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    • 1. 发明授权
    • Electrospray and nanospray ionization of discrete samples in droplet format
    • 液滴形式的离散样品的电喷雾和纳米喷雾电离
    • US08431888B2
    • 2013-04-30
    • US13378858
    • 2010-06-18
    • Robert KennedyJian PeiQiang LiMike S. LeeGary A. Valaskovic
    • Robert KennedyJian PeiQiang LiMike S. LeeGary A. Valaskovic
    • H01J49/26
    • H01J49/165B01L3/502784
    • Droplets or plugs within multiphase microfluidic systems have rapidly gained interest as a way to manipulate samples and chemical reactions on the femtoliter to microliter scale. Chemical analysis of the plugs remains a challenge. It has been discovered that nanoliter plugs of sample separated by air or oil can be analyzed by electrospray ionization mass spectrometry when pumped directly into a fused silica nanospray emitter nozzle. Using leu-enkephalin in methanol and 1% acetic acid in water (50:50 v:v) as a model sample, we found carry-over between plugs was
    • 在多相微流体系统中的液滴或塞子已经迅速获得兴趣,作为将飞蓟素的样品和化学反应操纵到微量级的方法。 插头的化学分析仍然是一个挑战。 已经发现,当直接泵送到熔融石英纳米喷雾发射器喷嘴中时,可以通过电喷雾离子化质谱法分析由空气或油分离的样品的纳升塞塞。 在甲醇和1%乙酸水溶液(50:50 v:v)中使用左脑啡肽作为模型样品,发现栓塞之间的滞留量<0.1%,一系列塞子的信号相对标准偏差为3 %。 检测限为1nM。 通过泵送在75毫米内径管中由3mm长气隙分离的13nL样品来实现0.8Hz的样品分析速率。 分析速率受到离子阱质谱仪扫描时间的限制。 该系统为分段流量系统中样品的化学分析提供了强大,快速和信息丰富的方法。
    • 3. 发明授权
    • Method and apparatus for feedback controlled electrospray
    • 用于反馈控制电喷雾的方法和装置
    • US06744046B2
    • 2004-06-01
    • US10154767
    • 2002-05-24
    • Gary A. ValaskovicMike S. Lee
    • Gary A. ValaskovicMike S. Lee
    • H01J4900
    • H01J49/165
    • A feedback control system for an electrospray nozzle and counter-electrode, comprising a source of light which intersects, one or snore of the liquid cone, jet and plume of the fluid exiting the nozzle, one or more photo detectors to detect light patterns and generate photo-electronic signals in response thereto, an electronic detection and amplification system to convert the photo-electronic signals to electronic signals, a computer or micro-processor to interpret said electronic signals and a second computer or microprocessor to communicate with the first computer and generate a signal to a controller which adjusts the electric field surrounding the nozzle either by changing the distance between the nozzle and counter-electrode or changing the voltage of the nozzle or counter-electrode.
    • 一种用于电喷雾喷嘴和对电极的反馈控制系统,包括与离开喷嘴的流体的液体锥体,喷射和羽流中的一个或多个相交的光源,一个或多个光电检测器,用于检测光图案并产生 响应于此的光电子信号,将光电子信号转换为电子信号的电子检测和放大系统,计算机或微处理器来解释所述电子信号,以及第二计算机或微处理器与第一计算机通信并产生 通过改变喷嘴和对置电极之间的距离或改变喷嘴或对电极的电压来调节喷嘴周围电场的信号。
    • 8. 发明授权
    • Method and apparatus for multiple electrospray sample introduction
    • 多种电喷雾样品介绍的方法和装置
    • US06690006B2
    • 2004-02-10
    • US10155646
    • 2002-05-23
    • Gary A. Valaskovic
    • Gary A. Valaskovic
    • B01D5944
    • G01N30/7266G01N30/466G01N2030/628H01J49/04H01J49/165
    • A method for the coupling of a plurality of sample streams eluting from a plurality of High Pressure Liquid Chromatography columns into a single inlet mass spectrometer, wherein samples from individual chromatography columns are suppled to individual electrospray nozzles in an array of a plurality of electrospray nozzles positioned in front of said single inlet, each nozzle being switchable to an on or off state, and each nozzle being supplied by a sample supply tube or channel and having, in addition to said sample supply tube or channel, a separate fluid removal tube or channel, and wherein each nozzle, when in the off state, is held at a voltage that is between the voltage of the mass spectrometer inlet and the electrospray threshold value for that nozzle.
    • 将从多个高压液相色谱柱洗脱的多个样品流耦合到单个入口质谱仪中的方法,其中来自单个色谱柱的样品被提供给位于多个电喷雾喷嘴的阵列中的各个电喷雾喷嘴 在所述单个入口的前面,每个喷嘴可切换到打开或关闭状态,并且每个喷嘴由样品供应管或通道提供,并且除了所述样品供应管或通道之外,还具有单独的流体去除管或通道 并且其中当处于关闭状态时,每个喷嘴保持在质谱仪入口的电压和该喷嘴的电喷雾阈值之间的电压。
    • 10. 发明授权
    • Electrospray ionization source and method of using the same
    • 电喷雾电离源及其使用方法
    • US5788166A
    • 1998-08-04
    • US703644
    • 1996-08-27
    • Gary A. ValaskovicFred W. McLafferty
    • Gary A. ValaskovicFred W. McLafferty
    • B05B5/025G01N27/447H01J49/04B05B5/057
    • H01J49/167B05B5/0255G01N27/44717
    • An ultra-low flow rate electrospray ionization (ESI) source provides flow rates in the range of 1.0 nL/min or less. The source is comprised of a needle which is fabricated by laser-heated pulling of fused-silica tubing, followed by chemical etching and surface metallization. The pulling results in formation of a slowly tapering capillary within the needle which tapers to a tip having a very small inner diameter. The etching process sharpens the outer wall of the needle to a very sharp tip, and the combination of these parameters results in the ultra-low flow rate capability. After a metal electrical contact is formed on the exterior wall of the needle, an electrically insulating overcoating is preferably deposited thereon which locks the contact in place, thereby greatly increasing needle life, and also restricting the electrical contact point to the very tip of the needle. Although the use of the ultra-low flow rate ESI sources increases sensitivity to sampling errors, a mechanism is also provided to minimize one primary source of such errors, evaporation induced hydrodynamic flow, in capillary electrophoresis (CE). An injection system is provided which enables a retractable droplet of buffer solvent to be positioned in contact with the tip end of the ESI needle during sample loading. This prevents evaporation from the tip end, thereby eliminating hydrodynamic flow into the distal end of the capillary column used in the CE process.
    • 超低流速电喷雾电离(ESI)源提供1.0nL / min以下范围内的流速。 该源包括通过激光加热熔化石英管制造的针,然后化学蚀刻和表面金属化制成的针。 牵引导致针内的缓慢变细的毛细管的形成,其逐渐变细到具有非常小的内径的尖端。 蚀刻工艺将针的外壁锐化为非常尖的尖端,并且这些参数的组合导致超低流量能力。 在针的外壁上形成金属电接触之后,优选在其上沉积电绝缘的外涂层,其将接触锁定就位,从而大大增加针的使用寿命,并且还限制电接触点到针的最前端 。 尽管使用超低流速的ESI源增加了对采样误差的敏感性,但也提供了一种机制来最小化毛细管电泳(CE)中这种错误,蒸发诱导的流体动力学流量的一个主要来源。 提供了一种注射系统,其在样品加载期间使缓冲溶剂的可收缩液滴定位成与ESI针的末端接触。 这防止了从尖端的蒸发,从而消除了进入CE过程中使用的毛细管柱的远端的流体动力学流动。