The applicants' teachings relate to a system and method of mass spectrometry. More specifically, the applicants' teachings relate to curtain gas flow in a mass spectrometer.
The most common solvents used in liquid chromatography (LC) are methanol, acetonitrile, and water. The same solvents are used with Liquid Chromatography/Mass Spectrometry (LC/MS). In typical electrospray ion sources, the solvent is a sprayed or nebulized in the form of small highly charged droplets. These droplets must be evaporated to release the analyte ions in the droplets into the gas phase. Typically, some fraction of the droplets is not evaporated, or some of the droplets are only partially evaporated, leaving a mixture of ions, droplets, and clusters in the ion source. Clusters are essentially microscopic droplets.
Water is particularly difficult to evaporate since it is less volatile than methanol or acetonitrile. Thus, if the LC solvent contains a mixture of water and methanol or acetonitrile, any remaining droplets and clusters will largely consist of water.
As it is known in the art, a gas curtain consists of a flowing curtain of gas, typically nitrogen, that covers the orifice separating the ion source from the first vacuum chamber of the mass spectrometer. The curtain gas flow direction is generally away from the orifice into the ion source, with some of the gas flow being drawn into the vacuum chamber. The counterflow of the gas acts as a curtain or membrane to exclude gases and contaminants as well as particles, droplets, and clusters from entering the vacuum chamber while allowing higher mobility ions to be focused and transmitted into the vacuum system. However, at high liquid flow rates, the gas curtain can be less efficient in excluding the droplets. Turbulent gas flow in the ion source region can cause droplets to penetrate through the curtain gas and be carried by suction into the vacuum chamber. Therefore, a need exists to provide a system and apparatus for applying a curtain gas that is more efficient in excluding particles, droplets, and clusters, while allowing more of the ions to be transmitted into the vacuum chamber.
In accordance with an aspect of the applicants' teachings, there is provided a mass spectrometer system comprising an ion source for generating ions at substantially atmospheric pressure, a sampling member having an orifice therein, the sampling member forming a vacuum chamber with a mass spectrometer, a curtain plate between the ion source and the sampling member, the curtain plate having an aperture therein, the aperture having a cross-section and being spaced from the sampling member to define a flow passage between the curtain plate and the sampling member, and to define an annular gap between the orifice and the aperture, the area of the annular gap being less than the cross-sectional area of the aperture, a power supply for applying a voltage to the curtain plate to direct ions from the ion source to the aperture in the curtain plate, and a curtain gas flow mechanism for directing a curtain gas into the flow passage and the annular gap.
In accordance with another aspect of the applicant's teachings there is provided a mass spectrometer system comprising an ion source for generating ions at substantially atmospheric pressure, at least two curtain plates, each curtain plate of the at least two curtain plates having an aperture, each curtain plate spaced to form a plurality of flow passages therebetween, a sampling member having an orifice therein, the sampling member forming a vacuum chamber with a mass spectrometer, the sampling member being spaced away from the at least two curtain plates forming a flow passage therebetween, a power supply voltage for applying independent voltages to each curtain plate to direct ions through each of the apertures of each curtain plate, and at least one gas flow mechanism for directing curtain gases into each of the plurality of flow passages. In various embodiments, the curtain gases have different composition.
In accordance with another aspect of the applicant's invention there is provided a mass spectrometer system comprising an ion source for generating ions at substantially atmospheric pressure, a first curtain plate having a first aperture, a second curtain plate having a second aperture being spaced away from the first curtain plate defining a first curtain chamber therebetween, a sampling member having an orifice therein, the sampling member forming a vacuum chamber with a mass spectrometer, the sampling member being spaced away from the second curtain plate defining a second curtain chamber therebetween, a first curtain gas flow mechanism for directing a first curtain gas into the first curtain chamber, a power supply for applying a first voltage to the first curtain plate to direct ions from the ion source to the first aperture and for applying a second voltage to the second curtain plate to direct ions from the first aperture to the second aperture, and a second curtain gas flow for directing a second curtain gas into the second curtain chamber. In various embodiments, the first and second curtain gases have different composition.
In accordance with a further aspect of the applicant's invention there is provided an ion sampling interface for receiving ions from an ion source, the ion sampling interface comprising a first curtain plate having a first aperture therein for receiving the ions from the ion source, a second curtain plate having a second aperture therein, the second curtain plate spaced from the first curtain plate to form a curtain chamber therebetween, a sampling member having an orifice therein, the sampling member forming a vacuum chamber with a mass spectrometer; the sampling member, spaced from the second curtain plate to form a curtain flow channel therebetween, the sampling member defining an annular gap between the orifice and the second aperture, the area of the annular gap being less than the cross-sectional area of the aperture, a first power supply for applying a voltage to the curtain plate to direct ions from the ion source to the first aperture in the first curtain plate, a second power supply for applying a voltage to the second curtain plate to direct ions to the orifice, and a curtain gas flow mechanism for directing a curtain gas into the flow passage and the annular gap, the curtain gas generating a high velocity jet of gas across the orifice as the curtain gas flow passes through the annular gap.
These and other features of the applicants' teachings are set forth herein.
The skilled person in the art will understand that the drawings, described below, are for illustration purposes only. The drawings are not intended to limit the scope of the applicants' teachings in anyway.
In the drawings, like reference numerals indicate like parts.
Reference is first made to
Ions 103 are sent in the direction 101 towards a mass spectrometer sample inlet structure which includes a curtain plate aperture 106 located in a curtain plate 104. These ions are drawn through the aperture 106 through a curtain flow gas 107 towards an orifice 112 located in sampling member 108 which leads into the vacuum stage of the mass spectrometer (not shown). As is known in the art, sampling member 108 can be but is not limited to a plate or an intake tube. The curtain plate 104 and the sampling member 108 are spaced to form a curtain chamber 109 through which the curtain gas 107 is discharged. The curtain chamber 109 is typically at a pressure of close to or slightly greater than atmospheric pressure so that at least some of the flowing curtain gas 107 flows outward into the ion source, while some of the flowing curtain gas 107 flows into the vacuum chamber. In this example, both the aperture 106 and the orifice 112 are aligned along a common axis 101 so that both the aperture 106 and the orifice 112 are “coaxially aligned” as the term is used herein.
Typical voltages applied by a power source (not shown) to the curtain plate 104, and the sampling plate 108 are 1000V and 100V, respectively. These voltages ensure the positive ions are directed from the ion source 102 to the sampling plate aperture 108 whereupon the atmosphere gas flow carries them into the low pressure region of the first stage of a mass spectrometer. For negative ion detection the polarity of these typical voltages are −1000V and −100V, respectively. The spacing between the curtain plate aperture 106 and the sampling plate orifice 112 is selected to be sufficiently small that ions can be efficiently focused through the space toward the sampling plate with minimal losses. However, the spacing is also selected to be sufficiently large that droplets and clusters are either excluded from the space, so that they do not reach the sampling orifice, or else they have sufficient residence time in the curtain gas region to become completely or nearly completely evaporated. Since these two design considerations are contradictory, a compromise is sought.
Existing prior art curtain gas configurations may have spacings that are small enough for sufficient ion focusing and therefore high sensitivity. However, this allows some droplets to penetrate and reach the sampling orifice and be carried into the vacuum chamber. For example, when the solvent flow from the LC is high, for example 0.5 mL/min or larger, and contains high concentrations of water, for example greater than 50%, then the desolvation may be insufficient, and droplets from ion source 102 can be sampled into the mass spectrometer. Therefore, contaminating particles can enter the mass spectrometer, decreasing stability, ruggedness and ease of use.
In various embodiments, there can be provided a mass spectrometer system comprising an ion source for generating ions at substantially atmospheric pressure. In various aspects, a sampling member can be provided having an orifice therein, the sampling member forming a vacuum chamber with a mass spectrometer. In various aspects, a curtain plate can be provided between the ion source and the sampling member, the curtain plate having an aperture therein, the aperture having a cross-section and being spaced from the sampling member to define a flow passage between the curtain plate and the sampling member, and to define an annular gap between the orifice and the aperture. In various embodiments, the area of the annular gap can be less than the cross-sectional area of the aperture, a power supply for applying a voltage to the curtain plate to direct ions from the ion source to the aperture in the curtain plate, and a curtain gas flow mechanism can be provided for directing a curtain gas into the flow passage and the annular gap.
In various embodiments, the area of the annular gap can be less than 50% of the area of the aperture. In various aspects, the annular gap can be less than 0.5 mm. In various aspects, the annular gap can be less than 0.3 mm. In various aspects, the curtain gas can form a high velocity jet in front of the orifice.
In various embodiments, there can be provided a mass spectrometer system comprising an ion source for generating ions at substantially atmospheric pressure. In various aspects, at least two curtain plates can be provided, each curtain plate of the at least two curtain plates can have an aperture. In various aspects, each curtain plate can be spaced to form a plurality of flow passages therebetween. In various embodiments, a sampling member can be provided. In various aspects, the sampling member can have an orifice therein. In various aspects, the sampling member can form a vacuum chamber with a mass spectrometer. In various aspects, the sampling member can be spaced away from the at least two curtain plates forming a flow passage therebetween. In various embodiments, a power supply voltage can be provided for applying independent voltages to each curtain plate to direct ions through each of the apertures of each curtain plate. In various aspects, at least one gas flow mechanism can be provided for directing curtain gases into each of the plurality of flow passages. In various embodiments, the curtain gases have different composition.
In various embodiments, there can be provided a mass spectrometer system comprising an ion source for generating ions at substantially atmospheric pressure. In various aspects, a first curtain plate can be provided having a first aperture. In various embodiments, a second curtain plate can be provided having a second aperture being spaced away from the first curtain plate defining a first curtain chamber therebetween. In various aspects, a sampling member can be provided having an orifice therein. In various embodiments, the sampling member can form a vacuum chamber with a mass spectrometer.
In various aspects, the sampling member can be spaced away from the second curtain plate defining a second curtain chamber therebetween. In various embodiments, a first curtain gas flow mechanism can be provided for directing a first curtain gas into the first curtain chamber. In various aspects, a power supply can be provided for applying a first voltage to the first curtain plate to direct ions from the ion source to the first aperture and for applying a second voltage to the second curtain plate to direct ions from the first aperture to the second aperture. In various embodiments, a second curtain gas flow can be provided for directing a second curtain gas into the second curtain chamber. In various embodiments, the first and second curtain gases have different composition.
In various embodiments, there can be provided an ion sampling interface for receiving ions from an ion source. In various aspects, the ion sampling interface can comprise a first curtain plate having a first aperture therein for receiving the ions from the ion source. In various aspects, a second curtain plate can be provided having a second aperture therein. In various embodiments, the second curtain plate can be spaced from the first curtain plate to form a curtain chamber therebetween. In various embodiments, a sampling member can have an orifice therein. In various aspects, the sampling member can form a vacuum chamber with a mass spectrometer. In various aspects, the sampling member can be spaced from the second curtain plate to form a curtain flow channel therebetween. In various embodiments, the sampling member can define an annular gap between the orifice and the second aperture. In various aspects, the area of the annular gap can be less than the cross-sectional area of the aperture. In various embodiments, a first power supply can be provided for applying a voltage to the curtain plate to direct ions from the ion source to the first aperture in the first curtain plate. In various aspects, a second power supply can be provided for applying a voltage to the second curtain plate to direct ions to the orifice. In various aspects, a curtain gas flow mechanism can be provided for directing a curtain gas into the flow passage and the annular gap. In various aspects, the curtain gas can generate a high velocity jet of gas across the orifice as the curtain gas flow passes through the annular gap.
When a curtain gas is introduced into the flow channel 410, the curtain gas is forced through narrower annular gap 405 between the orifice 408 and the aperture 404, establishing a non-uniform high velocity jet of gas across the orifice 408. The narrower the annular gap 405, the higher the velocity of the jet of gas across the orifice 408. This jet of gas across the orifice 408 repels droplets and clusters. Since a high velocity jet is produced as a result of the geometries and proximities of the curtain plate 402 and the sampling member 406, a lower curtain gas flow can be used than would be used in a standard sampling interface configuration.
The width across the annular gap 405 (or x) can vary from 0.1 mm to 1 mm, and is typically 0.5 mm. The diameter of the aperture 404 (or D) can vary from 2 mm to 10 mm, and is typically 4 mm. The diameter of the orifice 408 can vary from 0.3 mm to 2 mm, and is typically 0.75 mm.
It will be understood by those skilled in the art that orifice 408 and aperture 404 can be non-circular in shape. For example, orifice 408 and aperture 404 can be rectangular in shape. The narrow annular gap 405 between the curtain plate 402 and the sampling member 406 can be maintained around the circumference of the aperture 404 for any chosen shape.
Placement of the curtain gas in the configuration of
For the time prior to the beginning of period A, the LC pump is turned off, and no water droplets are created in the ion source. The water vapor signal prior to period A is due to water vapor desorbed from the walls of the vacuum chamber. At the beginning of period A, the LC pump is turned on, flowing 0.5 mL/min through the electrospray ion source. At the beginning of period B, the flow rate is increased to 1 mL/min, and at the beginning of period C, the flow rate is increased to 2 mL/min.
As shown in
A first curtain gas flow is directed into the first curtain gas chamber 710 and a second curtain gas flow is directed into the second curtain gas chamber 712. The first and second curtain gas flows can be adjusted independently or together. Each curtain plate 702 and 704 is isolated electrically from the other, permitting independent voltages to be applied to each plate with separate power supplies (not shown). Ions from the ion source 102 are focused through the first curtain gas chamber 710 and then through the second curtain gas chamber 712 before they are carried into the vacuum chamber (not shown) by the gas suction through the orifice 716. In a further alternate configuration, the sampling interface is not limited to two curtain plates defining two curtain chambers but can have a plurality of curtain plates defining a plurality of curtain chambers. The voltages applied to each plate can be adjusted to provide optimum focusing of the ions. The use of two or more curtain gas chambers can provide better protection of the sampling orifice, with greater efficiency of preventing droplets and clusters from entering the vacuum chamber. This better protection is a result of the greater thickness or depth of the region of curtain gas, thus providing more time for the droplets to evaporate, and providing greater resistance to the droplets being carried toward the sampling orifice and into the vacuum chamber.
The use of two separate curtain gas chambers can allow the use of different flows and different flow velocities in the two chambers. For example, the outward flow velocity in the first curtain chamber 710 may be high in order to exclude larger droplets. The flow in the second curtain gas chamber 712 can be lower in order to make it easier to focus the ions through, because the large droplets have been excluded from this region by the flow in the first curtain gas chamber 710. Additionally, different gas compositions can be used in the two chambers. For example, nitrogen gas can be used in the first chamber 710 because it has larger heat capacity than helium, and can more effectively dry the droplets. Helium can be used in the second chamber 712, allowing ions to be easily focused through the lighter helium gas due the higher mobility of ions in helium gas than in nitrogen, and allowing only helium gas to enter the vacuum chamber. This can be advantageous to minimize fragmentation of the ions in the first vacuum chamber, because collisions between ions and lighter helium gas can result in less unwanted fragmentation than collisions with nitrogen gas, which is heavier.
Additionally, other gases can be added to the first or second chamber in order to react with the ions. Some reagent gases can be used to reduce chemical noise, or to reduce the charge state of multiply-charged ions, or to react with the ions to produce specific adducts or product ion species that make the analysis more specific. In many cases, it is desirable to prevent reactive gas species from entering into the vacuum chamber. The second curtain gas chamber 712 can therefore be supplied with a pure gas such as nitrogen in order to prevent reactive gases from the first curtain gas region from entering the vacuum chamber. This keeps the vacuum chamber clean, and minimizes clustering of ions in the free jet expansion that can occur if polar reactive species are present in the gas expanding into vacuum. Therefore multiple curtain gas chambers can be used to separate reaction regions from the vacuum chamber, and thereby keep reactive species out of the vacuum chamber. In some cases, ionic species can be added to the first curtain gas chamber 710 in order to react with the ions from the ion source (for example specific negative ions can react with positive ions to form specific product ions). In some cases, two or more different reagent gases can be added to the two or more separate curtain gas chambers to cause sequential reactions as the ions pass through the two chambers.
When a first curtain gas is released in the flow channel 814, the curtain gas is forced through narrower annular gap 807 between the first aperture 808 and the second aperture 810, establishing a non-uniform high velocity jet of gas across the second aperture 810. The narrower the annular gap 807, the higher the velocity of the jet of gas across the second aperture 810. This jet of gas across the second aperture 810 repels droplets and clusters. Since a high velocity jet is produced as a result of the geometries and proximities of the first curtain plate 802 and the second curtain plate 804, a lower first curtain gas flow can be used than would be used in a standard sampling interface configuration. As the ions enter the curtain chamber 816 between the second curtain plate 804 and the sampling member 806, a second curtain gas is directed in the curtain chamber 816 before they a carried into the vacuum chamber (not shown) by the gas suction through the orifice 812.
Ions 103 move through the first curtain gas in the first curtain chamber 914, which is formed by the space between the first curtain plate 902 and the second curtain plate 906. The ions 103 move towards the second aperture 908. The second curtain plate 906 and the sampling member 910 are spaced to form a curtain flow channel 916 through which the second curtain gas is directed. In this example, the center of the first aperture 904 is lower than the common axis 901. Momentum from the first curtain gas carries the heavier droplets and clusters down away from the second aperture 906 and orifice 912, whereas the lighter ions will turn and flow into the orifice 912.
When a second curtain gas is released in the flow channel 916, the second curtain gas is forced through narrower annular gap 918 between the second aperture 908 and the orifice 912, establishing a non-uniform high velocity jet of gas (indicated by the arrows) across the orifice 912. The narrower the annular gap 918, the higher the velocity of the jet of gas across the orifice 912. This jet of gas across the orifice 912 repels droplets and clusters. Since a high velocity jet is produced as a result of the geometries and proximities of the second curtain plate 906 and the sampling member 910, a lower second curtain gas flow can be used than would be used in a standard sampling interface configuration. The ions 103 are then carried into the vacuum chamber (not shown) by the gas suction through the orifice 918.
While the applicants' teachings have been particularly shown and described with reference to specific illustrative embodiments, it should be understood that various changes in form and detail may be made without departing from the spirit and scope of the teachings. Therefore, all embodiments that come within the scope and spirit of the teachings, and equivalents thereto, are claimed. The descriptions and diagrams of the methods of the applicants' teachings should not be read as limited to the described order of elements unless stated to that effect.
While the applicants' teachings have been described in conjunction with various embodiments and examples, it is not intended that the applicants' teachings be limited to such embodiments or examples. On the contrary, the applicants' teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art, and all such modifications or variations are believed to be within the sphere and scope of the invention.
This application claims priority to U.S. provisional application no. 61/561,977 filed Nov. 21, 2011, which is incorporated herein by reference in its entirety.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/IB2012/002436 | 11/21/2012 | WO | 00 | 5/21/2014 |
Number | Date | Country | |
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61561977 | Nov 2011 | US |