123株菌株,用MALDI-TOF-MS对其进行鉴定,对比2种方法的鉴定结果。结果 采用混合溶液法进行预处理,3%NaCl营养琼脂培养基, 36℃培养24 h,分析菌量为8 mg,用MALDI-TOF-MS进行分析所得到的特征峰多、峰型稳定、杂峰少,质谱图的准确性和重复性高、与生化鉴定匹配性好。分离得到的123株副溶血性弧菌鉴定分值大于2.000的达98.4%。结论 MALDI-TOF-MS作为一种快速、准确、高效的检测方法,可用于食品中副溶血性弧菌快速检测。     

四氮烯起爆药的电喷雾电离质谱裂解研究

为了更好地了解含能材料燃烧和爆炸机理,对四氮烯进行了电喷雾电离质谱分析。根据质谱图中碎片离子的信息,总结了四氮烯的裂解途径,发现四氮烯裂解时主要有NH2、HCN、HCN2、N3、N4中性碎片的丢失,推测它的裂解机理是C—N、N—N键的断裂反应和分子内重排反应;同时发现四唑环碎片离子m/z68.9的相对丰度较高,初步断定四氮烯分子结构中的四唑环是相对比较稳定的结构;并且由m/z68.9峰和m/z95.8峰的相对丰度接近,推测分子中C(5)—N(1)键和N(2)—N(3)键的键能相当(以四氮烯命名),且容易断裂,生成四唑自由基、氨基胍自由基和N2。     

Survey of bottled waters for perchlorate by electrospray ionization mass spectrometry (ESI‐MS) and ion chromatography (IC)

Perchlorate has been identified in ground and surface waters around the USA including some that serve as supplies for drinking water. Because perchlorate salts are used as solid oxidants in rockets and ordnance, water contamination may occur near military or aerospace installations or defense industry manufacturing facilities. This ion has been added to the Environmental Protection Agency's Contaminant Candidate List and the Unregulated Contaminant Monitoring Rule. Concern over perchlorate has prompted many residents in affected areas to switch to bottled water; however, bottled waters have not previously been examined for perchlorate contamination. Should the EPA promulgate a regulation for municipal water systems, US law requires the Food and Drug Administration to take action on bottled water. Methods will therefore be required to determine perchlorate concentrations not only in tap water, but also in bottled waters. Ion chromatography (IC) is the primary technique used for its analysis in drinking water, but it does not provide a unique identification. Confirmation by electrospray ionization mass spectrometry (ESI‐MS) can serve in this capacity. The ESI‐MS method can be applied to these products, but it requires an understanding of matrix effects, especially of high ionic strength that can suppress electrospray. When using methyl isobutyl ketone (MIBK) as the extraction solvent, the ESI‐MS method can reach lower limits of detection of 6 ng ml ⁻¹ for some bottled waters. However, dilution required to negate ionic strength effects in mineral waters can raise this by a factor of 10 or more, depending on the sample. Decyltrimethylammonium cation (added as the bromide salt) is used to produce an ion pair that is extracted into MIBK. After extraction, the sum of the peak areas of the ions C₁₀H₂₁NMe₃(Br)(ClO₄)⁻ (m/z = 380) and C₁₀H₂₁NMe₃(ClO₄)₂⁻ (m/z = 400) is used to quantitate perchlorate. Standard additions are used to account for most of the matrix effects. In this work, eight domestic brands and eight imported brands of bottled water were comparatively analyzed by the two techniques. For comparison, a finished potable water known to contain perchlorate was also tested. None of the bottled waters were found to contain any perchlorate within the lower limit of detection for the IC method. Recoveries on spiked samples subjected to the IC method were ≥98%. Published in 2000 for SCI by John Wiley & Sons, Ltd     

170MeV硫离子入射引起的反冲氩离子产额

利用１７０ＭｅＶ的Ｓ＾９＋与Ａｒ原子气体靶发生碰撞反应,采用高能离子引起的多重电离的飞行时间技术,测量了反冲击离子相对产额,并与多体经典轨道蒙特卡罗理论的计算结果进行了对比分析,发现理论低估了较高电荷态反冲离子的产额。     

基体辅助激光解吸电离飞行时间质谱仪的离子延时引出新技术研究

为了提高基体辅助激光解吸电离飞行时间质谱仪 ( MALDI- TOF- MS)的分辨率 ,在自行研制的研究级激光飞行时间质谱仪上进行了离子延时引出的( Delay Extraction,DE)新技术的实验研究 ,建立了新结构离子源和离子延迟引出的电子控制系统及相应软件。通过电场模拟和实验 ,研究了样品相对质量、延迟引出时间、引出电压对提高分辨率的影响。在使用 40 MHz瞬态记录仪的情况下 ,测得环十肽 ( m/z=1 2 1 4)分辨率为 1 734,胰岛素 ( m/z=5375)为 2 1 2 4。     

High-resolution PIXE instrumentation survey. Part II

High-resolution PIXE facilities (X-ray crystal spectrometers working on ion beams of accelerators) and their applications in chemical analysis and in basic research are surveyed.     

Gas Ionization During Carbothermal Reduction in Microwave Field and Its Effect

The reduction kinetic condition of the direct solid-phase reduction of metal oxide powder containing coal by microwave heating is better than that by the conventional heating process. The research shows that the gas ionization during carbothermal reduction accelerates the carbon gasification reaction and interface chemical reaction, and it also improves the kinetic conditions of carbothermal reduction. Thus, the formation mechanism and process of gas ionization as well as its effect during the carbothermal reduction of metal oxides containing coal by microwave heating are studied.     

对氯苯酚的共振增强多光子电离研究

在自行研制的具有恒温加热进样系统的激光质谱仪上实验研究了气相对氯苯酚分子的共振增强多光子电离飞行时间质谱(REMPI-TOFMS),获得了在275～285 nm激发波段的母体离子和主要碎片离子(C6H5O ,C5H5Cl C6H5 ,C5H 5,C4H 3,C3H 3)的(I I)REMPI激发光谱.通过质谱光谱分析,结合分子在中间激发态的能级和结构特征,对主要碎片离子的形成机理进行了研究.结果显示:各个碎片离子与对氯苯酚的母体离子具有相似的光激发谱,并且各个谱峰与S,1态的振动能级是一一对应的.说明各个碎片离子和母体离子的产生经历了相同的共振中间态.分子先吸收一个光子到达中间共振态,然后再吸收一个光子到达电离态电离.根据碎片离子光强指数的阶梯形分布和分子在S,1态的结构特点.判断各个碎片离子经历了母体离子的阶梯式离解,并给出了主要碎片离子的离解通道.