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WO2016116012A1 - 高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法 - Google Patents

高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法 Download PDF

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WO2016116012A1
WO2016116012A1 PCT/CN2016/071030 CN2016071030W WO2016116012A1 WO 2016116012 A1 WO2016116012 A1 WO 2016116012A1 CN 2016071030 W CN2016071030 W CN 2016071030W WO 2016116012 A1 WO2016116012 A1 WO 2016116012A1
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mass
free fatty
fatty acid
correction
sample target
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钟鸿英
唐雪妹
黄璐璐
张文洋
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Central China Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0009—Calibration of the apparatus
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J27/00—Ion beam tubes
    • H01J27/02—Ion sources; Ion guns
    • H01J27/028—Negative ion sources
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0027—Methods for using particle spectrometers

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  • the invention belongs to the field of mass spectrometry, and particularly relates to a mass calibration kit and a calibration method for a low-mass region of a negative ion mode of a high-resolution mass spectrometer.
  • MALDI refers to matrix-assisted-laser analytical dissociation mass spectrometry, which is widely used for accurate mass determination of various sample molecules.
  • sample molecules usually need to be mixed with an organic small molecule.
  • a functional group capable of absorbing laser energy and transferring energy to the sample molecules, gasifying, ionizing the sample molecules, and finally being detected by the detector.
  • the substrate used is generally a small molecule organic acid.
  • the main disadvantages of this method include: (1) usually producing a series of background peaks in the low mass region; (2) inconsistent crystal particle sizes; and (3) suppressing low quality sample signals.
  • these matrices cause significant contamination of the ion source, not only destroying the quantitative relationship between the absolute signal intensity of the mass spectrometer and the amount of sample, but also affecting the resolution.
  • MALDI mass spectrometers cannot use conventional matrices for low-quality molecular analysis. Especially in negative ion mode, there is currently no commercially available calibration kit, making such low-quality molecules impossible to analyze with MALDI.
  • the present invention is directed to the deficiencies of the prior art, and aims to provide a mass correction kit and a correction method for a low-mass region of a negative ion mode of a high-resolution mass spectrometer.
  • a high-resolution mass spectrometer in a negative ion mode low mass region mass calibration kit comprising a semiconductor nanomaterial suspension, a free fatty acid standard solution, and a MALDI sample target cleaning solution.
  • the semiconductor nanomaterial is ZnO, (Bi 2 O 3 ) 0.07 (CoO) 0.03 (ZnO) 0.9 , BN, AlN, TiO 2 , or Ga 2 O 3 .
  • the solvent of the semiconductor nanomaterial suspension is isopropyl alcohol.
  • the free fatty acid standard solution contains free fatty acid C6:0, free fatty acid C8:0, free fatty acid C10:0, free fatty acid C12:0, free fatty acid C14:0, free fatty acid C16:0, free Fatty acid C18:0, free fatty acid C20:0 and free fatty acid C22:0 a total of 9 free fatty acids, the 9 free fatty acids having the same amount of substances.
  • the solvent of the free fatty acid standard solution is n-hexane.
  • the components of the MALDI sample target cleaning solution are: acetone having a volume concentration of 50% and n-hexane having a volume concentration of 50%.
  • a quality correction method for a low-mass region of a negative ion mode of a high-resolution mass spectrometer includes the following steps:
  • the MALDI sample target cleaning solution is used to clean the MALDI mass spectrometer sample target, and the sample target voltage, the hexadecimal voltage, the ion extraction voltage and the slit voltage in the ion source of the mass spectrometer are adjusted, so that the sample target and the slit voltage difference is 20 volts. ;
  • the mass spectrometric detection process of the sample is: taking 1 microliter of the sample solution onto the surface of the semiconductor nanomaterial on the sample target, naturally drying, and placing the sample target into the mass spectrometer for mass spectrometric detection of the sample.
  • the quality correction is a real-time correction or an offline correction.
  • the selection of the semiconductor nanomaterial of the present invention is based on the principle that the energy gap of the semiconductor nanomaterial is smaller than the laser photon energy of the MALDI mass spectrometer, and the electron mobility of the semiconductor material is sufficiently large to have sufficient tunneling probability under the applied electric field.
  • the invention utilizes the laser-induced tunneling electron trapping effect of the semiconductor nano material, first accelerates the tunneling electron under an applied electric field, and then utilizes the trapping of the tunneling electron by the electron-deficient atom in the adsorbed free fatty acid, so that the neutral fatty acid carries negative The charge has an unpaired electron. These molecular ions with unpaired electrons have very high reactivity, which further triggers the cleavage of the ⁇ -position chemical bond.
  • control electron kinetic energy is lower than 20 eV, making the de Broglie wavelength smaller than the bond of the general chemical bond. Long, under these conditions, tunneling electrons are only captured without redistributing the molecular vibrational energy, thus avoiding mass spectral peaks generated by non-specific chemical bond cleavage.
  • a series of low-mass mass spectra were obtained in the negative ion mode of MALDI mass spectrometer. The mass of these mass spectral peaks was 28D, and the exact mass of all fatty acids was known. It can therefore be used for quality correction.
  • the semiconductor nanomaterial itself is not vaporized and ionized, so it does not cause background interference and does not pollute the ion source.
  • the present invention utilizes laser induced tunneling electrons of semiconductor nanomaterials.
  • the trapping principle is to ionize different small molecules of free fatty acids. Because the semiconductor nanomaterials produce background interference ions, and after the fatty acid ionization, under the condition of controlling the applied electric field, only a molecular ion with known accurate mass is produced, which greatly improves the
  • the low mass correction capability of the MALDI negative ion mode overcomes the limitations of conventional MALDI matrices.
  • the calibration kit of the invention is green, safe, practical, simple to prepare, easy to store, can effectively perform the correction of the low-mass region of the negative ion mode of the MALDI mass spectrometer, and can accurately measure the quality of the small molecule compound after the mass calibration.
  • the relative error is less than 6 ppm.
  • the operation method of the calibration method of the invention is simple and easy to control, and the obtained mass spectrum signal has no background interference, uniform mass distribution, high accuracy, high resolution and stable property.
  • Figure 1 shows the mass spectra of nine free fatty acids C6:0, C8:0, C10:0, C12:0, C14:0, C16:0, C18:0, C20:0 and C22:0. Peak map.
  • Example 2 is a mass spectrum of a sample in Example 1.
  • Figure 3 is a mass spectrum of the sample in Example 2.
  • the mass correction method of the low-mass region of the negative ion mode of the high-resolution mass spectrometer including the following steps:
  • the MALDI sample target cleaning solution is used to clean the MALDI mass spectrometer sample target, and the sample target voltage, the hexadecimal voltage, the ion extraction voltage and the slit voltage in the ion source of the mass spectrometer are adjusted, so that the sample target and the slit voltage difference is 20 volts. ;
  • the components of the above MALDI sample target cleaning solution are: acetone having a volume concentration of 50% and n-hexane having a volume concentration of 50%;
  • the above quality correction is real time quality correction or offline quality correction.
  • the mass spectrometry signal has no background interference, uniform mass distribution, high accuracy, high resolution, stable nature, and can accurately determine the mass of small molecule compounds (such as estrogen diethylstilbestrol) after quality correction.
  • the relative error between the actual detected value and the theoretical value is less than 6 ppm.
  • the mass spectrometry signal has no background interference, uniform mass distribution, high accuracy, high resolution, stable nature, and accurate mass determination of small molecule compounds (such as gibberellin) after mass calibration.
  • the relative error between the actual detected value and the theoretical value is less than 6 ppm.

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Abstract

一种高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法，所述质量校正试剂盒包括半导体纳米材料悬浮液、游离脂肪酸标准溶液和MALDI样品靶清洗液。所述校正方法包括：调节质谱仪样品靶和狭缝电压差为20伏特；取半导体纳米材料悬浮液滴于样品靶表面，待溶剂完全挥发干燥；取游离脂肪酸标准溶液滴于所述半导体纳米材料的表面，待溶剂完全挥发干燥，将样品靶放入质谱仪进行质量校正，仪器校正后所得校正系数可用于校正样品质谱检测结果。所述校正试剂盒能有效进行MALDI质谱仪负离子模式低质量区的校正，质谱信号没有背景干扰，能够进行小分子化合物质量的准确测定，相对误差小于6ppm。

Description

高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法 技术领域
本发明属于质谱检测领域，具体涉及一种高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法。
背景技术
MALDI指基质辅助-激光解析离解质谱，这种质谱仪广泛用于各种样品分子的准确质量测定，在这种技术中，样品分子通常需要与一种有机小分子混合，这种有机小分子含有能够吸收激光能量的官能团并将能量传递给样品分子，使样品分子气化、离子化，最终被检测器所检测。
现有的MALDI质谱技术中，所采用的基质一般是小分子有机酸。这种方法的主要缺点包括：(1)通常在低质量区产生一系列背景峰；(2)晶体颗粒大小不一致；(3)抑制低质量样品信号。此外，这些基质对离子源产生很大的污染，不仅破坏质谱绝对信号强度与样品量之间的定量关系，而且还影响分辨率。由于以上原因，MALDI质谱仪不能采用常规基质进行低质量分子的分析，尤其是在负离子模式下，目前没有商品化的校正试剂盒，使得这类低质量分子无法用MALDI进行分析。
发明内容
本发明针对现有技术的不足，目的在于提供一种高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法。
一种高分辨质谱仪负离子模式低质量区的质量校正试剂盒，包括半导体纳米材料悬浮液、游离脂肪酸标准溶液和MALDI样品靶清洗液。
按上述方案，所述半导体纳米材料为ZnO、(Bi2O3)0.07(CoO)0.03(ZnO)0.9、BN、AlN、TiO2、或Ga2O3。
按上述方案，所述半导体纳米材料悬浮液的溶剂为异丙醇。
按上述方案，所述游离脂肪酸标准溶液中包含有游离脂肪酸C6：0，游离脂肪酸C8：0，游离脂肪酸C10：0，游离脂肪酸C12：0，游离脂肪酸C14：0，游离脂肪酸C16：0，游离脂肪酸C18：0，游离脂肪酸C20：0和游离脂肪酸C22：0共9种游离脂肪酸，所述9种游离脂肪酸具有相同的物质的量。
按上述方案，所述游离脂肪酸标准溶液的溶剂为正己烷。
按上述方案，所述MALDI样品靶清洗液的组分为：体积浓度为50％的丙酮和体积浓度为50％的正己烷。
一种高分辨质谱仪负离子模式低质量区的质量校正方法，包括如下步骤：
(1)使用MALDI样品靶清洗液清洗MALDI质谱仪样品靶，调节质谱仪离子源中样品靶电压、六级杆电压、离子提取电压和狭缝电压，使样品靶和狭缝电压差为20伏特；
(2)滴取1微升半导体纳米材料悬浮液于样品靶表面，将样品靶置于室温中，待半导体纳米材料悬浮液中的溶剂完全挥发干燥，得到表面覆盖有半导体纳米材料的样品靶；
(3)取1微升游离脂肪酸标准溶液滴于步骤(2)所述的样品靶上的半导体纳米材料的表面，待游离脂肪酸标准溶液中的溶剂完全挥发干燥后，将样品靶放入质谱仪，在质谱仪的校正模式下进行质量校正，仪器校正后所得校正系数将自动地用于校正样品质谱检测结果；
所述样品质谱检测过程为：取1微升样品溶液滴于上述样品靶上的半导体纳米材料的表面，自然晾干，将样品靶放入质谱仪进行样品的质谱检测。
按上述方案，所述质量校正为实时校正或离线校正。
本发明对半导体纳米材料的选择是基于以下原则：半导体纳米材料的能隙小于MALDI质谱仪的激光光子能量，且半导体材料的电子迁移速率足够大，在外加电场作用下具有足够的隧穿几率。本发明利用半导体纳米材料的激光诱导隧道电子俘获效应，首先使隧穿电子在外加电场下加速，然后再利用所吸附的游离脂肪酸中缺电子原子对隧穿电子的俘获，使中性脂肪酸携带负电荷并具有一个未配对电子，这些具有未配对电子的分子离子具有非常高的反应活性，进一步引发α位化学键的断裂；控制电子动能低于20eV，使其德布罗意波长小于一般化学键的键长，在这种条件下隧穿电子只会被俘获，而不会引起分子振动能的再分配，因此避免非特异性化学键断裂所产生的质谱峰。本发明中，游离脂肪酸C6：0，游离脂肪酸C8：0，游离脂肪酸C10：0，游离脂肪酸C12：0，游离脂肪酸C14：0，游离脂肪酸C16：0，游离脂肪酸C18：0，游离脂肪酸C20：0和游离脂肪酸C22：0气化、离子化后，在MALDI质谱仪负离子模式下获得一系列低质量质谱峰，这些质谱峰的质量均匀相差28Da，并且所有脂肪酸的准确质量均是已知的，因此可以将其用于质量校正。此外，半导体纳米材料本身并不气化、离子化，因此不产生背景干扰，不污染离子源。
本发明的有益效果如下：
(1)与现有MALDI校正试剂盒相比，目前只有正离子模式高质量的校正试剂盒，没有一个商品化试剂盒可用于负离子模式低质量校正，本发明利用半导体纳米材料的激光诱导隧道电子俘获原理，使不同的小分子游离脂肪酸电离，由于半导体纳米材料部产生背景干扰离子，而脂肪酸电离后在控制外加电场大小的条件下，只产生一个已知准确质量的分子离子，大大提高了对MALDI负离子模式低质量的校正能力，克服了常规MALDI基质的局限性。
(2)本发明所述校正试剂盒绿色环保，安全实用，配制简单，保存容易，能有效进行MALDI质谱仪负离子模式低质量区的校正，经过质量校正后能够进行小分子化合物质量的准确测定，相对误差小于6ppm。
(3)本发明所述校正方法操作过程简单易控，得到的质谱信号没有背景干扰，质量分布均匀，准确度高，分辨率高，性质稳定。
附图说明
图1为九种游离脂肪酸C6：0、C8：0、C10：0、C12：0、C14：0、C16：0、C18：0、C20：0和C22：0产生的质量均匀相差28Da的质谱峰图。
图2为实施例1中的样品质谱图。
图3为实施例2中的样品质谱图。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
以下实施例中，采用高分辨质谱仪负离子模式低质量区的质量校正方法，包括如下步骤：
(1)使用MALDI样品靶清洗液清洗MALDI质谱仪样品靶，调节质谱仪离子源中样品靶电压、六级杆电压、离子提取电压和狭缝电压，使样品靶和狭缝电压差为20伏特；
(2)滴取1微升半导体纳米材料悬浮液于样品靶表面，将样品靶置于室温中，待半导体纳米材料悬浮液中的溶剂完全挥发干燥，得到表面覆盖有半导体纳米材料的样品靶；
(3)取1微升游离脂肪酸标准溶液滴于步骤(2)所述的样品靶上的半导体纳米材料的表面，待游离脂肪酸标准溶液中的溶剂完全挥发干燥后，将样品靶放入质谱仪，在质谱仪的校正模式下进行质量校正，得到九种游离脂肪酸C6：0、C8：0、C10：0、C12：0、C14：0、C16：0、C18：0、C20：0和C22：0产生的质量均匀相差28Da的质谱峰图，见图1；
上述半导体纳米材料悬浮液的制备：称取10mg半导体纳米颗粒(Bi2O3)0.07(CoO)0.03(ZnO)0.9、溶解于1mL异丙醇中，超声震荡1分钟，使纳米颗粒均匀分散；
上述游离脂肪酸标准溶液的制备：取相同的物质的量的游离脂肪酸C6：0，游离脂肪酸C8：0，游离脂肪酸C10：0，游离脂肪酸C12：0，游离脂肪酸C14：0，游离脂肪酸C16：0，游离脂肪酸C18：0，游离脂肪酸C20：0和游离脂肪酸C22：0，以正己烷为溶剂配制得到溶液浓度为5mg/mL的游离脂肪酸标准溶液；
上述MALDI样品靶清洗液的组分为：体积浓度为50％的丙酮和体积浓度为50％的正己烷；
上述质量校正为实时质量校正或离线质量校正。
实施例1
雌性激素己烯雌酚的质谱检测，具体的操作步骤如下：
(1)配制样品溶液：称取100mg己烯雌酚，溶解于1mL乙醇中；
(2)移取1微升样品溶液置于上述样品靶上覆盖的半导体纳米材料的表面上，自然晾干；
(3)调节样品靶、六级杆、提取板、狭缝电压，使样品靶和狭缝之间的电压差为20伏特；将样品靶放入质谱仪进行质谱检测，检测结果用C6：0，C8：0，C10：0，C12：0，C14：0，C16：0，C18：0，C20：0和C22：0的质谱峰图进行校正后，得到样品质谱图，见图2。
结合图1和图2的结果说明：质谱信号没有背景干扰，质量分布均匀，准确度高，分辨率高，性质稳定，经过质量校正后能够进行小分子化合物(如雌性激素己烯雌酚)质量的准确测定，实际检测值与理论值的相对误差小于6ppm。
实施例2
植物激素赤霉素的质谱检测，具体的操作步骤如下：
(1)配制样品溶液：称取100mg赤霉素，溶解于1mL乙醇中；
(2)移取1微升样品溶液置于上述样品靶上覆盖的半导体纳米材料的表面上，自然晾干；
(3)调节样品靶、六级杆、提取板、狭缝电压，使样品靶和狭缝之间的电压差为20伏特；将样品靶放入质谱仪进行质谱检测，检测结果用C6：0，C8：0，C10：0，C12：0，C14：0，C16：0，C18：0，C20：0和C22：0的质谱峰图进行校正后，得到样品质谱图，见图3。
结合图1和图3的结果说明：质谱信号没有背景干扰，质量分布均匀，准确度高，分辨率高，性质稳定，经过质量校正后能够进行小分子化合物(如赤霉素)质量的准确测定，实际检测值与理论值的相对误差小于6ppm。
显然，上述实施例仅仅是为清楚地说明所作的实例，而并非对实施方式的限制。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。

Claims (7)

  1. 一种高分辨质谱仪负离子模式低质量区的质量校正试剂盒，其特征在于，包括半导体纳米材料悬浮液、游离脂肪酸标准溶液和MALDI样品靶清洗液；所述半导体纳米材料为ZnO、(Bi2O3)0.07(CoO)0.03(ZnO)0.9、BN、AlN、TiO2、或Ga2O3。
  2. 根据权利要求1所述的质量校正试剂盒，其特征在于所述半导体纳米材料悬浮液的溶剂为异丙醇。
  3. 根据权利要求1所述的质量校正试剂盒，其特征在于，所述游离脂肪酸标准溶液中包含有游离脂肪酸C6：0，游离脂肪酸C8：0，游离脂肪酸C10：0，游离脂肪酸C12：0，游离脂肪酸C14：0，游离脂肪酸C16：0，游离脂肪酸C18：0，游离脂肪酸C20：0和游离脂肪酸C22：0共9种游离脂肪酸，所述9种游离脂肪酸具有相同的物质的量。
  4. 根据权利要求1所述的质量校正试剂盒，其特征在于，所述游离脂肪酸标准溶液的溶剂为正己烷。
  5. 根据权利要求1所述的质量校正试剂盒，其特征在于，所述MALDI样品靶清洗液的组分为：体积浓度为50％的丙酮和体积浓度为50％的正己烷。
  6. 根据权利要求1～6任一高分辨质谱仪负离子模式低质量区的质量校正试剂盒的校正方法，其特征在于，包括如下步骤：
    (1)使用MALDI样品靶清洗液清洗MALDI质谱仪样品靶，调节质谱仪离子源中样品靶电压、六级杆电压、离子提取电压和狭缝电压，使样品靶和狭缝电压差为20伏特；
    (2)滴取1微升半导体纳米材料悬浮液于样品靶表面，将样品靶置于室温中，待半导体纳米材料悬浮液中的溶剂完全挥发干燥，得到表面覆盖有半导体纳米材料的样品靶；
    (3)取1微升游离脂肪酸标准溶液滴于步骤(2)所述的样品靶上的半导体纳米材料的表面，待游离脂肪酸标准溶液中的溶剂完全挥发干燥后，将样品靶放入质谱仪，在质谱仪的校正模式下进行质量校正，仪器校正后所得校正系数可自动地用于校正样品质谱检测结果；
    所述样品质谱检测过程为：取1微升样品溶液滴于上述样品靶上的半导体纳米材料的表面，自然晾干，将样品靶放入质谱仪进行样品的质谱检测。
  7. 根据权利要求7所述的校正方法，其特征在于，所述质量校正为实时校正或离线校正。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114088801A (zh) * 2020-07-03 2022-02-25 中国科学院大连化学物理研究所 一种离子迁移谱仪分析标定用的混合标准液

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104597114B (zh) * 2015-01-21 2016-03-30 华中师范大学 高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法
CN104931572B (zh) * 2015-05-14 2018-08-21 中国疾病预防控制中心传染病预防控制所 微生物鉴定用质谱仪分子量校正标准品及其制备方法与应用
CN105869984B (zh) * 2016-04-15 2017-06-20 浙江大学 高分辨四极杆飞行时间质谱仪质量轴用校正液及其使用方法
WO2018059346A1 (zh) * 2016-09-28 2018-04-05 华中师范大学 一种界面光电子转移及材料光催化活性的测定方法及四维显微成像分析仪
CN106323921B (zh) * 2016-10-11 2018-07-17 华中师范大学 一种界面光电子转移及材料光催化活性的测定方法及四维显微成像分析仪
CN108051504A (zh) * 2017-10-31 2018-05-18 北京毅新博创生物科技有限公司 校正质谱检测糖基正确率的方法及产品
CN108107103B (zh) * 2017-12-14 2020-10-16 华中师范大学 谷氨酸受体的质谱探针及其在脑组织中的空间分布规律检测方法
CN112540139B (zh) * 2020-12-16 2022-07-15 杭州汇健科技有限公司 一种代谢谱检测用的分子量校准品试剂盒及其制备方法、使用方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007017701A1 (en) * 2005-08-09 2007-02-15 University Of Sunderland Fingerprint analysis using mass spectrometry
CN100504378C (zh) * 2007-01-25 2009-06-24 上海交通大学 基质辅助激光解吸质谱样品功能靶盘制备方法
CN102645481A (zh) * 2012-04-28 2012-08-22 中国科学院化学研究所 发光纳米碳点作为maldi基质分析小分子的应用
CN103227096A (zh) * 2012-01-30 2013-07-31 华中师范大学 一种激光诱导电子捕获质谱解析离解脂质分子方法
CN103245717A (zh) * 2012-02-10 2013-08-14 华中师范大学 高压成型基质薄膜辅助-激光解析离解质谱定量分析方法
CN104597114A (zh) * 2015-01-21 2015-05-06 华中师范大学 高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005030981A2 (en) * 2003-09-25 2005-04-07 Invitrogen Corporation Homogeneous populations of molecules
CN101531993B (zh) * 2008-03-12 2013-05-29 中国医学科学院肿瘤研究所 稳定荧光标记细胞核的方法和试剂盒
CN101907601A (zh) * 2009-06-08 2010-12-08 许洋 重度妊娠期高血压生化标记物的质谱试剂盒及制备方法
US8313789B2 (en) * 2009-06-10 2012-11-20 The United States Of America, As Represented By The Secretary Of Agriculture Methods of promoting the growth of beneficial bacteria in the gut
EP2691973B1 (en) * 2011-03-31 2019-05-08 DH Technologies Development Pte. Ltd. Composition, method, and kit for calibrating a mass spectrometer
CA2857374A1 (en) * 2011-09-02 2013-03-07 The Trustees Of Columbia University In The City Of New York Camkii, ip3r, calcineurin, p38 and mk2/3 inhibitors to treat metabolic disturbances of obesity
US20130123131A1 (en) * 2011-11-09 2013-05-16 Nodality, Inc. Process for Ensuring Consistency and Reproducibility of a Diagnostic or Research Method
CN104198572A (zh) * 2014-08-26 2014-12-10 宜昌捷诺威医药科技有限公司 用于检测脂类组合物c18：2ce和sm22：0含量的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007017701A1 (en) * 2005-08-09 2007-02-15 University Of Sunderland Fingerprint analysis using mass spectrometry
CN100504378C (zh) * 2007-01-25 2009-06-24 上海交通大学 基质辅助激光解吸质谱样品功能靶盘制备方法
CN103227096A (zh) * 2012-01-30 2013-07-31 华中师范大学 一种激光诱导电子捕获质谱解析离解脂质分子方法
CN103245717A (zh) * 2012-02-10 2013-08-14 华中师范大学 高压成型基质薄膜辅助-激光解析离解质谱定量分析方法
CN102645481A (zh) * 2012-04-28 2012-08-22 中国科学院化学研究所 发光纳米碳点作为maldi基质分析小分子的应用
CN104597114A (zh) * 2015-01-21 2015-05-06 华中师范大学 高分辨质谱仪负离子模式低质量区的质量校正试剂盒及校正方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG, SEN ET AL.: "Matrixes for Small Molecule Analysis Based on MALDI-MS", PROGRESS IN CHEMISTRY, vol. 26, no. 1, 31 January 2014 (2014-01-31), pages 158 - 166 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114088801A (zh) * 2020-07-03 2022-02-25 中国科学院大连化学物理研究所 一种离子迁移谱仪分析标定用的混合标准液

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