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71. 发明授权

US06653626B2 Ion sampling for APPI mass spectrometry 有权
公开(公告)号：US06653626B2
公开(公告)日：2003-11-25
申请号：US10155364
申请日：2002-05-23
申请人： Steven M. Fischer , Darrell L. Gourley , Patricia H. Cormia , James L. Bertsch
发明人： Steven M. Fischer , Darrell L. Gourley , Patricia H. Cormia , James L. Bertsch
IPC分类号： H01J4926
CPC分类号： G01N30/7253 , H01J27/24 , H01J49/0431 , H01J49/145 , H01J49/162
摘要： An atmospheric pressure ion source, e.g. for a mass spectrometer, that produces ions by atmospheric pressure photoionization (APPI). It includes a vaporizer, a photon source for photoionizing vapor molecules upon exit from the vaporizer, a passageway for transporting ions to, for example, a mass spectrometer system, and a means for directing the ions into the passageway. The center axis of the vaporizer and the center axis of the passageway form an angle that may be about 90 degrees. Included in the invention is a method for creating ions by atmospheric pressure photoionization along an axis and directing them into a passageway oriented at an angle to that axis.

72. 发明申请

US20030155497A1 Electrospray ionization mass analysis apparatus and system thereof 有权
标题翻译：电喷雾电离质量分析装置及其系统
公开(公告)号：US20030155497A1
公开(公告)日：2003-08-21
申请号：US10221844
申请日：2003-02-11
发明人： Yoshiaki Kato
IPC分类号： H01J049/00 , B01D059/44
CPC分类号： H01J49/0031 , H01J49/0431 , H01J49/165
摘要： Because of a low flow rate of the micro LC/MS, the dead volume or the diameter of a capillary tube must be minimized, and a sample and salt are likely to deposit in the capillary tube, with the result that clogging of the capillary tube and ESI nozzle often occurs. An electrospray ionization mass analysis apparatus and its system of the present invention predicts clogging, permit earlier cleaning or parts replacement, and detect clogging even if it has occurred, thereby suspending measurement and preventing samples from being introduced into an injector, with the result that waste of samples is avoided and effective data is ensured. The aforementioned electrospray ionization mass analysis apparatus directly coupled to the micro LC prevents a micro LC, piping and ESI capillary tube from being clogged, and records an alarm in the data and stops the system whenever clogging has occurred, whereby highly reliable direct coupling with micro LC is ensured. In the aforementioned electrospray ionization mass analysis apparatus and its system, a sample solution from a chromatograph is introduced into a capillary tube, and an electrospray ion source arranged for generating ions under atmospheric pressure generates ions, which are led into a mass spectrometer disposed in a vacuum chamber where the ion is subjected to mass analysis. The current value or strength of the ion having a specified mass in the sample solution is measured, and, when the current value has reduced below a threshold value, an error state is displayed.
摘要翻译：由于微LC / MS的流速低，毛细管的死体积或直径必须最小化，并且样品和盐可能沉积在毛细管中，导致毛细管堵塞和ESI喷嘴经常发生。本发明的电喷雾离子化质量分析装置及其系统预测堵塞，允许更早的清洁或部件更换，并且即使发生堵塞也可以检测到堵塞，从而悬挂测量并防止样品被引入注射器，结果是浪费避免了样品，确保了有效的数据。直接耦合到微LC的上述电喷雾电离质量分析装置防止微LC，管道和ESI毛细管被堵塞，并且在数据中记录报警并且每当发生堵塞时停止系统，由此高度可靠的与微观的直接耦合 LC保证。在上述电喷雾离子化质量分析装置及其系统中，将来自色谱仪的样品溶液引入毛细管中，并且设置用于在大气压下产生离子的电喷雾离子源产生离子，将其引入设置在真空室，离子进行质量分析。测定样品溶液中具有特定质量的离子的当前值或强度，并且当当前值降低到阈值以下时，显示错误状态。

73. 发明申请

US20030075680A1 Orthogonal ion sampling for APCI mass spectrometry 失效
公开(公告)号：US20030075680A1
公开(公告)日：2003-04-24
申请号：US10265943
申请日：2002-10-07
发明人： James A. Apffel JR. , Mark H. Werlich , James L. Bertsch , Paul C. Goodley , Kent D. Henry
IPC分类号： H01J049/04
CPC分类号： H01J49/145 , G01N30/7253 , H01J49/0431 , H01J49/165 , H01J49/168
摘要： A method and apparatus are disclosed wherein a plurality of electric fields and of orthogonal spray configurations of vaporized analyte are so combined as to enhance the efficiency of analyte detection and mass analysis. The invention provides reduced noise and increased signal sensitivity in both API electrospray and APCI operating modes.

74. 发明申请

US20020063208A1 Median filter for liquid chromatography-mass spectrometry data 失效
标题翻译：用于液相色谱 - 质谱数据的中值过滤器
公开(公告)号：US20020063208A1
公开(公告)日：2002-05-30
申请号：US09994575
申请日：2001-11-27
申请人： SURROMED, INC.
发明人： Curtis Hastings
IPC分类号： H01J049/00
CPC分类号： H01J49/0036 , G01N30/72 , G01N30/8624 , G01N30/8641 , H01J49/0431
摘要： High-intensity, spiked noise is reduced in chromatography-mass spectrometry data by applying a nonlinear filter such as a moving median filter to the data. The filter is applied to individual mass chromatograms, plots of ion abundance versus retention time for each detected mass-to-charge ratio, and the filtered chromatograms are combined to form a filtered total ion current chromatogram. Standard linear filters are not effective for reducing noise in liquid chromatography-mass spectrometry (LC-MS) data because they assume a normal distribution of noise. LC-MS noise, however, is not normally distributed.
摘要翻译：通过对数据应用诸如移动中值滤波器的非线性滤波器，在色谱 - 质谱数据中降低了高强度，加标噪声。将过滤器应用于单个质量色谱图，每种检测质量 - 电荷比的离子丰度曲线与保留时间曲线，并将滤出的色谱图合并形成过滤的总离子电流色谱图。标准线性滤波器对于降低液相色谱 - 质谱（LC-MS）数据中的噪声无效，因为它们假设噪声的正态分布。然而，LC-MS噪声不是正态分布的。

75. 发明授权

US06054709A Method and apparatus for determining the rates of reactions in liquids by mass spectrometry 失效
标题翻译：用于通过质谱测定液体中反应速率的方法和装置
公开(公告)号：US06054709A
公开(公告)日：2000-04-25
申请号：US986140
申请日：1997-12-05
申请人： Donald J. Douglas , Lars Konermann , Bruce Collings
发明人： Donald J. Douglas , Lars Konermann , Bruce Collings
IPC分类号： G01N27/62 , G01N35/08 , H01J49/04
CPC分类号： H01J49/0431 , G01N35/085
摘要： A method and apparatus are provided for determining rates and mechanisms of reactions in solution. The method comprises mixing reactants together and then passing the reactants, after mixing, to an electrospray or other ion source. The apparatus is configured so that the reaction time can be determined. This can either be by way of a capillary of known length and volume extending from a reaction tee or other mixing device, so that the reaction time can be determined from the capillary volume and flow rate, and/or by way of a container of fixed volume from which the reactants pass. From the ion source, ions pass into a mass spectrometer, where a mass spectrum is measured. By varying the reaction time, and measuring the different mass spectra, the rate of reaction can be determined.
摘要翻译：提供了一种用于确定溶液中反应速率和机制的方法和装置。该方法包括将反应物混合在一起，然后将混合后的反应物通入电喷雾或其它离子源。该装置被配置成可以确定反应时间。这可以通过已知长度的毛细管和从反应三通或其它混合装置延伸的体积，使得反应时间可以从毛细管体积和流速确定，和/或通过固定的容器确定反应物通过的体积。从离子源，离子进入质谱仪，其中测量质谱。通过改变反应时间，测量不同的质谱，可以测定反应速率。

76. 发明授权

US5792663A High efficiency continuous flow through fractional-volatilization separator system, and method of use 失效
$High efficiency continuous flow through fractional-volatilization separator system, and method of use$
标题翻译：通过分级挥发分离器系统的高效率连续流动及其使用方法
公开(公告)号：US5792663A
公开(公告)日：1998-08-11
申请号：US722781
申请日：1996-09-27
申请人： Robert C. Fry , Michael R. Dyas , Jason A. Rivers , Robert M. Brown, Jr.
发明人： Robert C. Fry , Michael R. Dyas , Jason A. Rivers , Robert M. Brown, Jr.
IPC分类号： B01D1/22 , G01N1/40 , G01N33/00 , H01J49/04 , G01N33/20 , G01N21/00 , G01N1/10
CPC分类号： H01J49/0431 , B01D1/22 , G01N1/40 , G01N2001/4033 , Y10T436/24 , Y10T436/25875
摘要： Fractional-volatilization separation systems and methods are disclosed which enable a stable, continuous, non-bubbling liquid flow, essentially constant surface area/volume ratio, temperature controlled, fractional volatilization of volatile/semi-volatile components in a liquid analyte or component containing sample. The fractional volatilization separator system can be utilized in small scale analytical and large scale chemical purification, concentration and desalinization applications. Continuous rapid removal of residual liquid sample can provide concentrated non-volatile component/analyte solution, and allows quick and easy washout between sequential use with different liquid samples. Examples of relevant analytical chemistry applications of the present invention system are found in conjunction with long-path absorbance-cell "cold-vapor" mercury analyzers, cold vapor mercury fluorescense photometers, infrared spectrophotometers, organic mass spectrometers, plasma emission spectrometers, and plasma mass spectrometers.
摘要翻译：公开了分散挥发分离系统和方法，其能够在液体分析物或含部件的样品中实现稳定，连续，非鼓泡液体流动，基本恒定的表面积/体积比，温度控制，挥发性/半挥发性组分的分数挥发。分级挥发分离系统可用于小规模分析和大规模化学纯化，浓缩和脱盐应用。残留液体样品的连续快速去除可以提供浓缩的非挥发性成分/分析物溶液，并且允许在不同液体样品的顺序使用之间快速和容易地冲洗。本发明系统的相关分析化学应用的实例结合长途吸收 - 电池“冷蒸气”汞分析仪，冷汽汞汞荧光光度计，红外分光光度计，有机质谱仪，等离子体发射光谱仪和等离子体质量光谱仪

77. 发明授权

US5359196A Mass spectrometry with gas counterflow for particle beam 失效
标题翻译：用于粒子束的气体逆流质谱
公开(公告)号：US5359196A
公开(公告)日：1994-10-25
申请号：US66369
申请日：1993-05-24
申请人： Robert T. Whitt
发明人： Robert T. Whitt
IPC分类号： G01N30/02 , G01N30/46 , G01N30/72 , H01J49/04
CPC分类号： H01J49/0431 , G01N30/7246 , H01J49/0422 , G01N2030/025 , G01N2030/027 , G01N30/462 , G01N30/465 , G01N30/7206 , G01N30/7273 , G01N30/7293
摘要： In an LC mode, the GC system of a GC/LC/MS system provides a counterflow to an LC particle beam. The counterflow increases signal strength and, for some relatively high molecular mass analytes, reduces fragmentation.
摘要翻译：在LC模式下，GC / LC / MS系统的GC系统提供了对LC粒子束的逆流。逆流增加了信号强度，并且对于一些相对较高的分子量分析物，减少了碎裂。

78. 发明授权

US5311016A Apparatus for preparing a sample for mass spectrometry 失效
标题翻译：用于制备质谱样品的装置
公开(公告)号：US5311016A
公开(公告)日：1994-05-10
申请号：US933151
申请日：1992-08-21
申请人： Eliel Villa-Aleman
发明人： Eliel Villa-Aleman
IPC分类号： H01J49/40 , B01D59/44 , H01J49/00
CPC分类号： H01J49/0431 , H01J49/18
摘要： An apparatus for preparing a sample for analysis by a mass spectrometer system. The apparatus has an entry chamber and an ionization chamber separated by a skimmer. A capacitor having two space-apart electrodes followed by one or more ion-imaging lenses is disposed in the ionization chamber. The chamber is evacuated and the capacitor is charged. A valve injects a sample gas in the form of sample pulses into the entry chamber. The pulse is collimated by the skimmer and enters the ionization chamber. When the sample pulse passes through the gap between the electrodes, it discharges the capacitor and is thereby ionized. The ions are focused by the imaging lenses and enter the mass analyzer, where their mass and charge are analyzed.
摘要翻译：一种用于通过质谱仪系统制备用于分析的样品的装置。该装置具有由分离器分离的入口室和离子化室。具有两个间隔开的电极和一个或多个离子成像透镜的电容器设置在电离室中。将室抽真空，并对电容器进行充电。阀将样品脉冲形式的样品气体注入进入室。脉冲由撇渣器准直并进入电离室。当采样脉冲通过电极之间的间隙时，它会放电电容器，从而电离。离子被成像透镜聚焦并进入质量分析仪，在此分析其质量和电荷。

79. 发明授权

US4994165A Liquid junction coupling for capillary zone electrophoresis/ion spray spectrometry 失效
标题翻译：用于毛细管区带电泳/离子喷射光谱法的液体接头
公开(公告)号：US4994165A
公开(公告)日：1991-02-19
申请号：US311500
申请日：1989-02-16
申请人： Edgar D. Lee , Thomas R. Covey , John D. Henion
发明人： Edgar D. Lee , Thomas R. Covey , John D. Henion
IPC分类号： G01N27/447 , H01J49/04
CPC分类号： H01J49/0431 , G01N27/44717 , H01J49/165 , G01N27/4473
摘要： An improved capillary zone electrophoresis (CZE)/ mass spectrometer interface comprises a liquid junction adapted to makeup the volume/flow rate of the CZE column eluent stream to be more compatible with the ion spray LC/MS interface flow rates required by mass spectrometer detectors in on-line separation/detection systems for variouscompositions and mixtures including biological fluids and environmental samples. Analytes eluting from the CZE capillary column are diluted with a suitable buffer thereby adjusting the volume and flow rates to prevent flow and pressure discrepanies which would otherwise result in peak broadening.The new liquid junction system for CZE/MS and CZE/MS/MS is useful in separating, detecting and analyzing compositions and mixtures such as amino acids, pesticides, peptides, mucleotides, sulfonated azo dyes and enzymatic digests such as tryptic digest of recombinant bovine somatotropan. Detection can be carried out in both positive and negative ion modes. High separation efficiencies ranging from 50,000 to 1,000,000 theoretical plates and peak asymmetries of 1.2 to 1.8 for tryptic digest are achieved.
摘要翻译：改进的毛细管区带电泳（CZE）/质谱仪界面包括适于补充CZE柱洗脱液流的体积/流速的液体接头，以便与质谱仪检测器所需的离子喷雾LC / MS界面流速更相容用于各种组合物和混合物的在线分离/检测系统，包括生物流体和环境样品。从CZE毛细管柱洗脱的分析物用合适的缓冲液稀释，由此调节体积和流速，以防止否则会导致峰值变宽的流动和压力差异。用于CZE / MS和CZE / MS / MS的新型液体接头系统可用于分离，检测和分析组合物和混合物，如氨基酸，农药，肽，核苷酸，磺化偶氮染料和酶消化物，如重组牛胰蛋白酶消化生长激素检测可以在正离子和负离子两种模式下进行。实现了50,000至1,000,000理论塔板的高分离效率和胰蛋白酶消化物的峰值不对称性为1.2至1.8。

80. 发明授权

US4908512A Apparatus and methods of use in the mass analysis of chemical samples 失效
标题翻译：化学样品质量分析中使用的仪器和方法
公开(公告)号：US4908512A
公开(公告)日：1990-03-13
申请号：US767819
申请日：1985-08-21
申请人： Richard M. Caprioli , John S. Cottrell
发明人： Richard M. Caprioli , John S. Cottrell
IPC分类号： G01N23/225 , H01J49/04 , H01J49/14
CPC分类号： H01J49/0431 , H01J49/0404 , H01J49/14
摘要： A probe for supporting a sample in an ion source of a mass spectrometer comprises a target formed by a copper probe tip for a liquid sample in which the sample passes through a fine bore 18a of the tip on to the end surface of the tip where it is held as a droplet by surface tension. In order to replenish the droplet surface, capillary tubing leads from a syringe to the inlet end of the bore in the probe tip.
摘要翻译：用于在质谱仪的离子源中支撑样品的探针包括由用于液体样品的铜探针尖端形成的靶，其中样品通过尖端的细孔18a到达尖端的端面，其中通过表面张力作为液滴保持。为了补充液滴表面，毛细管从注射器引导到探针尖端的孔的入口端。

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