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公开(公告)号：US20110272573A1
公开(公告)日：2011-11-10
申请号：US13103672
申请日：2011-05-09
申请人： Markus Kostrzewa , Jochen Franzen
发明人： Markus Kostrzewa , Jochen Franzen
IPC分类号： H01J49/40
CPC分类号： H01J49/0027 , H01J49/164 , H01J49/40
摘要： The invention relates to acquisition techniques for time-of-flight mass spectra with ionization of the analyte substances by matrix assisted laser desorption. Generally speaking, these acquisition techniques involve adding together a large number of individual time-of-flight spectra, each with restricted dynamic measuring range, to form a sum spectrum. The invention provides a method that improves, in particular, the reproducibility, the concentration accuracy and therefore the ability to quantify the mass spectra. Particular embodiments also increase the dynamic range of measurement. For this purpose, multiple series of mass spectra are acquired, whereby the energy density in the laser spot is increased in discrete steps. As a result, many ion signals saturate the detector and can therefore no longer be evaluated. However, it is possible to employ a technique in which the ion beam is increasingly defocused, or, secondly, to replace parts of the spectrum that are subject to saturation by intensity extrapolations from mass spectra acquired with lower energy density. In the first case, hundreds or thousands of individual mass spectra must be added together in order to increase the dynamic measuring range. In the second case, the finally acquired mass spectrum, with its replacements, forms a mass spectrum with a high dynamic measuring range, improved reproducibility and better concentration accuracy. The gradient of the increasing intensities of the ion signals, as a function of the energy density, supplies additional information about the proton affinity of the analyte ions. The concentration accuracy is enhanced because the increase in the number of proton donors in the ionization plasma leads to an increase in the ionization of those analyte substances that have a lower proton affinity.
摘要翻译： 本发明涉及通过基质辅助激光解吸附物质分析物质离子化的飞行时间质谱采集技术。 一般来说，这些采集技术包括将大量具有限制动态测量范围的单个飞行时间频谱相加在一起以形成和频谱。 本发明提供了一种特别改进重现性，浓度精度以及因此量化质谱的能力的方法。 具体实施例还增加了测量的动态范围。 为此，获得了多个质谱系列，从而在离散步骤中激光斑点的能量密度增加。 因此，许多离子信号使检测器饱和，因此不再能被评估。 然而，可以采用这样一种技术，其中离子束越来越散焦，或者其次，通过由具有较低能量密度获得的质谱的强度外推替代经受饱和的部分光谱。 在第一种情况下，为了增加动态测量范围，必须将数百或数千个单个质谱加在一起。 在第二种情况下，最终获得的质谱与其替代物形成具有高动态测量范围，改进的再现性和更好的浓度精度的质谱。 作为能量密度的函数的离子信号的增加强度的梯度提供关于分析物离子的质子亲和力的附加信息。 由于离子化等离子体中的质子供体的数量的增加导致具有较低质子亲和力的分析物质的电离增加，所以浓度精度得到提高。
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公开(公告)号：US20090305327A1
公开(公告)日：2009-12-10
申请号：US12224388
申请日：2007-02-15
CPC分类号： G01N33/6848 , C12Q1/37 , C12Q1/56 , G01N2333/75 , G01N2333/976
摘要： The invention relates to the determination of the nature and strength of enzymatic activity in blood using mass spectrometric measurement of a profile of the reaction products. The determination of the enzymatic activity can be used for medical diagnostics, for example, and also to check the effectiveness of medication. The invention provides a method whereby adding probe substances usually not present in blood offers standardized substrates for measuring the enzymatic activity. The probe substances may be added to whole blood, plasma, or serum. The mass spectrometric measurement of the reaction products, after their reversible immobilization on actively binding surfaces of solids, for example, can deliver biomarker patterns of the reaction products which may be indicators for metabolic anomalies or diseases, since these are often accompanied by the formation or activation of characteristic enzymes.
摘要翻译： 本发明涉及使用反应产物分布的质谱测量来测定血液中酶活性的性质和强度。 酶活性的测定可以用于医学诊断，例如，以及检查药物的有效性。 本发明提供了通过添加通常不存在于血液中的探针物质来提供用于测量酶活性的标准化底物的方法。 探针物质可以添加到全血，血浆或血清中。 反应产物在其可固定地固定在固体的活性结合表面上之后的质谱测量可以提供反应产物的生物标志物模式，其可以是代谢异常或疾病的指标，因为它们通常伴随着形成或 特征酶的活化。
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公开(公告)号：US08142996B2
公开(公告)日：2012-03-27
申请号：US12224388
申请日：2007-02-15
CPC分类号： G01N33/6848 , C12Q1/37 , C12Q1/56 , G01N2333/75 , G01N2333/976
摘要： The invention relates to the determination of the nature and strength of enzymatic activity in blood using mass spectrometric measurement of a profile of the reaction products. The determination of the enzymatic activity can be used for medical diagnostics, for example, and also to check the effectiveness of medication. The invention provides a method whereby adding probe substances usually not present in blood offers standardized substrates for measuring the enzymatic activity. The probe substances may be added to whole blood, plasma, or serum. The mass spectrometric measurement of the reaction products, after their reversible immobilization on actively binding surfaces of solids, for example, can deliver biomarker patterns of the reaction products which may be indicators for metabolic anomalies or diseases, since these are often accompanied by the formation or activation of characteristic enzymes.
摘要翻译： 本发明涉及使用反应产物分布的质谱测量来测定血液中酶活性的性质和强度。 酶活性的测定可以用于医学诊断，例如，以及检查药物的有效性。 本发明提供了通过添加通常不存在于血液中的探针物质来提供用于测量酶活性的标准化底物的方法。 探针物质可以添加到全血，血浆或血清中。 反应产物在其可固定地固定在固体的活性结合表面上之后的质谱测量可以提供反应产物的生物标志物模式，其可以是代谢异常或疾病的指标，因为它们通常伴随着形成或 特征酶的活化。
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公开(公告)号：US10006076B2
公开(公告)日：2018-06-26
申请号：US14113354
申请日：2011-07-29
CPC分类号： C12Q1/04 , G01N21/77 , G01N33/6851 , G01N2021/7786 , G01N2800/26
摘要： The invention relates to methods and instruments for the rapid detection and rapid mass spectrometric identification of microbial infective agents in blood or other body fluids. The invention recognizes that blood is not a good environment for the cultivation of microbes and provides a method which (a) largely destroys or dissolves the human particles in body fluids, such as erythrocytes and leukocytes in blood, without impairing the ability of the microbes to reproduce, (b) separates the microbial pathogens from the fluid, (c) cultivates them in a nutrient broth which contains none of the antimicrobial components of the body fluids, (d) separates them from the nutrient broth, and (e) identifies the microbes by a mass spectrum of the microbial proteins. The dissolution of the human particles also releases the microbes nesting in macrophages. The cultivation in an optically clear nutrient broth with optimum composition not only accelerates the propagation of the microbes compared to all other cultivation methods, but also makes it possible to continuously measure their quantitative growth starting from a low microbe density. This firstly allows the mass spectrometric identification to be carried out at the earliest possible time, secondly provides a positive detection of microbes far ahead of their identification, which can be lifesaving for the patient; and thirdly makes it possible to start the determination of resistances early.
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公开(公告)号：US20110275113A1
公开(公告)日：2011-11-10
申请号：US13102212
申请日：2011-05-06
申请人： Markus Kostrzewa , Jochen Franzen
发明人： Markus Kostrzewa , Jochen Franzen
IPC分类号： C12Q1/04
CPC分类号： G01N33/6851 , G01N33/569
摘要： A method of detecting specified target microbes in different types of sample uses only one to two cultivation steps for the enrichment of the target microbes from the sample, preferably in selective culture media, combined with a mass spectrometric detection method that identifies the target microbes in mixtures with other microbes even if the target microbes account for only a small proportion of the mixture. The sample may be a food sample, a sample from bodies of water used for bathing, a soil sample, a swabbed sample, a stool sample, an impactor sample with collected aerosol particles, amongst many others. The detection method is several days faster than standard methods and less expensive.
摘要翻译： 在不同类型样品中检测特定目标微生物的方法仅使用一至两个培养步骤，用于富集样品中的目标微生物，优选在选择性培养基中，与质谱检测方法结合，鉴定混合物中的目标微生物 与其他微生物一样，即使目标微生物仅占混合物的一小部分。 样品可以是食品样品，用于洗浴的水体样品，土壤样品，拭子样品，粪便样品，具有收集的气溶胶颗粒的冲击器样品等等。 检测方法比标准方法快几天，成本较低。
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公开(公告)号：US08384019B2
公开(公告)日：2013-02-26
申请号：US12767273
申请日：2010-04-26
申请人： Claus Köster , Jochen Franzen
发明人： Claus Köster , Jochen Franzen
IPC分类号： B01D59/44
CPC分类号： H01J49/02 , H01J49/26 , H01J49/425
摘要： In a Kingdon ion trap in which harmonic ion oscillation in a potential well in a longitudinal direction is completely decoupled from ion oscillation in a direction transverse to the longitudinal direction, ions enter the trap via an entrance tube extending through, but electrically insulated from, one of the Kingdon trap housing electrodes and located outside the minimum of the potential well in the longitudinal direction. The geometry of the Kingdon trap is arranged so that the oscillating ions introduced through the entrance tube cannot return to the entrance tube until they have performed several longitudinal oscillations during which time heavy ions can be introduced into the trap.
摘要翻译： 在Kingdon离子阱中，纵向方向的势阱中的谐波离子振荡在垂直于纵向的方向上与离子振荡完全解耦，离子通过入口管进入陷阱，该入口管延伸通过一个 的Kingdon陷阱壳体电极并且位于纵向方向上的势阱的最小值之外。 Kingdon陷阱的几何形状被布置成使得通过入口管引入的振荡离子不能返回到入口管，直到它们执行几个纵向振荡，在该时间期间可以将重离子引入陷阱。
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公开(公告)号：US08319180B2
公开(公告)日：2012-11-27
申请号：US13208803
申请日：2011-08-12
申请人： Evgenij Nikolaev , Jochen Franzen
发明人： Evgenij Nikolaev , Jochen Franzen
CPC分类号： H01J49/4245
摘要： The invention relates to measuring devices of an electrostatic Fourier transform mass spectrometer and measurement methods for the acquisition of mass spectra with high mass resolution. The measuring device includes electrostatic measuring cells according to the Kingdon principle, in which ions can, when appropriate voltages are applied, orbit on circular trajectories around the cylinder axis between two concentric cylindrical surfaces, which are composed of specially shaped sheath electrodes, insulated from each other by parabolic gaps, and can harmonically oscillate in the axial direction, independently of their orbiting motion. In the longitudinal direction, the two cylindrical surfaces of the measuring cell are divided by the parabolic separating gaps into different types of double-angled and tetragonal sheath electrode segments. Appropriate voltages at the sheath electrode segments generate a potential distribution between the two concentric cylindrical surfaces which forms a parabolic potential well in the axial direction for orbiting ions. The ion clouds oscillating harmonically in the axial direction in this potential well induce image currents in suitable electrodes, from which the oscillation frequencies can be determined by Fourier analyses.
摘要翻译： 本发明涉及静电傅立叶变换质谱仪的测量装置和用于以高质量分辨率采集质谱的测量方法。 测量装置包括根据Kingdon原理的静电测量单元，其中当适当的电压施加时，离子可以在围绕圆柱体轴线的圆周轨迹上轨道在两个同心圆柱表面之间，这两个同心圆柱表面由特殊形状的护套电极组成 另一个是抛物线间隙，并且可以在轴向方向上谐振振荡，而不受其轨道运动的影响。 在纵向方向上，测量单元的两个圆柱形表面被抛物线分离间隔分成不同类型的双角和四角形电极段。 护套电极段处的适当电压在两个同心圆柱形表面之间产生电位分布，这两个同心圆柱形表面在轴向方向上很好地形成抛物线势垒，用于轨道离子。 在该势阱中在轴向上谐波振荡的离子云在合适的电极中引起图像电流，通过傅立叶分析可以确定振荡频率。
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公开(公告)号：US20120264162A1
公开(公告)日：2012-10-18
申请号：US13523167
申请日：2012-06-14
IPC分类号： G01N27/62
CPC分类号： G01N33/6851 , C12Q1/18
摘要： Microorganisms, particularly bacteria, are identified and characterized on the basis of a mass spectrometric measurement of their protein profiles with ionization by matrix-assisted laser desorption. In order to measure the microbial resistance to antibiotics, the protein profiles of microorganisms are measured after cultivation for a short time duration in nutrient media containing the antibiotics.
摘要翻译： 基于通过基质辅助激光解吸电离的蛋白质谱的质谱测定，鉴定和表征微生物，特别是细菌。 为了测量微生物对抗生素的抗性，微生物的蛋白质分布在含有抗生素的营养培养基中培养短时间后测量。
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公开(公告)号：US20120228492A1
公开(公告)日：2012-09-13
申请号：US13503202
申请日：2010-11-15
申请人： Jochen Franzen
发明人： Jochen Franzen
IPC分类号： H01J49/26
CPC分类号： H01J49/421 , H01J49/401
摘要： The invention relates to ions guided by gas flows in mass spectrometers, particularly in RF multipole systems, and to RF quadrupole mass filters and their operation with gas flows in tandem mass spectrometers. The invention provides a tandem mass spectrometer in which the RF quadrupole mass filter is operated at vacuum pressures in the medium vacuum pressure regime, utilizing a gas flow to drive the ions are through the mass filter. Vacuum pressures between 0.5 to 10 pascal are maintained in the mass filter. The mass filter may be enclosed by a narrow enclosure to guide the gas flow. The quadrupole mass filter may be followed by an RF multipole system, operated at the same vacuum pressure, serving as fragmentation cell to fragment the selected parent ions. The fragmentation cell may be enclosed by the same enclosure which already encloses the mass filter, so the ions may be driven by the same gas flow at the same vacuum pressure, greatly simplifying the required vacuum pumping system in tandem mass spectrometers. There are many other applications utilizing gas flows including supersonic gas jets in mass spectrometry.
摘要翻译： 本发明涉及在质谱仪，特别是RF多极系统中的气流引导的离子，以及RF串联质谱仪和其在串联质谱仪中的气流的操作。 本发明提供一种串联质谱仪，其中RF四极杆质量过滤器在中等真空压力状态下在真空压力下操作，利用气流驱动离子通过质量过滤器。 在质量过滤器中保持0.5至10帕斯卡之间的真空压力。 质量过滤器可以被狭窄的外壳包围以引导气流。 四极质量过滤器之后可以是在相同的真空压力下操作的RF多极体系统，用作碎裂细胞以分离所选择的母体离子。 分裂单元可以被已经包围质量过滤器的相同外壳封闭，因此离子可以在相同的真空压力下由相同的气流驱动，大大简化了串联质谱仪中所需的真空泵送系统。 在质谱法中还有许多其他的应用，包括使用超声波气体射流的气流。
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公开(公告)号：US20120043461A1
公开(公告)日：2012-02-23
申请号：US13208803
申请日：2011-08-12
申请人： Evgenij Nikolaev , Jochen Franzen
发明人： Evgenij Nikolaev , Jochen Franzen
IPC分类号： H01J49/28
CPC分类号： H01J49/4245
摘要： The invention relates to measuring devices of an electrostatic Fourier transform mass spectrometer and measurement methods for the acquisition of mass spectra with high mass resolution. The measuring device includes electrostatic measuring cells according to the Kingdon principle, in which ions can, when appropriate voltages are applied, orbit on circular trajectories around the cylinder axis between two concentric cylindrical surfaces, which are composed of specially shaped sheath electrodes, insulated from each other by parabolic gaps, and can harmonically oscillate in the axial direction, independently of their orbiting motion. In the longitudinal direction, the two cylindrical surfaces of the measuring cell are divided by the parabolic separating gaps into different types of double-angled and tetragonal sheath electrode segments. Appropriate voltages at the sheath electrode segments generate a potential distribution between the two concentric cylindrical surfaces which forms a parabolic potential well in the axial direction for orbiting ions. The ion clouds oscillating harmonically in the axial direction in this potential well induce image currents in suitable electrodes, from which the oscillation frequencies can be determined by Fourier analyses.
摘要翻译： 本发明涉及静电傅立叶变换质谱仪的测量装置和用于以高质量分辨率采集质谱的测量方法。 测量装置包括根据Kingdon原理的静电测量单元，其中当适当的电压施加时，离子可以在围绕圆柱体轴线的圆周轨迹上轨道在两个同心圆柱形表面之间，这两个同心圆柱表面由特殊形状的护套电极组成 另一个是抛物线间隙，并且可以在轴向方向上谐振振荡，而不受其轨道运动的影响。 在纵向方向上，测量单元的两个圆柱形表面被抛物线分离间隔分成不同类型的双角和四角形电极段。 护套电极段处的适当电压在两个同心圆柱形表面之间产生电位分布，这两个同心圆柱形表面在轴向方向上很好地形成抛物线势垒，用于轨道离子。 在该势阱中在轴向上谐波振荡的离子云在合适的电极中引起图像电流，通过傅立叶分析可以确定振荡频率。
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