Robust, rapid, secure sample manipulation before during and after ionization for a spectroscopy system

Information

  • Patent Grant
  • 9105435
  • Patent Number
    9,105,435
  • Date Filed
    Friday, October 31, 2014
    9 years ago
  • Date Issued
    Tuesday, August 11, 2015
    8 years ago
Abstract
This invention provides for the efficient positioning of a sample to be analyzed by using either magnetic or electro-mechanical fields to retain the sample in the ionization region. In an embodiment of the present invention, the sample is contacted with a sampler device, which is inserted into a chamber and accurately positioned using electro-mechanical devices. In an embodiment of the invention, the influence of an electro-mechanical field on the sampler device enables the sample to be positioned in the ionization region to be contacted by particles that result in ionization of the sample whereby rendering the resulting ions available for analysis.
Description
FIELD OF THE INVENTION

The present invention permits desorption ionization of powders, plant materials, and loose substances by securing the position of these materials which are otherwise easily displaced during sample handling and analysis.


BACKGROUND OF THE INVENTION

Ambient pressure desorption ionization sources, such as direct analysis in real time (DART®) and desorption electrospray ionization, enable detection of chemicals present as or embedded in a solid object or condensed on surfaces. Examples of sources include: using a flowing heated gas containing metastable atoms or molecules in DART, using a flowing gas containing ions and metastable atoms or molecules in Flowing Atmospheric Pressure Afterglow (FAPA), and using a flowing high pressure mixture of gas and solvent droplets in desorption electro spray ionization (DESI).


A common occurrence in Homeland Security associated ‘security alerts’ is the report describing the presence of a “white powder”. Identification of such materials requires a determination of composition. Enabling direct determination of composition without the requirement for dissolving the material facilitates reduced sample handling and thus affords greater protection to the humans undertaking the analysis as well as reduced time for analysis.


SUMMARY OF THE INVENTION

In various embodiments of the present invention, metal powders are used to disperse and retain samples for analysis. In an embodiment of the invention, a device for ionizing a sample comprises a sampler device for maintaining or constraining the position of the sample relative to the flowing gases and liquids exiting an ionization source. The device further includes a chamber or open region where the sample can be positioned and an entrance into a spectroscopy system where analysis occurs.





BRIEF DESCRIPTION OF THE DRAWINGS

This invention is described with respect to specific embodiments thereof. Additional features can be appreciated from the Figures in which:



FIG. 1 shows a schematic diagram of a prior art sample device;



FIG. 2 shows a schematic diagram of a magnetically enabled sampling device according to an embodiment of the invention;



FIG. 3 shows a schematic diagram of the mixing chamber for sample preparation according to an embodiment of the invention;



FIG. 4 shows a schematic diagram of sample loading using a magnetically enabled sampling device as shown in the mixing chamber for sample preparation as shown in FIGS. 2 and 3 according to an embodiment of the invention;



FIG. 5 shows a schematic diagram of the photograph shown in FIG. 6 where sample loading using a magnetically enabled sampling device locates sample on three sites on a surface for analysis according to an embodiment of the invention;



FIG. 6 shows a photograph of sample loading which is using a magnetically enabled sampling device to locate a sample on three sites on a surface for analysis according to an embodiment of the invention;



FIG. 7 shows a schematic diagram of an off axis system of analysis enabled with a spectroscopy system as shown in the line drawing of FIG. 10 according to an embodiment of the invention;



FIG. 8 shows a schematic diagram of the sampling device used to position a sample in a spectroscopy system according to an embodiment of the invention;



FIG. 9 shows a schematic diagram of the sampling device used to position multiple samples in a spectroscopy system according to an embodiment of the invention; and



FIG. 10 shows a line drawing of an off axis system of analysis enabled with a spectroscopy system;





DETAILED DESCRIPTION OF THE INVENTION

The development of efficient desorption ionization sources for use with spectroscopy systems has enabled rapid analysis of samples without requiring laborious sample preparation. These desorption ionization sources require that the sample be positioned in a small region at the exit of the source to permit interaction of the ionizing gases with the sample for analysis.


Atmospheric pressure desorption ionization sources such as direct analysis real time (DART®) and desorption electrospray ionization function well for the ionization of solids and samples adsorbed onto surfaces because they can be fixed in position and not displaced by the action of the flowing gases and solvents. Once formed the ions can, for example, be introduced into a mass spectrometer for mass analysis. However, in the case of chemicals present in powder form, the direct desorption ionization analysis can become problematic due to displacement of the powder by the action of the flowing gases and liquids utilized in the experiment. Without retention of the sample in the desorption ionization region, analysis of these compounds is either compromised and/or results in contamination of the spectroscopy system as the desorbed chemicals contaminate surfaces and entrances to the spectroscopy system.


Thus, for loose powders the utility of the desorption ionization technology is reduced since powders and other light weight or loose samples often cannot be anchored without altering their chemical state (e.g., making into a solution). In an embodiment of the present invention, a simple method to retain powder type samples for surface desorption ionization at atmospheric pressure with increased certainty, involves the co-mixing and thereby the dispersal of a heavy weight powder with the sample powder prior to analysis in order to secure the powder in position. In an embodiment of the present invention, the heavy weight powder can be a metal powder. In an embodiment of the invention, the sample with the metal powder dispersed and therefore coating the sample can be maintained in its position by the weight of the metal powder. In an alternative embodiment of the present invention, the sample with the metal powder dispersed and thereby coating the sample can be maintained in its position by a magnetic field used to fix the metal in position for analysis. In an embodiment of the present invention, a device provides the means for positioning of a sample powder in a desorption ionization region.


In various embodiments of the invention, the metal powder or granules can be selected from the group consisting of metals and non-metals. In various embodiments of the invention, the powder or granules can be selected from the group consisting of magnetic and non-magnetic metals. In various embodiments of the invention, the powder or granules can be one or both a paramagnetic and a ferromagnetic material.


Paramagnetism is a form of magnetism which occurs only in the presence of an externally applied magnetic field. Ferromagnetism is the mechanism by which certain materials form permanent magnets or are attracted to magnets. Classical electro-magnetism indicates that two nearby magnetic dipoles will tend to align in opposite directions, so their magnetic fields will oppose one another and cancel out. However, in ferromagnetic materials the dipoles tend to align in the same direction. The Pauli Exclusion Principle teaches that two electrons with the same spin cannot also have the same ‘position’. Under certain conditions, the Pauli Exclusion Principle can be satisfied if the position of the outer orbitals of the aligned electrons is sufficiently distant. In these ferromagnetic materials, the electrons having parallel spins result in the distribution of electric charge in space being further apart and therefore the energy of these systems is at a minimum. The unpaired electrons align in parallel to an external magnetic field in paramagnetic materials. Only atoms with partially filled shells can have a net magnetic moment, so ferromagnetism and paramagnetism only occur in materials with partially filled outer electron shells. Non-magnetic metals typically have filled outer electron shells (e.g., Beryllium, Cadmium, Calcium, Magnesium, Mercury, and Zinc) or form covalently bound molecules fulfilling this condition (e.g., Aluminum, Barium, Copper, Gold, Lead, Lithium, Platinum, Potassium, Radium, Rhodium, Strontium, Silver, Tin, Titanium and Tungsten). As the temperature of ferromagnetic materials increase, the entropy of the system reduces the ferromagnetic alignment of the dipoles. When the temperature rises above the Curie temperature, the system can no longer maintain spontaneous magnetization, although the material still responds paramagnetically to an external field (see Table I for list of ferromagnetic and ferrimagnetic materials and their Curie temperature).









TABLE I







List of ferromagnetic and ferrimagnetic


materials and their Curie temperature










Material
Curie temperature (° K.)














Co
1388



Fe
1043



FeOFe2O3
858



NiOFe2O3
858



CuOFe2O3
728



MgOFe2O3
713



MnBi
630



Ni
627



MnSb
587



MnOFe2O3
573



Y3Fe5O12
560



CrO2
386



MnAs
318



Gd
292



Dy
88



EuO
69










In various embodiments of the invention, the powder or granules can be selected from the group consisting of one or more iron containing substances including Fe, FeO, FeOFe2O3, Fe2O3, MnOFe2O3, MgOFe2O3, Y3Fe5O12 and Fe3O4. In various embodiments of the invention, the powder or granules can be selected from the group consisting of one or more copper containing substances including Cu, CuO, CuOFe2O3 and Cu2O. In various embodiments of the invention, the powder or granules can be selected from the group consisting of one or more aluminum containing substances including Al and Al2O3. In various embodiments of the invention, the powder or granules can be selected from the group consisting of one or more nickel containing substances including Ni, NiO, Ni2O3, Ni(OH)2 and NiOFe2O3. In various embodiments of the invention, the powder or granules can be selected from the group consisting of one or more cobalt containing substances including Co, NaCoO2 and Co3O4. In various embodiments of the invention, the powder or granules can be selected from the group consisting of one or more lanthanide metals. In various embodiments of the invention, the powder or granules can be selected from the group consisting of one or more ferromagnetic and/or ferrimagnetic materials of Table I. In various embodiments of the invention, the powder or granules can be selected from the group consisting of physical mixing of two or more of Fe, FeO, FeOFe2O3, Fe2O3, Fe3O4, Cu, CuO, and Cu2O, Al and Al2O3. In various embodiments of the invention, the powder or granules can be selected from a physical combination of two or more metals or alloys that can either be magnetic or non-magnetic.


When a security alert reports the presence of a “white powder” or other unknown substance, there is an immediate and real need for determining the composition of the powder and specifically whether the powder is anthrax or any other dangerous biological or chemical agent. The first step in analysis of these ‘unknowns’ often involves isolation of the material in specialized containers for transfer to protect the analyst and his or her environment from contamination. In order to determine the chemical composition or organism present in the powder, the analyst often creates a soluble solution by dissolving the powder in water or an appropriate solvent. The use of expensive and often elaborate testing equipment is needed when using such a soluble solution and since not all powders are soluble valuable time is lost as the analyst labors to create that solution. Ultimately, the sample represents no security threat but the time used in determination of its composition is lengthened by each step of manipulation.


The challenge to rapid chemical analysis is designing a process that uses a minimum of sample manipulation in order to complete chemical analysis in mere seconds. The ability to complete rapid analysis of the sample can be facilitated if real time ionization can be used as a screening method. Thus, the development of a more practical device for positioning samples with minimal human intervention can be an important requirement for deploying real time monitoring, beyond the confines of the laboratory. Utilizing metal powders with ionization techniques to sample and retain the ‘unknown’ powder and subsequently permit its positioning for analysis can provide a means to facilitate the rapid determination of composition which is necessary to either dismiss or elevate the threat level.


A vacuum of atmospheric pressure is 1 atmosphere=760 torr. Generally, ‘approximately’ in this pressure range encompasses a range of pressures from below 101 atmosphere=7.6×103 torr to 10−1 atmosphere=7.6×101 torr. A vacuum of below 10−3 torr would constitute a high vacuum. Generally, ‘approximately’ in this pressure range encompasses a range of pressures from below 5×10−3 torr to 5×10−6 torr. A vacuum of below 10−6 torr would constitute a very high vacuum. Generally, ‘approximately’ in this pressure range encompasses a range of pressures from below 5×10−6 torr to 5×10−9 torr. In the following, the phrase ‘high vacuum’ encompasses high vacuum and very high vacuum. The sampler/chamber system can be at atmospheric pressure.


Movement of Samples into and Through the Ionization Region for Analysis


In atmospheric pressure desorption ionization experiments solid objects placed in close proximity to the exit of the source interact with the gas exiting that source. The solid object is often positioned manually or by using devices such as tweezers. In an embodiment of the present invention, a sample in powder form can be immersed into or deposited into a container for co-mixing with metal powder. After mixing to disperse the powder in with the metal, a small fraction of the sample can be removed from the tube along with the metal, enabling its analysis as it is placed in the desorption ionization region. For rapid qualitative determination of samples, the quantity of sample retained on the metal is not critical; therefore, the acquisition of even a small quantity of material can enable a successful analysis. In an alternative embodiment of the present invention, automation of the sampling technology for desorption ionization involves fabrication of a partially glass and partially metal rod sampler tip to which a small magnet can be fixed to cause the magnetized metal coated with “unknown” powder to be retained in its position for analysis. In another embodiment of the invention, by using a microscope slide-sized flat surface (i.e. a flat surface the size of a microscope slide) to which one or more magnets have been fixed on the underside, the metal coated with powder can be deposited on the surface for analysis. In a variety of embodiments of the invention, electro-magnetic fields can be used to automate the movement of the sample from container to container or from container to sample surface for analysis. In an embodiment of the invention, a non-magnetic metal coated with powder can be deposited onto a surface for analysis where the weight of the metal can be sufficient to cause the sample to maintain position in the presence of the flowing gas stream used for desorption ionization.


In an embodiment of the present invention, the mixing of a metal powder with an ‘unknown’ powder or ‘unknown’ sample present in crystalline form facilitates mechanical control of the positioning of the sample with magnetic or electro-magnetic fields. A ‘sampler device’ can be fabricated such that the sample can be inserted into an enclosed chamber attached to a desorption ionization region. Using the ‘sampler device’ the sample can be reliably transferred from the enclosed chamber into the desorption ionization region by mechanical or electro-mechanical means. In an embodiment of the invention a method is described for depositing the ‘unknown’ or material of interest onto a sampler and dropping the sampler into the chamber and subsequently manipulating the sampler into position using robotics without requiring human intervention to physically touch or contact the sample. Once the sample is placed in the desorption ionization region, chemical analysis can take place.


A mechanical device is operated by a mechanism. An electro-mechanical device or system is a mechanical device or system that is actuated or controlled by electricity. An electro-magnetic device is operated, actuated or controlled by magnetism produced by electricity. An electro-mechanical force is a force formed by electro-magnetic induction.


Sampler Device



FIG. 1 shows prior art of a desorption ionization source coupled to a mass spectrometer. In FIG. 1, the ‘sampler device’ 116 is a 1.4 mm outside diameter, 0.5 mm inside diameter by 6 mm long glass tube with one end sealed. The sampler device has a coating of material on its exterior surface at the closed end. The coating was generated by dissolving the sample in a solvent and then applying a solution to the sampler device 116. The device 116 is positioned between the ionization source 101 which is directing a flow of gas or liquid at the device 116. Materials desorbed from the surface are ionized and those products enter the spectrometer through an atmospheric pressure inlet 121. In various embodiments of the invention, as shown in FIG. 2, one or more small magnets or pieces of either paramagnetic or ferromagnetic susceptible metal 234 are secured to a metal rod 216 having similar dimensions to the glass rod of FIG. 1. The device 216 can be positioned between the ionization source 201 which is directing a flow of gas or liquid at the device 216. Materials desorbed from the surface can be ionized and those products can enter the spectrometer through an atmospheric pressure inlet 221. A sample of magnetic susceptible metal powder or granules co-mixed with sample powder can then be applied to the closed-end of the tube of the sampler. Preparation of the sample for analysis is depicted in FIG. 3 where a powder sample 341 represented on a common laboratory spatula 356 is added to a container 318 containing an excess of metal 307. As shown in FIG. 4 after mixing of the sample with the metal powder in the container, the metal sampler device 416 to which one or more small magnets or pieces of magnetic susceptible metal 434 have been secured can be inserted into the volume of the container 418 containing an excess of metal powder coated with the sample 407 to permit collection of a portion of the metal powder coated with sample 447. In an embodiment of the invention shown in FIG. 5 the sampler device 516 is a small magnetically susceptible piece of metal such as an iron nail to which a small magnet 534 has been positioned approximately one (1) inch above the closed end of the nail 516, referred to as a ‘magnetized nail’ 516. The magnetized nail 516 can be used as a sample transfer device to move sample from the container 418 shown in FIG. 4 to a surface for sampling. In FIG. 5 sample positioning of sample (mixed with metal powder 547) for analysis is facilitated by using a surface 553 under which a small magnet 537 or series of magnets can be placed in order to retain the magnetically susceptible metal powder coated with sample in position for analysis. A photograph of the device described in FIG. 5 is shown in FIG. 6. Implementation of the device of FIG. 5 with a direct analysis in real time ionization source is shown schematically in FIG. 7. FIG. 7 shows the surface 753 with magnet 737 positioned to locate sample positioned between the ionization source 701 which is directing a flow of gas or liquid at the sample. Materials desorbed from the surface are ionized and those products enter the spectrometer through an atmospheric pressure inlet 721. A line drawing of the device of FIG. 7 with a direct analysis in real time ionization source is shown in FIG. 10. In an embodiment of the invention shown in FIG. 8, the end of the metal powder coated sample device 816 (utilizing a magnet 834 to hold the sample) can be positioned inside a sampling chamber 836 to allow sampling in a closed volume to protect the analyst from harmful chemicals and toxins. The end of the sampling device 816 can be positioned between the ionization source 801, which can be directing a flow of gas or liquid at the device 816. Materials desorbed from the surface can be ionized and those products enter the spectrometer through an atmospheric pressure inlet 821. In an embodiment of the invention shown in FIG. 9, the sampler device 953 can be inserted through port 924 and positioned inside a sampling chamber 936 to allow sampling in a closed volume to protect the analyst from harmful chemicals and toxins. The sampler device 953 can be positioned between the ionization source 901 which can be directing a flow of gas or liquid at the sampler device 953. Materials desorbed from the surface can be ionized and those products can enter the spectrometer through an atmospheric pressure inlet 921. Orientation of the sampler device 953 can be manipulated without concern for loss of sample since the action of the magnetic field derived from the small magnets 937 retains the sample on the surface. Once analysis is complete the sampler device 953 can exit the chamber 936 through port 939. The sample can be manipulated in the closed environment to permit analysis.


Electro-Mechanical Chamber


In an embodiment of the present invention, the ‘electro-mechanical chamber’ can be a cylinder having an opening through which the sampler can be inserted. The open ‘electro-mechanical chamber’ can be of sufficient dimension to permit insertion of a variety of objects. In an embodiment of the present invention, the open ‘electro-mechanical chamber’ can accept 1×10−4 m diameter tubes. In an alternative embodiment of the present invention, the open ‘electro-mechanical chamber’ can accept 1×10−3 m diameter tubes. In another embodiment of the present invention, the open ‘electro-mechanical chamber’ can accept 1×10−2 m diameter tubes. In another alternative embodiment of the present invention, the open ‘electro-mechanical chamber’ can accept 1×10−1 m diameter tubes. In various embodiment of the present invention, the open ‘electro-mechanical chamber’ can accept a non-cylindrical sampler device.


In an embodiment of the invention shown in FIG. 7 a sampler with the configuration shown in FIG. 5 can be depicted as a plate 753 with the ionization gun 701 directing species at the sample which forms ions that enter the spectrometer through aperture 721. As shown in FIG. 10 the sampler with the configuration shown in FIG. 5 is depicted as a rectangular plate 1053 with the sample mixed with metal powder 1057 has been deposited, with the ionization gun 1001 directing species at the sample which forms ions that enter the spectrometer through aperture 1021. The location of the sample mixed with metal powder 1057 in front of the ionization gun 1001 can be changed using a location locking device 1024. The rectangular plate 1053 enters the proximal end of the ‘electro-mechanical chamber. FIG. 9 illustrates a series of events starting with capture of the ‘sampler device’ 953 in a fixed position such that the sample itself does not touch any surface of the ‘electro-mechanical chamber’. The sample may be pushed through an entrance 924 and exit 939 of the chamber to permit rapid, safe detection of powder with the spectroscopy system 921. In an embodiment of the invention, a series of magnets to which a magnetically susceptible metal coated powder of interest can be positioned along a conveyor belt serves to transfer the powder coated metal to the desorption ionization region by using an electro-magnetic field. The interaction of the sample coated magnet with the electro-magnet element serves to hold the sampler in an intermediate position prior to analysis. A sampling zone 901, where the analysis occurs, can be at the distal end of the ‘electro-mechanical chamber’ of the desorption ionization source. At the proximal end of the ‘electro-mechanical chamber a lid capable of closing and forming an airtight seal once the sampler had been placed inside the ‘electro-mechanical chamber’ in a fixed position. The function of the lid can be to maintain enough pressure to keep gases from escaping through the proximal end of the cylindrical ‘electro-mechanical chamber’. Closure of the lid can also initiate the sampling sequence by depressing a switch or completing an electrical or optical contact, and thus connecting an initiation event marker of electrical, digital or mechanical design.


In an embodiment of the invention with the ‘electro-mechanical chamber’ containing the ‘sampler device’ closed and sealed, the composition of the chemical environment surrounding the sample can be controlled. In an embodiment of the invention, the sealed ‘electro-mechanical chamber’ can be used to support one or more functions selected from the group consisting of atmospheric pressure chemical ionization; negative ion chemical ionization; prevention of oxidation or reduction of the sample; or exposure of the sample to one or more other ionization sources. With the sampler under the influence of the electro-magnetic field, the sample can be positioned for desorption ionization. In the case where the sample is a large object with one or more distinct surfaces, the electro-magnetic field can be used to move the entire object in order to affect desorption of different areas of the sample by use of the electro-magnetic fields. In the case where the sample requires different ionization conditions using the same ionization source, the electro-magnetic field can be used to move the entire object in order to affect desorption of the same area of the sample with similar DART guns operated at different conditions by use of the electro-magnetic fields.


In an embodiment of the invention, after the analysis is complete and to facilitate analysis of the next sample, the electro-magnetic field can be used to expel the ‘sampler device’ out from the ionization region from the ‘electro-mechanical chamber’. Once the analysis is complete, the electro-magnetic field can either be turned off and a spring mechanism used to release the sampler device, or the electro-magnetic field can be reversed. In an embodiment of the invention, the opening of an exit port door located at the distal end of the ‘electro-mechanical chamber’ can deactivate the electro-magnetic field elements and release the sampler device allowing the sample to fall under the effect of gravity through the exit port located at the distal end of the ‘electro-mechanical chamber’.


In another embodiment of the invention, a series of electro-magnetic devices including rings, plates, balls, or other shapes designed to capture specific objects can be used to transport the sample into the ideal position for desorption ionization. Once the analysis is complete, the series of electro-magnetic rings can be used to eject the ‘sampler device’ back into the ‘electro-mechanical chamber’. In another embodiment of the invention, concerted action of the electro-magnetic fields results in a high throughput apparatus for rapid sampling by desorption ionization at atmospheric pressure.


The sampler device can have a segment of metal comprised of a band of metal or a strip of metal positioned remote from the desorption ionization region. In this manner, the magnetic fields would not deflect or defocus ions that must be transferred to the spectroscopy system for analysis. In an embodiment of the invention the metal or magnets can be enclosed in the body of the sampler at a position remote from the desorption ionization region. The ‘sampling device’ objects can be made of glass, ceramic, plastic, wood, fabric or other suitable material shaped into tubes, rod, plates, or other objects customized for sampling. The metal pin, crimping cap, shank, brad, staple, wire or band can be inserted into or bonded to the sampling device in order to secure that sample to the sampling object.


The ‘sampler device’ and the ‘electro-mechanical chamber’ system can be automatically operated at increased sample turnaround speed without requiring an analyst or other human intervention. A significant utility of the sampler/chamber system embodied in the invention lies in unattended operation which thereby increases sampling speed.


In an embodiment of the invention a device for ionizing an analyte comprises a chamber with at least three ports, where a first port allows the analyte to enter the chamber and the chamber is adapted to mix the analyte with a material using a magnetic field source where the magnetic field source is adapted to constrain the analyte mixed with the material within the chamber. The device further comprises an atmospheric pressure ionization source adapted to be directed at the analyte mixed with the material to form analyte ions which exit out of a second port. The magnetic field source is further adapted to remove the analyte mixed with the material from the chamber through a third port to dispose of the analyte.


In an embodiment of the invention a method of ionizing a sample comprises mixing the sample with a ferromagnetic material with a lower ionization efficiency relative to the sample and constraining the sample mixed with the material using a magnetic field and generating one or more analyte ions of the sample and then using the magnetic field to dispose of the sample.


In an embodiment of the invention a kit for handling a sample for atmospheric pressure ionization comprises a vial adapted to be opened and resealed containing a material, where opening the vial and locating the sample in the vial and resealing the vial mixes the sample and the material. The kit further comprises a probe including a proximal end, a distal end, a coil situated at the distal end and a switch, where the switch is adapted to apply or discontinue an electro-magnetic field through the coil to position the material mixed with the sample onto the probe, where the probe is adapted to enter the vial and thereby position the material mixed with the sample onto the probe for removal from the vial. The kit further comprises an analysis plate with one or both a fixed magnet and an electro-magnet adapted to move the material mixed with the sample from the probe onto the analysis plate while constraining the material mixed with the sample to one or more regions on the plate for atmospheric pressure ionization.


Example embodiments of the methods, systems, and components of the present invention have been described herein. As noted elsewhere, these example embodiments have been described for illustrative purposes only, and are not limiting. Other embodiments are possible and are covered by the invention. Such embodiments will be apparent to persons skilled in the relevant art(s) based on the teachings contained herein. For example, it is envisaged that, irrespective of the actual shape depicted in the various Figures and embodiments described above, the outer diameter exit of the inlet tube can be tapered or non-tapered and the outer diameter entrance of the outlet tube can be tapered or non-tapered.


Thus, the breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

Claims
  • 1. A device for ionizing an analyte comprising: a chamber with at least one port to allow the analyte to enter the chamber and adapted to mix the analyte with a material;a lid adapted to close and form a seal with the chamber;a magnetic field source adapted to constrain the analyte mixed with the material within the sealed chamber; andan ionization source directed at the analyte mixed with the material to form analyte ions.
  • 2. The device of claim 1, where the magnetic field source is generated by one or both a magnet and an electro-magnet.
  • 3. The device of claim 1, further comprising controlling the position of the sample in the chamber with one or both the presence and absence of one or both of an electric field and the magnetic field source.
  • 4. The device of claim 1, where the position of the sample can be adjusted relative to the ionization source prior to an ionization event.
  • 5. The device of claim 1, where the position of the sample can be adjusted relative to the ionization source during an ionization event.
  • 6. The device of claim 1, where the position of the sample can be adjusted relative to the ionization source after an ionization event.
  • 7. The device of claim 1, where the ionization source is an atmospheric pressure ionization source.
  • 8. The device of claim 7, where the atmospheric pressure ionization is selected from the group consisting of a Direct Ionization in Real Time source, a desorption electro spray ionization (DESI) source, an atmospheric laser desorption ionization source, a Corona discharge source, an inductively coupled plasma (ICP) source and a glow discharge source.
  • 9. The device of claim 1, further comprising a spectroscopic analyzer adapted to analyze the sample ions.
  • 10. The device of claim 9, where the spectroscopic analyzer is selected from the group consisting of a mass spectrometer, Raman spectrometer, electro-magnetic absorption spectrometer, electro-magnetic emission spectrometer, surface detection spectrometer, differential scanning mobility spectrometer and ion mobility mass spectrometer.
  • 11. The device of claim 1, where the material includes a metal with one or both a magnetic dipole moment and an inducible magnetic dipole moment.
  • 12. The device of claim 1, where the sample is selected from the group consisting of a powder, lyophilized sample, plant material, fine grains, and a loose substance.
  • 13. The device of claim 1, where the material and the sample are physically mixed.
  • 14. A method of disposing of an analyzed sample comprising the steps of: receiving a sample mixed with a material that is heavier than the sample;sealing the sample in an analysis chamber adapted to close and form a seal such that no additional sample mixed with the material enters the analysis chamber;analyzing the sample in the analysis chamber the analyzing comprising directing an ionization source at the sample mixed with the material to form sample ions;determining the analysis of the sample in the analysis chamber is complete; andremoving the sample mixed with the material using a magnetic field to eject the sample from the analysis chamber.
  • 15. The method of claim 14, where the magnetic field is generated by one or both a magnet and an electro-magnet.
  • 16. The method of claim 14, further comprising providing an electric field to position the sample mixed with the material prior to removing the sample.
  • 17. The method of claim 16, further comprising using the magnetic field and the electric field to remove the sample.
  • 18. A method of disposing of an analyzed sample comprising the steps of: receiving a sample with a material that is heavier than the sample;inserting the sample with the material in an analysis chamber;sealing the sample with the material in the analysis chamber adapted to close and form a seal such that no additional sample mixed with the material can enter the analysis chamber;analyzing the sample in the sealed analysis chamber the analyzing comprising directing an ionization source at the sample mixed with the material to form sample ions;determining the analysis of the sample in the sealed analysis chamber is complete; andremoving the sample mixed with the material using an electro-mechanical device to eject the sample from the analysis chamber.
  • 19. The method of claim 18, further comprising providing an electric field to position the sample mixed with the material prior to removing the sample.
  • 20. The method of claim 18, where the electro-mechanical device opens an exit port to eject the sample.
PRIORITY CLAIM

This application is a continuation of (1) U.S. patent application Ser. No. 13/449,615 entitled “ROBUST, RAPID, SECURE SAMPLE MANIPULATION BEFORE DURING AND AFTER IONIZATION FOR A SPECTROSCOPY SYSTEM”, inventor: Brian D. Musselman, filed Apr. 18, 2012 which issued Dec. 2, 2014 as U.S. Pat. No. 8,901,488 which claims priority to (2) U.S. Provisional Patent Application Ser. No. 61/476,380 entitled: “ROBUST, RAPID, SECURE SAMPLE MANIPULATION BEFORE DURING AND AFTER IONIZATION FOR A SPECTROSCOPY SYSTEM”, inventor: Brian D. Musselman, and filed Apr. 18, 2011, the contents of each of which ((1)-(2)) are herein incorporated by reference in their entireties.

US Referenced Citations (223)
Number Name Date Kind
3633027 Rhyage Jan 1972 A
3957470 Dawes May 1976 A
4016421 Hull Apr 1977 A
4144451 Kambara Mar 1979 A
4213326 Brodasky Jul 1980 A
4542293 Fenn Sep 1985 A
4546253 Tsuchiya Oct 1985 A
4654052 Sharp Mar 1987 A
4662914 Hansen May 1987 A
4861988 Henion Aug 1989 A
5012052 Hayes Apr 1991 A
5055677 Amirav Oct 1991 A
5137553 Dawes Aug 1992 A
5192865 Zhu Mar 1993 A
5306412 Whitehouse Apr 1994 A
5352892 Mordehai Oct 1994 A
5367163 Otsuka Nov 1994 A
5381008 Tanner Jan 1995 A
5412208 Covey May 1995 A
5448062 Cooks Sep 1995 A
5552599 Giessmann Sep 1996 A
5559326 Goodley Sep 1996 A
5614711 Li Mar 1997 A
5624537 Turner Apr 1997 A
5684300 Taylor Nov 1997 A
5716825 Hancock et al. Feb 1998 A
5736741 Bertsch Apr 1998 A
5788166 Valaskovic Aug 1998 A
5868322 Loucks, Jr. Feb 1999 A
5889404 Abdel Mar 1999 A
5959297 Weinberg Sep 1999 A
5997746 Valaskovic Dec 1999 A
6107628 Smith Aug 2000 A
6124675 Betrand Sep 2000 A
6190559 Valaskovic Feb 2001 B1
6225623 Turner May 2001 B1
6297499 Fenn Oct 2001 B1
6359275 Bertsch Mar 2002 B1
6395183 Valaskovic May 2002 B1
6562211 Kunnecke May 2003 B1
6583408 Smith Jun 2003 B2
6600155 Andrien, Jr. Jul 2003 B1
6646256 Gourley Nov 2003 B2
6649907 Ebeling Nov 2003 B2
6670608 Taylor Dec 2003 B1
6690006 Valaskovic Feb 2004 B2
6713757 Tanner Mar 2004 B2
6717139 Taniguchi Apr 2004 B2
6723985 Schultz Apr 2004 B2
6744041 Sheehan Jun 2004 B2
6744046 Valaskovic Jun 2004 B2
6784424 Willoughby Aug 2004 B1
6794642 Bateman Sep 2004 B2
6803565 Smith Oct 2004 B2
6806468 Laiko Oct 2004 B2
6818889 Sheehan Nov 2004 B1
6861647 Reilly Mar 2005 B2
6875980 Bateman Apr 2005 B2
6878930 Willoughby Apr 2005 B1
6888132 Sheehan May 2005 B1
6914243 Sheehan Jul 2005 B2
6943347 Willoughby Sep 2005 B1
6949739 Franzen Sep 2005 B2
6949740 Sheehan Sep 2005 B1
6949741 Cody Sep 2005 B2
6956205 Park Oct 2005 B2
6977372 Valaskovic Dec 2005 B2
6979816 Tang Dec 2005 B2
6987264 Whitehouse Jan 2006 B1
6992299 Lee Jan 2006 B2
7015466 Takats Mar 2006 B2
7019289 Wang Mar 2006 B2
7034292 Whitehouse Apr 2006 B1
7041972 Bajic May 2006 B2
7049584 Whitehouse May 2006 B1
7053368 Thakur May 2006 B2
7064317 McLuckey et al. Jun 2006 B2
7071464 Reinhold Jul 2006 B2
7081618 Laprade Jul 2006 B2
7081621 Willoughby Jul 2006 B1
7095019 Sheehan Aug 2006 B1
7098452 Schneider Aug 2006 B2
7112785 Laramee Sep 2006 B2
7138626 Karpetsky Nov 2006 B1
7157698 Makarov Jan 2007 B2
7161145 Oser Jan 2007 B2
7196525 Sparkman Mar 2007 B2
7247495 Amirav Jul 2007 B2
7253406 Sheehan Aug 2007 B1
7332345 Darrach Feb 2008 B2
7423261 Truche Sep 2008 B2
7429731 Karpetsky Sep 2008 B1
7462826 Schneider Dec 2008 B2
7544933 Cooks Jun 2009 B2
7569812 Karpetsky Aug 2009 B1
7582864 Verentchikov Sep 2009 B2
7700913 Musselman Apr 2010 B2
7705297 Musselman Apr 2010 B2
7714281 Musselman May 2010 B2
7777181 Musselman Aug 2010 B2
7858926 Whitehouse Dec 2010 B1
7893408 Hieftje Feb 2011 B2
7923681 Collings Apr 2011 B2
7928364 Musselman Apr 2011 B2
7929138 Webb Apr 2011 B1
7982183 Makarov Jul 2011 B2
7982185 Whitehouse Jul 2011 B2
8003935 Robinson Aug 2011 B2
8026477 Musselman Sep 2011 B2
8044346 Kostiainen Oct 2011 B2
RE43078 Cody Jan 2012 E
8101910 Loboda Jan 2012 B2
8207497 Musselman Jun 2012 B2
8217341 Musselman Jul 2012 B2
8242459 Sun Aug 2012 B2
8278619 Makarov Oct 2012 B2
8304718 Ouyang Nov 2012 B2
8308339 Karpetsky Nov 2012 B2
8334507 Whitehouse Dec 2012 B1
8362418 Xu Jan 2013 B2
8410431 Ouyang Apr 2013 B2
8421005 Musselman Apr 2013 B2
8481922 Musselman Jul 2013 B2
8519354 Charipar Aug 2013 B2
8525109 Musselman Sep 2013 B2
8563945 Musselman Oct 2013 B2
RE44603 Cody Nov 2013 E
8592756 Ouyang Nov 2013 B2
8592758 Nilles Nov 2013 B1
8604423 Enke Dec 2013 B2
8648295 Enke Feb 2014 B2
8664000 Yang Mar 2014 B2
8686351 Ouyang Apr 2014 B2
8704167 Cooks Apr 2014 B2
8710437 Cooks Apr 2014 B2
8729496 Musselman May 2014 B2
8754365 Krechmer Jun 2014 B2
8766178 Ouyang Jul 2014 B2
8803085 Ouyang Aug 2014 B2
8816275 Ouyang Aug 2014 B2
8822949 Musselman Sep 2014 B2
8853627 Ouyang Oct 2014 B2
8859956 Ouyang Oct 2014 B2
8859957 Ouyang Oct 2014 B2
8859958 Ouyang Oct 2014 B2
8859959 Ouyang Oct 2014 B2
8890063 Ouyang Nov 2014 B2
20020005478 Hillenkamp Jan 2002 A1
20020121596 Laiko Sep 2002 A1
20020121598 Park Sep 2002 A1
20020162967 Atkinson Nov 2002 A1
20020185593 Doring Dec 2002 A1
20020185595 Smith Dec 2002 A1
20020185606 Smith Dec 2002 A1
20030052268 Doroshenko Mar 2003 A1
20040094706 Covey May 2004 A1
20040129876 Franzen Jul 2004 A1
20040159784 Doroshenko Aug 2004 A1
20040169137 Westphall Sep 2004 A1
20050079631 Laiko Apr 2005 A1
20050230635 Takats Oct 2005 A1
20050236374 Blankenship Oct 2005 A1
20050236565 Oser Oct 2005 A1
20060071665 Blake Apr 2006 A1
20060079002 Gologan Apr 2006 A1
20060097157 Ouyang May 2006 A1
20060163468 Wells Jul 2006 A1
20060249671 Karpetsky Nov 2006 A1
20060266941 Vestal Nov 2006 A1
20070114389 Karpetsky May 2007 A1
20070187589 Cooks Aug 2007 A1
20070228271 Truche Oct 2007 A1
20070278397 Bateman Dec 2007 A1
20080073548 Denton Mar 2008 A1
20080156985 Venter Jul 2008 A1
20080202915 Hieftje Aug 2008 A1
20080217254 Anderson Sep 2008 A1
20090168162 Ham et al. Jul 2009 A1
20090272893 Hieftje Nov 2009 A1
20100078550 Wiseman Apr 2010 A1
20100102222 Musselman Apr 2010 A1
20100140468 Musselman Jun 2010 A1
20100294925 Musselman Nov 2010 A1
20100301209 Ouyang Dec 2010 A1
20110042560 Ouyang Feb 2011 A1
20110101216 Musselman May 2011 A1
20110215798 Beer Sep 2011 A1
20120006983 Cody Jan 2012 A1
20120119082 Musselman May 2012 A1
20120145890 Goodlett Jun 2012 A1
20120199735 Krechmer Aug 2012 A1
20120208004 Wolcott Aug 2012 A1
20120223226 Rafferty Sep 2012 A1
20120280119 Musselman Nov 2012 A1
20120295276 Cooks Nov 2012 A1
20120312979 Cooks Dec 2012 A1
20120312980 Whitehouse Dec 2012 A1
20120322683 Liu et al. Dec 2012 A1
20130020482 Enke Jan 2013 A1
20130037710 Wu Feb 2013 A1
20130092832 Enke et al. Apr 2013 A1
20130105683 Ouyang May 2013 A1
20130112017 Ouyang May 2013 A1
20130112866 Ouyang May 2013 A1
20130112867 Ouyang May 2013 A1
20130126723 Ouyang May 2013 A1
20130181010 Ouyang Jul 2013 A1
20130273552 Ohashi Oct 2013 A1
20130273560 Cooks Oct 2013 A1
20130330714 Cooks Dec 2013 A1
20130344610 Cooks Dec 2013 A1
20140008529 Ouyang Jan 2014 A1
20140008532 Ouyang Jan 2014 A1
20140011282 Ouyang Jan 2014 A1
20140024822 Connolly et al. Jan 2014 A1
20140048697 Cooks Feb 2014 A1
20140051180 Cooks Feb 2014 A1
20140138538 Hieftje May 2014 A1
20140141466 Cooks May 2014 A1
20140158882 Ouyang Jun 2014 A1
20140231643 Ouyang Aug 2014 A1
20140264004 Cooks Sep 2014 A1
20140299764 Ouyang Oct 2014 A1
Foreign Referenced Citations (24)
Number Date Country
102007015542 Oct 2007 DE
1741120 Mar 2014 EP
2263578 Jul 1993 GB
50-106694 Aug 1975 JP
51-120288 Oct 1976 JP
52-91494 Aug 1977 JP
60-41748 Mar 1985 JP
2005-150027 Jun 2005 JP
WO03025973 Mar 2003 WO
WO03081205 Oct 2003 WO
WO2004068131 Aug 2004 WO
WO2005094389 Oct 2005 WO
WO2005104182 Nov 2005 WO
WO2007103693 Sep 2007 WO
WO2007140349 Dec 2007 WO
WO2007140351 Dec 2007 WO
WO2008046111 Apr 2008 WO
WO2008054393 May 2008 WO
WO2008082603 Jul 2008 WO
WO2009023361 Feb 2009 WO
WO2011072130 Jun 2011 WO
WO2011106656 Sep 2011 WO
WO2012100120 Jul 2012 WO
WO2014120552 Jul 2014 WO
Non-Patent Literature Citations (46)
Entry
Barber, M. et al., “Fast atom bombardment of solids (F.A.B.): a new ion source for mass spectrometry” J.Chem. Soc. Chem. Commun., 1981, 325.
Cody, R.B. et al., “Versatile New Ion Source for the Analysis of Materials in Open Air under Ambient Conditions” Anal. Chem., 2005, 77, 2297-2302.
Cooks, R.G. et al., “Ambient Mass Spectrometry”, Science, 2006, 311, 1566-1570.
Dalton, C.N. et al., “Electrospray-Atmospheric Sampling Glow Discharge Ionization Source for the Direct Analysis of Liquid Samples”, Analytical Chemistry, Apr. 1, 2003, vol. 75, No. 7, pp. 1620-1627.
Fenn et al., “Electrospray Ionization for Mass Spectrometry of Large Biomolecules,” Science, vol. 246, No. 4926, Oct. 6, 1989, pp. 64-71.
Garimella, S. et al., “Gas-flow assisted ion transfer for mass spectrometry”, J. Mass Spectrom. 2012, 17, 201-207.
Guzowski, J.P. Jr. et al., “Development of a Direct Current Gas Sampling Glow Discharge Ionization Source for the Time-of-Flight Mass Spectrometer”, J. Anal. At. Spectrom., 14, 1999, pp. 1121-1127.
Haddad, R., et al., “Easy Ambient Sonic-Spray Ionization Mass Spectrometry Combined with Thin-Layer Chromatography,” Analytical Chemistry, vol. 80, No. 8, Apr. 15, 2008, pp. 2744-2750.
Hill, C.A. et al., “A pulsed corona discharge switchable high resolution ion mobility spectrometer-mass spectrometer”, Analyst, 2003, 128, pp. 55-60.
Hiraoka, K. et al., “Atmospheric-Pressure Penning Ionization Mass Spectrometry”, Rapid Commun. Mass Spectrom., 18, 2004, pp. 2323-2330.
Hites, Gas Chromatography Mass Spectrometry, Chapter 39, Jun. 24, 1997, pp. 609-626.
Karas, M. et al., “Laser desorption ionization of proteins with molecular masses exceeding 10,000 daltons” Anal. Chem. 1988, 60, 2299-2301.
Kojiro, D.R. et al., “Determination of C.sub.1-C.sub.4 Alkanes by Ion Mobility Spectrometry”, Anal. Chem., 63, 1991, pp. 2295-2300.
Leymarie, N. et al., “Negative Ion Generation Using a MAB Source”, presented at the Annual Meeting of the American Society of Mass Spectrometry, 2000.
McLuckey, S.A. et al., “Atmospheric Sampling Glow Discharge Ionization Source for the Determination of Trace Organic Compounds in Ambient Air”, Anal. Chem., 60, 1988, pp. 2220-2227.
Otsuka, K. et al., “An Interface for Liquid Chromatograph/Liquid Ionization Mass Spectrometer”, Analytical Sciences, Oct. 1988, vol. 4, pp. 467-472.
Takáts et al., “Mass Spectrometry Sampling Under Ambient Conditions with Desorption Electrospray Ionization,” Science, vol. 306, No. 5695, Oct. 15, 2004, pp. 471-473.
Tanaka, K. et al., “Protein and polymer analyses up to m/z 100,000 by laser ionization time-of-flight”, Rapid Commun. Mass Spectrom., 1988, 2, 151-153.
Tembreull, R., et al., “Pulsed Laser Desorption with Resonant Two-Photon Ionization Detection in Supersonic Beam Mass Spectrometry,” Anal. Chem., vol. 58, 1986, pp. 1299-1303, p. 1299.
Zhao, J. et al., Liquid Sample Injection Using an Atmospheric Pressure Direct Current Glow Discharge Ionization Source, Analytical Chemistry, Jul. 1, 1992, vol. 64, No. 13, pp. 1426-1433.
International Search Report, Application No. PCT/US2007/63006, Feb. 5, 2008.
Extended European Search Report, Application No. 07757665.0 PCT/US2007/063006 Jan. 7, 2010, 8 pages.
Article 94(3) European Communication, Application No. 07757665.0 PCT/US2007/063006, Mar. 14, 2012, 9 pages.
International Search Report, Application No. PCT/US2007/69823, Feb. 15, 2008.
Extended European Search Report, Application No. 07797812.0 PCT/US2007/069823, Apr. 4, 2010, 9 pages.
Article 94(3) European Communication, Application No. 07797812.0 PCT/US2007/069823, Jul. 27, 2012, 9 pages.
International Search Report, Application No. PCT/US2007/69821, Feb. 7, 2008.
Extended European Search Report, Application No. 07797811.2 PCT/US2007/069821, Mar. 25, 2010, 9 pages.
European Summons, Application No. 07797811.2 PCT/US2007/069821, Feb. 18, 2013, 39 pages.
International Search Report, Application No. PCT/US2007/81439, Mar. 20, 2008.
Extended European Search Report, Application No. 07844307.4 PCT/US2007/081439, Apr. 14, 2010, 12 pages.
Japanese Office Action, Application No. 2008-558459 PCT/US2007/063006, Jan. 19, 2012, 4 pages.
Unofficial Translation of Japanese Office Action, Application No. 2008-558459 PCT/US2007/063006, Jan. 19, 2012, 5 pages.
Chinese Office Action, Application No. 200780015974.5 PCT/US2007/063006, Feb. 2, 2012, 5 pages.
Chinese Office Action, Application No. 200780015974.5 PCT/US2007/063006, Sep. 25, 2012, 8 pages.
Chinese Office Action, Application No. 200780015974.5 PCT/US2007/063006, Dec. 26, 2012, 7 pages.
International Search Report, Application No. PCT/US2012/000061, Aug. 6, 2013.
Oral Proceedings European Communication, Application No. 07757665.0 PCT/US2007/063006, Mar. 9, 2013, 5 pages.
Korean Patent Application 7024130/2008, Jun. 29, 2013, 6 pages.
Article 94(3) European Communication, Application No. 07797811.2 PCT/US2007/069821, Feb. 2, 2012, 8 pages.
Summons Application No. 07797811.2 PCT/US2007/069821, Feb. 18, 2013, 12 pages.
The AccuTOF-DART Mass Spectrometer, Jan. 1, 2006, pp. 1-6; www.jeolusa.com/SERVICESUPPORT/ApplicationsResources/AnalyticalInstruments/Docume nts/Downloads/tabid/337/DMXModule/693/CommandCore—Download/Default.aspx?EntryId=171.
Busch, Kenneth L., Desorption Ionization Mass Spectrometry, J. Mass Spectrometry, vol. 30, pp. 233-240 (1995).
Harris, Glenn A. et al., Ambient Sampling/Ionization Mass Spectrometry: Applications and Current Trends, Apr. 15, 2011, Anal. Chem. 2011, 83, pp. 4508-4538.
Harris, Glenn A. et al., Simulations and Experimental Investigation of Atmospheric Transport in an Ambient Metastable-Induced Chemical Ionization Source, Anal. Chem. 2009, 81, pp. 322-329.
Kauppila, Tiina J., et al., Desorption atmospheric pressure photoionization—mass spectrometry in routine analysis of confiscated drugs, Forensic Science International 210 (2011) pp. 206-212.
Provisional Applications (1)
Number Date Country
61476380 Apr 2011 US
Continuations (1)
Number Date Country
Parent 13449615 Apr 2012 US
Child 14530621 US