AU4572299A – Resilient containers for hyperpolarized gases
– Google Patents
AU4572299A – Resilient containers for hyperpolarized gases
– Google Patents
Resilient containers for hyperpolarized gases
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Publication number
AU4572299A
AU4572299A
AU45722/99A
AU4572299A
AU4572299A
AU 4572299 A
AU4572299 A
AU 4572299A
AU 45722/99 A
AU45722/99 A
AU 45722/99A
AU 4572299 A
AU4572299 A
AU 4572299A
AU 4572299 A
AU4572299 A
AU 4572299A
Authority
AU
Australia
Prior art keywords
container
gas
hyperpolarized
chamber
container according
Prior art date
1998-06-17
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
AU45722/99A
Other versions
AU745398B2
(en
Inventor
Daniel M. Deaton
Bastiaan Driehuys
Kenton C. Hasson
David L. Zollinger
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Medi Physics Inc
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Medi Physics Inc
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1998-06-17
Filing date
1999-06-16
Publication date
2000-01-05
1998-07-30
Priority claimed from US09/126,448
external-priority
patent/US6128918A/en
1999-06-16
Application filed by Medi Physics Inc
filed
Critical
Medi Physics Inc
2000-01-05
Publication of AU4572299A
publication
Critical
patent/AU4572299A/en
2002-03-21
Application granted
granted
Critical
2002-03-21
Publication of AU745398B2
publication
Critical
patent/AU745398B2/en
2019-06-16
Anticipated expiration
legal-status
Critical
Status
Ceased
legal-status
Critical
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Classifications
G—PHYSICS
G01—MEASURING; TESTING
G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
G01R33/00—Arrangements or instruments for measuring magnetic variables
G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
G01R33/28—Details of apparatus provided for in groups G01R33/44 – G01R33/64
G01R33/282—Means specially adapted for hyperpolarisation or for hyperpolarised contrast agents, e.g. for the generation of hyperpolarised gases using optical pumping cells, for storing hyperpolarised contrast agents or for the determination of the polarisation of a hyperpolarised contrast agent
A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
A61K49/00—Preparations for testing in vivo
A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
A61K49/18—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes
A61K49/1806—Suspensions, emulsions, colloids, dispersions
A61K49/1815—Suspensions, emulsions, colloids, dispersions compo-inhalant, e.g. breath tests
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C13/00—Details of vessels or of the filling or discharging of vessels
F17C13/002—Details of vessels or of the filling or discharging of vessels for vessels under pressure
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C13/00—Details of vessels or of the filling or discharging of vessels
F17C13/005—Details of vessels or of the filling or discharging of vessels for medium-size and small storage vessels not under pressure
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C3/00—Vessels not under pressure
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2201/00—Vessel construction, in particular geometry, arrangement or size
F17C2201/01—Shape
F17C2201/0128—Shape spherical or elliptical
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2201/00—Vessel construction, in particular geometry, arrangement or size
F17C2201/01—Shape
F17C2201/0147—Shape complex
F17C2201/0157—Polygonal
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2201/00—Vessel construction, in particular geometry, arrangement or size
F17C2201/01—Shape
F17C2201/0176—Shape variable
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2203/00—Vessel construction, in particular walls or details thereof
F17C2203/03—Thermal insulations
F17C2203/0304—Thermal insulations by solid means
F17C2203/0308—Radiation shield
F17C2203/032—Multi-sheet layers
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2203/00—Vessel construction, in particular walls or details thereof
F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
F17C2203/0602—Wall structures; Special features thereof
F17C2203/0604—Liners
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2203/00—Vessel construction, in particular walls or details thereof
F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
F17C2203/0602—Wall structures; Special features thereof
F17C2203/0612—Wall structures
F17C2203/0614—Single wall
F17C2203/0619—Single wall with two layers
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2203/00—Vessel construction, in particular walls or details thereof
F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
F17C2203/0634—Materials for walls or layers thereof
F17C2203/0636—Metals
F17C2203/0646—Aluminium
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2203/00—Vessel construction, in particular walls or details thereof
F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
F17C2203/0634—Materials for walls or layers thereof
F17C2203/0658—Synthetics
F17C2203/066—Plastics
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2203/00—Vessel construction, in particular walls or details thereof
F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
F17C2203/068—Special properties of materials for vessel walls
F17C2203/0697—Special properties of materials for vessel walls comprising nanoparticles
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
F17C2205/01—Mounting arrangements
F17C2205/0103—Exterior arrangements
F17C2205/0115—Dismountable protective hulls
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
F17C2205/0323—Valves
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
F17C2205/0323—Valves
F17C2205/0329—Valves manually actuated
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
F17C2205/0352—Pipes
F17C2205/0364—Pipes flexible or articulated, e.g. a hose
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
F17C2205/0388—Arrangement of valves, regulators, filters
F17C2205/0394—Arrangement of valves, regulators, filters in direct contact with the pressure vessel
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2221/00—Handled fluid, in particular type of fluid
F17C2221/01—Pure fluids
F17C2221/016—Noble gases (Ar, Kr, Xe)
F17C2221/017—Helium
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2221/00—Handled fluid, in particular type of fluid
F17C2221/07—Hyperpolarised gases
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
F17C2223/0107—Single phase
F17C2223/0123—Single phase gaseous, e.g. CNG, GNC
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2260/00—Purposes of gas storage and gas handling
F17C2260/01—Improving mechanical properties or manufacturing
F17C2260/013—Reducing manufacturing time or effort
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2260/00—Purposes of gas storage and gas handling
F17C2260/01—Improving mechanical properties or manufacturing
F17C2260/018—Adapting dimensions
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2260/00—Purposes of gas storage and gas handling
F17C2260/02—Improving properties related to fluid or fluid transfer
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2260/00—Purposes of gas storage and gas handling
F17C2260/02—Improving properties related to fluid or fluid transfer
F17C2260/026—Improving properties related to fluid or fluid transfer by calculation
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2260/00—Purposes of gas storage and gas handling
F17C2260/05—Improving chemical properties
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2270/00—Applications
F17C2270/02—Applications for medical applications
F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
F17C2270/00—Applications
F17C2270/02—Applications for medical applications
F17C2270/025—Breathing
Abstract
A resilient multi-layer container (10) is configured to receive a quantity of hyperpolarized gas and includes a wall with at least two layers (41,44), a first layer with a surface which minimizes contact-induced spin-relaxation and second layer which, e.g., is substantially impermeable to oxygen. The container is especially suitable for collecting and transporting 3 He. The resilient container can be formed of material layers which are concurrently responsive to pressure such as polymers, deuterated polymers, or metallic films. The container can include a capillary stem (26s) and/or a port or valve isolation means (31i) to inhibit the flow of gas from the main volume of the container during transport. The resilient container can be configured to directly deliver the hyperpolarized noble gas to a target interface by deflating or collapsing the inflated resilient container.
Description
WO 99/66255 PCTIUS99/13597 RESILIENT CONTAINERS FOR HYPERPOLARIZED GASES This invention was made with Government support under AFOSR Grant No. F41624-97-C-9001 and NIH Grant No. 1 R43 HL59022-01. The United States Government has certain rights in this invention. Related Applications This application claims priority from United States Provisional Application No. 60/089,692 filed on June 17, 1998. Related Patent Application Serial No. 09/126,448 filed on July 30, 1998 is co-pending. The contents of these documents are 10 incorporated by reference as if recited in full herein. Field of the Invention The present invention relates to processing, storage, transport and delivery containers for hyperpolarized noble gases. 15 Background of the Invention Conventionally, Magnetic Resonance Imaging (“MRI”) has been used to produce images by exciting the nuclei of hydrogen molecules (present in water protons) in the human body. However, it has recently been discovered that polarized 20 noble gases can produce improved images of certain areas and regions of the body which have heretofore produced less than satisfactory images in this modality. Polarized Helium-3 (” 3 He”) and Xenon-129 (“1 29 Xe”) have been found to be particularly suited for this purpose. Unfortunately, as will be discussed further below, the polarized state of the gases are sensitive to handling and environmental conditions 25 and. undesirably. can decay from the polarized state relatively quickly.
WO 99/66255 PCT/US99/13597 Hyperpolarizers are used to produce and accumulate polarized noble gases. Hyperpolarizers artificially enhance the polarization of certain noble gas nuclei (such as 1 29 Xe or 3 He) over the natural or equilibrium levels, i.e., the Boltzmann polarization. Such an increase is desirable because it enhances and increases the 5 MRI signal intensity, allowing physicians to obtain better images of the substance in the body. See U. S. Patent No. 5,545,396 to Albert et al., the disclosure of which is hereby incorporated herein by reference as if recited in full herein. In order to produce the hyperpolarized gas, the noble gas is typically blended with optically pumped alkali metal vapors such as rubidium (“Rb”). These optically 10 pumped metal vapors collide with the nuclei of the noble gas and hyperpolarize the noble gas through a phenomenon known as “spin-exchange”. The “optical pumping” of the alkali metal vapor is produced by irradiating the alkali-metal vapor with circularly polarized light at the wavelength of the first principal resonance for the alkali metal (e.g., 795 nm for Rb). Generally stated, the ground state atoms become 15 excited, then subsequently decay back to the ground state. Under a modest magnetic field (10 Gauss), the cycling of atoms between the ground and excited states can yield nearly 100% polarization of the atoms in a few microseconds. This polarization is generally carried by the lone valence electron characteristics of the alkali metal. In the presence of non-zero nuclear spin noble gases, the alkali-metal vapor atoms can 20 collide with the noble gas atoms in a manner in which the polarization of the valence electrons is transferred to the noble-gas nuclei through a mutual spin flip “spin exchange”. After the spin-exchange has been completed, the hyperpolarized gas is separated from the alkali metal prior to introduction into a patient to form a non-toxic 25 or sterile composition. Unfortunately, during and after collection, the hyperpolarized gas can deteriorate or decay (lose its hyperpolarized state) relatively quickly and therefore must be handled, collected, transported, and stored carefully. The “T 1 ” decay constant associated with the hyperpolarized gas’s longitudinal relaxation time is often used to describe the length of time it takes a gas sample to depolarize in a given 30 container. The handling of the hyperpolarized gas is critical, because of the sensitivity of the hyperpolarized state to environmental and handling factors and the potential for undesirable decay of the gas from its hyperpolarized state prior to the planned end use, i.e., delivery to a patient. Processing, transporting, and storing the -2- WO 99/66255 PCTIUS99/13597 hyperpolarized gases — as well as delivery of the gas to the patient or end user — can expose the hyperpolarized gases to various relaxation mechanisms such as magnetic gradients, ambient and contact impurities, and the like. Typically. hyperpolarized gases such as 1 29 Xe and 3 He have been collected in 5 relatively pristine environments and transported in specialty glass containers such as rigid Pyrex TM containers. However, to extract the majority of the gas from these rigid containers, complex gas extraction means are typically necessary. Hyperpolarized gas such as 3 He and 1 2 Xe has also been temporarily stored in single layer resilient Tedlar® and Teflon® bags. However, these containers have produced relatively short 10 relaxation times. One way of inhibiting the decay of the hyperpolarized state is presented in U.S. Patent No. 5.612,103 to Driehuys et al. entitled “Coatings for Production of Hyperpolarized Noble Gases.” Generally stated, this patent describes the use of a modified polymer as a surface coating on physical systems (such as a PyrexTM 15 container) which contact the hyperpolarized gas to inhibit the decaying effect of the surface of the collection chamber or storage unit. However. there remains a need to address and reduce dominant and sub dominant relaxation mechanisms and to decrease the complexity of physical systems required to deliver the hyperpolarized gas to the desired subject. Minimizing the 20 effect of one or more of these factors can increase the life of the product by increasing the duration of the hyperpolarized state. Such an increase is desired so that the hyperpolarized product can retain sufficient polarization to allow effective imaging at delivery when transported over longer transport distances and/or stored for longer time periods from the initial polarization than has been viable previously. 25 Objects and Summary of the Invention In view of the foregoing, it is an object of the present invention to process and collect hyperpolarized gas in improved resilient containers which are configured to inhibit depolarization in the collected polarized gas and to provide a longer Ti for 3 He and 1 29 Xe than has been achieved in the past. 30 It is another object of the present invention to provide an improved container which can be configured to act as both a transport container and a delivery mechanism WO 99/66255 PCT/US99/13597 to reduce the amount of handling or physical interaction required to deliver the hyperpolarized gas to a subject. It is a further object of the present invention to provide an improved, relatively non-complex and economical container which can prolong the polarization life of the 5 gas in a container and reduce the amount of polarization lost during storage, transport, and delivery. It is yet another object of the invention to provide methods, surface materials and containers which will minimize the depolarizing effects of the hyperpolarized state of the gas (especially 3 He) attributed to one or more of paramagnetic impurities, 10 oxygen exposure, and surface relaxation. It is an additional object of the present invention to provide a method to determine the gas solubility in polymers or liquids with respect to hyperpolarized 129 Xe or ‘He. These and other objects are satisfied by the present invention which is directed 15 to resilient containers which are configured to reduce surface or contact-induced depolarization by forming an inner contact surface of a first material (of a predetermined thickness) which acts to minimize the associated surface or contact depolarization. In particular, a first aspect of the invention is directed to a container for receiving a quantity of hyperpolarized gas. The container includes at least one 20 wall comprising inner and outer layers configured to define an enclosed chamber for holding a quantity of hyperpolarized gas. The inner layer has a predetermined thickness and an associated relaxivity value which inhibits contact-induced polarization loss of the hyperpolarized gas. The outer layer defines an oxygen shield overlying the inner layer. Of course, the two layers can be integrated into one, if the 25 material chosen acts as a polarization-friendly contact surface and is also resistant to the introduction of oxygen molecules into the chamber of the container. The container also includes a quantity of hyperpolarized noble gas and a port attached to the wall in fluid communication with the chamber for capturing and releasing the hyperpolarized gas therethrough. 30 Preferably, the container material(s) are selected to result in effective TI’s of greater than 6 hours for 3 He and greater than about 4 hours for 1 29 Xe due to the material alone. It is also preferred that the oxygen shield is configured to reduce the migration of oxygen into the container to less than about 5 x 10~6 amgt/min, and more -4- WO 99/66255 PCT/US99/13597 preferably to less than about lx10 7 amgt/min. It is additionally preferred that the inner layer thickness (“Lth”) is at least as thick as the polarization decay length scale (“Lp”) which can be determined by the equation: 5 L1, = JT, D, where T, is the noble gas nuclear spin relaxation time in the polymer and Dp is the noble gas diffusion coefficient in the polymer. Advantageously, using a contact surface which has a thickness which is larger 10 than the polarization decay length scale can minimize or even prevent the hyperpolarized gas from sampling the substrate (the material underlying the first layer). Indeed, for hyperpolarized gases which can have a high diffusion constant (such as 3 He), surfaces with polymer coatings substantially thinner than the polarization decay length scale can have a more detrimental effect on the polarization 15 than surfaces having no such coating at all. This is because the polarized gas can be retained within the underlying material and interact with the underlying or substrate material for a longer time, potentially causing more depolarization than if the thin coating is not present. An additional aspect of the present invention is directed to a container with a 20 wall formed of a single or multiple layers of materials which defines an expandable chamber. The inner surface of the wall is formed of a material which has a low relaxivity value for the (non-toxic) hyperpolarized fluid (hyperpolarized gas which is at least partially dissolved or liquefied) held therein . The wall is configured to define an oxygen shield to inhibit the migration of oxygen into the chamber. The T 1 of the 25 hyperpolarized fluid held in the container is greater than about 6 hours. In a preferred embodiment, the container of the instant invention is configured to receive hyperpolarized 3 He and the inner layer is at least 16-20 microns thick. In another preferred embodiment, the container is an expandable polymer bag. Preferably, the polymer bag includes a metallized coating positioned over the polymer 30 which suppresses the migration of oxygen into the polymer and ultimately into the polarized gas holding chamber. In another preferred embodiment, a third layer is added onto the metallized layer (opposite the polymer chamber) for puncture resistance. Advantageously, the captured hyperpolarized gas can be delivered to the WO 99/66255 PCT/US99/13597 inhalation interface of a subject by exerting pressure on the bag to collapse the bag and cause the gases to exit the chamber. This, in turn, removes the requirement for a supplemental delivery mechanism. It is additionally preferred that the container use seals such as 0-rings which are substantially free of paramagnetic impurities. The 5 proximate position of the seal with the hyperpolarized gas can make this component a dominant factor in the depolarization of the gas. Accordingly, it is preferred that the seals or 0-rings be formed from substantially pure polyolefins such as polyethylene, polypropylene, copolymers and blends thereof. Of course, fillers which are friendly to hyperpolarization can be used (such as substantially pure carbon black and the 10 like). Alternatively, the 0-ring or seal can be coated with a surface material such as LDPE or deuterated HDPE or other low-relaxivity and property material and/or also preferably materials which have a low permeability for the hyperpolarized gas held in the chamber. In addition, the container can be configured such that once the gas is captured in the container to isolate a major portion of the hyperpolarized gas in the 15 container away from potentially depolarizing components (such as fittings, valves, and the like) during transport and/or storage. Similar to the preferred embodiment discussed above, another aspect of the present invention is a multi-layer resilient container for holding hyperpolarized gas. The container comprises a first layer of a first material configured to define an 20 expandable chamber to hold a quantity of hyperpolarized gas therein. Preferably, the first layer has a predetermined thickness sufficient to inhibit surface or contact depolarization of the hyperpolarized gas held therein wherein the first layer material has a relaxivity value “T”. It is also preferred that the relaxivity value “T” is less than about 0.0012cm/min for 3 He and less than about 0.01cm/min for 1 29 Xe. The container 25 also includes a second layer of a second material positioned such that the first layer is between the second layer and the chamber, wherein the first and second layers are concurrently responsive to the application of pressure and one or both of the first and second layers acts as an oxygen shield to suppress oxygen permeability into the chamber. 30 Additional layers of materials can be positioned intermediate the first layer and the second layer. In one preferred embodiment, hyperpolarized gas has a low relaxivity value in the first layer material and the second layer preferably comprises a material which can shield the migration of the oxygen into the first layer. In another -6- WO 99/66255 PCTIUS99/13597 preferred embodiment, the resilient container has a first layer formed of a metal film (which can act both as an oxygen shield and contact surface). In this embodiment, it is preferred that the relaxivity values are less than about .0023 cm/min and .0008 cm/min for 1 29 Xe and 3He respectively. Stated differently, it is preferred that the 5 hyperpolarized gas have a high mobility on the metal surface or small absorption energy relative to the metal contact surface such that the T 1 of the gas in the container approaches > 50% of its theoretical limit. An additional aspect of the present invention is directed to a method for storing, transporting, and delivering hyperpolarized gas to a target. The method 10 includes introducing a quantity of hyperpolarized gas into a multi-layer resilient container. The container has a wall comprising at least one material which provides an oxygen shield (i.e., is resistant to the transport of oxygen into the container). Preferably, the container is expanded to capture the quantity of hyperpolarized gas. The container is sealed to contain the hyperpolarized gas therein. The container is 15 transported to a site remote from the hyperpolarization site. The hyperpolarized gas is delivered to a target by compressing the chamber and thereby forcing the hyperpolarized gas to exit therefrom. Preferably, in order to maintain the hyperpolarized state, the container is substantially continuously, from the time of polarization to the delivery, shielded and/or exposed to a proximately maintained 20 homogeneous magnetic field to protect it from undesired external magnetic fields and/or field gradients. It is further preferred that the container be configured to be re useable (after re-sterilization) to ship additional quantities of hyperpolarized gases. Similarly, a further aspect of the present invention is configuring single or multi-layer resilient bags as described above with a capillary stem. The capillary stem 25 is configured to restrict the flow of the hyperpolarized gas from the container when the valve is closed. The capillary stem is preferably positioned intermediate the container port and a valve member and, as such, forms a portion of the hyperpolarized gas (or liquid) entrance and exit path. The capillary stem is preferably configured with an inner passage which is sized and configured to inhibit the flow of the 30 hyperpolarized gas and includes a gas contact surface formed of a polarization friendly material. The capillary stem is preferably operably associated with a valve for the resilient container to allow the gas to be releasably captured and yet protected from any potentially depolarizing affect of the gas when the valve is closed. -7- WO 99/66255 PCTIUS99/13597 Similarly. a further aspect of the present invention is configuring single or multi-laver resilient bags as described above with an isolation means for directing the gas or fluid away from the bag port during transport and storage. As such the isolation means inhibits a major portion of the hyperpolarized gas or fluid from 5 contacting selected components (fittings, valves, O-rings) operably associated with the bag. In a preferred embodiment, the isolation means is provided by a clamp positioned to compress the portion of the bag proximate to the port to inhibit the movement of gas thereabove. An additional aspect of the present invention is a method for preparing an 10 expandable storage container for receiving a quantity of hyperpolarized gas. The method includes providing a quantity of substantially pure purge gas such as nitrogen or helium (preferably Grade 5 or better) into the hyperpolarized gas container and expanding the hyperpolarized gas container. The container is then collapsed to remove the purge gas. The oxygen in the container walls is outgassed by decreasing 15 the oxygen partial pressure in the container, thereby causing a substantial amount of the oxygen trapped in the walls of the container to migrate into the chamber of the container in the gas phase where it can be removed. Preferably, after the outgassing step, the container is filled with a quantity of storage gas such as nitrogen (again, preferably Grade 5 or better). The gas is introduced into the container at a pressure 20 which reduces the pressure differential across the walls of the container to inhibit further outgassing of the container. Preferably, the container is then stored for future use (the use being spaced apart in time from the point of preconditioning). The storage nitrogen and outgassed oxygen are removed from the container before filling with a quantity of hyperpolarized gas. Preferably, after removal from storage and 25 prior to use, the nitrogen is removed by evacuating the container before filling with a quantity of hyperpolarized gas. Another aspect of the present invention is directed to a method for determining the hyperpolarized gas (129Xe or 3He) solubility in a (unknown) polymer or a particular fluid. The method includes introducing a first quantity of hyperpolarized 30 noble gas into a container having a known free volume and measuring a first relaxation time of the hyperpolarized gas in the container. A substantially clean sample of desired material is positioned into the container and a second quantity of hyperpolarized noble gas is introduced into the container. A second relaxation time of -8- WO 99/66255 PCT/US99/13597 the second hyperpolarized gas is measured in the container with the sample material. The gas solubility of the sample is determined based on the difference between the two measured relaxation times. The material sample can be a structurally rigid sample (geometrically fixed) with a known geometric surface area/volume which is 5 inserted into the free volume of the chamber or container. Alternatively, the material sample can be a liquid which partially fills chamber. Advantageously, the methods and containers of the present invention can improve the relaxation time (lengthen T 1 ) of the hyperpolarized gas or liquid or combinations of same held therein. The containers are configured such that the 10 surface contacting the hyperpolarized gas (the hyperpolarized gas contact surface) has a minimum depth or thickness of a low-relaxivity value material relative to the hyperpolarized noble gas. Further, the containers are configured to also inhibit oxygen migration into the gas chamber of the container. In addition, the container itself can define the contact surface by forming the container out of a resilient material 15 such as a metallic or polymer bag. Preferably, the bags are configured to inhibit the hyperpolarized gas from contacting potentially depolarizing components associated with the bag during transport or storage. The container is preferably a multi-layer container wherein each material layer provides one or more of strength, puncture resistance, and oxygen resistance to the 20 container. Further, at least the inner surface is configured to provide a polarization friendly contact surface. This resilient configuration provides a relatively non complex container and increased Ti’s and can conveniently be re-used. The gas contact surface is preferably formed of either a polymer or a high purity metal. Additionally, the resilient or collapsible containers can be used to deliver the 25 gas into the patient interface without the need for additional delivery vehicles/ equipment. This can reduce the exposure, handling, and physical manipulation of the hyperpolarized gas which, in turn, can increase the polarization life of the hyperpolarized gas. Resilient containers with high purity contact surfaces can be extremely advantageous for both 1 29 Xe and 3 He as well as other hyperpolarized gases; 30 however, the expandable (polymer) container and coatings/layers are especially suited for hyperpolarized 3 He. Further, the instant invention preferably positions the container with the hyperpolarized gas in a homogenous magnetic field within a -9- WO 99/66255 PCT/US99/13597 shipping container to shield the gas from stray magnetic fields, especially deleterious oscillating fields which can easily dominate other relaxation mechanisms. Additionally, the present invention can be used to determine the gas solubility in polymers or fluids which in the past has proven difficult and sometimes inaccurate, 5 especially for helium. Advantageously, one aspect of the present invention now provides a way to model the predictive behavior of surface materials and is particularly suited to determining the relaxation properties of polymers used as contact materials in physical systems used to collect, process, or transport hyperpolarized gases. For 10 example, the present invention successfully provides relaxation properties of various materials (measured and/or calculated). These relaxation values can be used to determine the relaxation time (TI) of hyperpolarized gas in containers corresponding to the solubility of the gas, the surface area of the contact material, and the free gas volume in the container. This information can be advantageously used to extend the 15 hyperpolarized life of the gas in containers over those which were previously achievable in high-volume production systems. The foregoing and other objects and aspects of the present invention are explained in detail herein. 20 Brief Description of the Drawings Figure 1 is a schematic diagram of a spin-down station used to measure relaxation times according to one aspect of the present invention. Figure 2 is a graph showing the polarization level of a gas associated with the distance x the gas moves into a polymer. 25 Figure 3 is a graph showing the results of the standardized relaxation times plotted against solubility (measured and theoretical) for various materials (Ticc representing the relaxation time for 1 29 Xe hyperpolarized gas in a one cubic centimeter sphere). Figure 4 is a graph similar to Figure 3 showing the results of standardized 30 relaxation times for 3 He. Figure 5 is a detailed chart of experimental material values for Xenon and Helium. -10- WO 99/66255 PCTIUS99/13597 Figure 6 is a detailed chart of predicted material values for Xenon and Helium. Figure 7 is a perspective view of a hyperpolarized gas container according to one embodiment of the present invention in a deflated state. 5 Figure 8 is a perspective view of the container of Figure 7, shown in an inflated state. Figure 9 is a sectional view of an alternate embodiment of a container according to the present invention. Figure 10 is an enlarged partial cutaway section view of the container wall 10 according to another embodiment of the present invention. Figure 11 is an enlarged partial cutaway section view of an additional embodiment of a container wall according to the present invention. Figure 12 is an enlarged partial cutaway section view of yet another embodiment of a container wall according to the present invention. 15 Figure 13 is a perspective view of a preferred embodiment of a container with a seal according to the present invention. Figure 14 illustrates the container of Figure 13 with an alternative external seal according to an additional embodiment of the present invention. Figure 15 illustrates another container with an alternative seal arrangement 20 according to another embodiment of the present invention. Figure 15A is an exploded view of the container shown in Figure 15. Figure 16 is a side perspective view of a shielded shipping receptacle configured to receive the container according to one embodiment of the present invention. 25 Figure 17 is a schematic illustration of the resilient container of Figure 13 shown attached to a user interface adapted to receive the container for delivering the hyperpolarized gas therein to the user according to one embodiment of the present invention. Figure 18 shows the container of Figure 17 in a deflated condition after 30 forces on the container cause the hyperpolarized gas to exit the container and enter the target. Figure 19 is a schematic illustration of the container of Figure 15 shown attached to a user interface according to one embodiment of the present invention. -11- WO 99/66255 PCTIUS99/13597 Figure 20 is a block diagram of a method for determining gas solubility in a polymer according to one embodiment of the present invention. Figures 21A-21C are perspective views of an alternative embodiment of a container with a port isolation means according to the present invention. 5 Detailed Description of the Preferred Embodiments The present invention will now be described more fully hereinafter with reference to the accompanying figures, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in many different 10 forms and should not be construed as limited to the embodiments set forth herein. Like numbers refer to like elements throughout. Layers and regions may be exaggerated for clarity. For ease of discussion, the term “hyperpolarized gas” will be used to describe a hyperpolarized gas alone, or a hyperpolarized gas which contacts or combines with one or more other components whether gaseous, liquid, or solid. Thus, 15 the hyperpolarized gas described herein can be a hyperpolarized gas composition/ mixture (non-toxic such that it is suitable for in vivo introduction) such that the hyperpolarized noble gas can be combined with other noble gases and/or other inert or active components. Also, as used herein, the term “hyperpolarized gas” can include a product where the hyperpolarized gas is dissolved into another liquid (such as a 20 carrier) or processed such that it transforms into a substantially liquid state, i.e., “a liquid polarized gas”. Thus, although the term includes the word “gas”, this word is used to name and descriptively track the gas produced via a hyperpolarizer to obtain a polarized “gas” product. In summary, as used herein, the term “gas” has been used in certain places to descriptively indicate a hyperpolarized noble gas which can include 25 one or more components and which may be present in one or more physical forms. Preferred hyperpolarized noble gases (either alone or in combination) are listed in Table I. This list is intended to be illustrative and non-limiting. -12- WO 99/66255 PCT/US99/13597 TABLE I Hyperpolarizable Noble Gases Isotope Natural Abundance (%) Nuclear Spin 3He ~10-6 1/2 21 Ne 0.27 3/2 83Kr 11.5 9/2 1 29 Xe 26.4 1/2 31 Xe 21.2 3/2 Hyperpolarization 5 Various techniques have been employed to polarize, accumulate and capture polarized gases. For example, U.S. Patent No. 5,642,625 to Cates et al. describes a high volume hyperpolarizer for spin polarized noble gas and U.S. Patent No. 5,809,801 to Cates et al. describes a cryogenic accumulator for spin-polarized 1 29 Xe. The disclosures of this patent and application are hereby incorporated herein by 10 reference as if recited in full herein. As used herein, the terms “hyperpolarize” and “polarize” are used interchangeably and mean to artificially enhance the polarization of certain noble gas nuclei over the natural or equilibrium levels. Such an increase is desirable because it allows stronger imaging signals corresponding to better MRI images of the substance and a targeted area of the body. As is known by those of skill 15 in the art, hyperpolarization can be induced by spin-exchange with an optically pumped alkali-metal vapor or alternatively by metastability exchange. See U.S. Patent No. 5,545,396 to Albert et al. The alkali metals capable of acting as spin exchange partners in optically pumped systems include any of the alkali metals. Preferred alkali metals for this hyperpolarization technique include Sodium-23, 20 Potassium-39, Rubidium-85, Rubidium-87, and Cesium-133. Alkali metal isotopes, and their relative abundance and nuclear spins are listed in Table II, below. This list is intended to be illustrative and non-limiting. -13- WO 99/66255 PCTIUS99/13597 TABLE II Alkali Metals Capable of Spin Exchange Isotope Natural Abundance (%) Nuclear Spin 23 Na 100 3/2 3 9K 93.3 3/2 8Rb 72.2 5/2 87 Rb 27.8 3/2 mCs 100 7/2 Alternatively, the noble gas may be hyperpolarized using metastability exchange. (See e.g., Schearer, L. D., Phys. Rev., 180:83 (1969); Laloe, F. et al., AIP 5 ConfProx #131 (Workshop on Polarized 3 He Beams and Targets) (1984)). The technique of metastability exchange involves direct optical pumping of, for example, 3He without need for an alkali metal intermediary. The method of metastability exchange usually involves the excitation of ground state 3He atoms (1 ‘So) to a metastable state (2 3
S
1 ) by weak radio frequency discharge. The 23SI atoms are then 10 optically pumped using circularly polarized light having a wavelength of 1.08 pim in the case of 3 He. The light drives transitions up to the 2 3 P states, producing high polarizations in the metastable state to which the 2 3 S atoms then decay. The polarization of the 2 3 SI states is rapidly transferred to the ground state through metastability exchange collisions between metastable and ground state atoms. 15 Metastability exchange optical pumping will work in the same low magnetic fields in which spin exchange pumping works. Similar polarizations are achievable, but generally at lower pressures, e.g., about 0-10 Torr. Generally described, for spin-exchange optically pumped systems, a gas mixture is introduced into the hyperpolarizer apparatus upstream of the polarization 20 chamber. Most xenon gas mixtures include a buffer gas as well as a lean amount of the gas targeted for hyperpolarization and is preferably produced in a continuous flow system. For example, for producing hyperpolarized 1 2 Xe, the pre-mixed gas mixture is typically about 85-89% He, about 5% or less 1 29 Xe, and about 10% N 2 . In contrast, -14- WO 99/66255 PCTIUS99/13597 for producing hyperpolarized 3 He, a mixture of 99.25% 3 He and 0.75% N 2 is pressurized to 8 atm or more and heated and exposed to the optical laser light source in a batch mode system. In any event, once the hyperpolarized gas exits the pumping chamber it is directed to a collection or accumulation container. 5 A 5-20 Gauss alignment field is typically provided for the optical pumping of Rb for both 1 29 Xe and 3 He polarization. The hyperpolarized gas is collected (as well as stored, transported, and preferably delivered) in the presence of a magnetic field. It is preferred for solid (frozen) 1 29 Xe that the field be on the order of at least 500 Gauss, and typically about 2 kilo Gauss, although higher fields can be used. Lower fields can 10 potentially undesirably increase the relaxation rate or decrease the relaxation time of the polarized gas. As regards 3 He, the magnetic field is preferably on the order of at least 5-30 gauss although, again, higher (homogeneous) fields can be used. The magnetic field can be provided by electrical or permanent magnets. In one embodiment, the magnetic field is provided by a plurality of permanent magnets 15 positioned about a magnetic yoke which is positioned adjacent the collected hyperpolarized gas. Preferably, the magnetic field is homogeneously maintained around the hyperpolarized gas to minimize field induced degradation. Polarized Gas Relaxation Processes 20 Once hyperpolarized, there is a theoretical upper limit on the relaxation time (TI) of the polarized gas based on the collisional relaxation explained by fundamental physics, i.e., the time it takes for a given sample to decay or depolarize due to collisions of the hyperpolarized gas atoms with each other absent other depolarizing factors. For example, 3 He atoms relax through a dipole-dipole interaction during 3 He 25 3 He collisions, while 1 29 Xe atoms relax through N-I spin rotation interaction (where N is the molecular angular momentum and I designates nuclear spin rotation) during 129Xe- Xe collisions. Stated differently, the angular momentum charge associated with flipping a nuclear spin over is conserved by being taken up by the rotational angular momentum of the colliding atoms. In any event, because both processes 30 occur during noble gas-noble gas collisions, both resulting relaxation rates are directly proportional to gas pressure (Ti is inversely proportional to pressure). At one atmosphere, the theoretical relaxation time (Ti) of 3 He is about 744-760 hours, while for 1 29 Xe the corresponding relaxation time is about 56 hours. See Newbury et al., -15- WO 99/66255 PCT/US99/13597 “Gaseous 3 He-‘He Magnetic Dipolar Spin Relaxation,” 48 Phys. Rev. A., No. 6, p. 4411 (1993); Hunt et al., Nuclear Magnetic Resonance of 1 29 Xe in Natural Xenon, 130 Phys. Rev. p. 2302 (1963). Unfortunately, other relaxation processes prevent the realization of these theoretical relaxation times. For example, the collisions of 5 gaseous 1Xe and 3 He with container walls (“surface relaxation”) have historically dominated most relaxation processes. For 3 He, most of the known longer relaxation times have been achieved in special glass containers having a low permeability to helium. In the past, a fundamental understanding of surface relaxation mechanisms has been elusive which has made the predictability of the associated Ti difficult. 10 U.S. Patent No. 5,612,103 to Driehuys et al. describes using coatings to inhibit the surface-induced nuclear spin relaxation of hyperpolarized noble gases, especially 129Xe. The contents of this patent are hereby incorporated by reference as if recited in full herein. Driehuys et al. recognized that nuclear spin relaxation of I 29 Xe on a polydimethoylsiloxane (“PDMS”) surface coating can be dominated by dipolar 15 coupling of the 129 Xe nuclear spin to the protons in the polymer matrix. Thus, it was demonstrated that paramagnetic contaminants (such as the presence of paramagnetic molecules like oxygen) were not the dominant relaxation mechanism in that system because the inter-nuclear dipole-dipole relaxation was found to dominate the system under investigation. This was because 129 Xe substantially dissolved into the particular 20 polymer matrix (PDMS) under investigation. See Bastiaan Driehuys et al., “Surface Relaxation Mechanisms of Laser-Polarized 1 2 9 Xe,” 74 Phys. Rev. Lett., No. 24, pp. 4943-4946 (1995). One aspect of the instant invention now provides a more detailed understanding of noble gas depolarization on polymer surfaces. Indeed, as will be 25 explained further below, noble gas solubility in large numbers of polymer systems (not just PDMS) can cause inter-nuclear dipole-dipole relaxation to dominate the polarization decay rate. Notably, this insight now indicates that polymers can be especially effective for the suppression of 3 He relaxation. In addition, a predictive explanation of noble gas relaxation on polymer surfaces is discussed below. 30 Advantageously. it is now possible to calculate and measure the relaxation properties of various materials. This information can be advantageously used with other parameters such as free gas volume and surface area of containers to provide more effective and advantageous surface configurations and material characteristics which -16- WO 99/66255 PCTIUS99/13597 can facilitate, preserve, and further improve the polarization life of the noble gas. This is especially useful in providing containers which can yield reliable, repeatable, and predictable high-volume polarization production and maintenance which in the past has been difficult to achieve outside the pristine conditions of a small production 5 laboratory. Generally stated, magnetic interactions can alter the time constant of relaxation, referred to as the longitudinal relaxation time (Ti), and typically occur when different atoms encounter one another. In the case of hyperpolarized noble gases held in containers, the nuclear magnetic moments of the gas atoms interact with 10 the surface materials to return the gas to the equilibrium or non-hyperpolarized state. The strength of the magnetic moment can be a determinative factor in determining the relaxation rate associated with the surface material. Since different atoms and molecules have different magnetic moments, relaxation rates are material-specific. 15 Relaxivity of Materials In order to compare the characteristic information of certain materials concerning their respective relaxing effects on hyperpolarized noble gases, the term “relaxivity” is used. As used herein, the term “relaxivity” (“T”) is used to describe a material property associated with the rate of depolarization (“1/Ti”) of the 20 hyperpolarized gas sample. For a container having a chamber volume “Ve” capable of holding a quantity of hyperpolarized gas and for a material sample with a surface area “A” in the container chamber, each time a polarized gas atom contacts the container surface, it has a probability (“p”) of depolarizing. The rate of depolarization (l/Tj) of this gas sample in the chamber can then be described by p times the rate at which gas 25 atoms collide with the surface (“R”). 1 – = Rp (2.1) T The average surface collision rate (R) per gas atom is known from statistical mechanics, R. Reif, Fundamentals of Statistical and Thermal Physics, McGraw-Hill, 30 Ch. 12-14, pp. 461-493 (1965): R = VA (2.2) 4V -17- WO 99/66255 PCT/US99/13597 In this equation, “v ” is the mean thermal velocity of the gas atoms. For the case of a one cubic centimeter (“1 cc”) sphere of 1Xe the area is A=4cr 2 and the volume is V=4nr3/3. Thus, for v =154 m/s, equation (2.2) yields a collision rate R=800 s1. In 5 other words, each atom of Xe is contacting the surface of the sphere 800 times in 1 second. Therefore, according to equation (2.1) long T 1 times must have a minute probability for depolarization during each collision (p<<1). Substituting equation (2.2) back into equation (2.1) yields: 1 = A vp (2.3) T 4V 10 Since measurements for this study are performed at room temperature, "v" will not vary. Therefore, the relaxivity term, ("T") which is defined as T=vp/4, results in: 1 (2.4) T V 15 Thus, relaxivity ("T") is a material property that can describe the depolarizing effect that a specific material has on a hyperpolarized gas sample. When considering hyperpolarized gas containers, it is important to notice the relationship between the 1/ Ti and A/V terms in Equation 2.4. Thus, the ratio "A/V" for a sphere with a radius "r", the ratio reduces to 3/r. Therefore, a one liter sphere 20 (1000 cc, r-6.2cm) has a T 1 that is 10 times longer than a sphere with a one cubic centimeter volume (Icc, r=-.62 cm) made of the same material. Therefore, preferably, in order to improve the T 1 of hyperpolarized gas in the containers, the containers are configured and sized to decrease the value of the ratio A/V -- i.e., to increase the volume relative to the area of the container, as will be discussed further below. 25 Determining Relaxivity Equation 2.4 can be used to calculate relaxivity of the gas if surface relaxation is the only (dominant) depolarizing effect at work. In the case of practical material studies, this is not the case. The surfaces of the test chamber, the chamber seal, and -18- WO 99/66255 PCT/US99/13597 other impurities also contribute to the relaxation of the gas. However, by using the relaxation time differences between hyperpolarized gas in an empty test chamber and the hyperpolarized gas in the chamber containing a material sample positioned to contact the hyperpolarized gas, the characteristic relaxivity of the material can be 5 determined. Note that the relaxation rates are additive in the following form: 1- = + 1 1 (2.5) T- T " Tj In general form, Tla can represent the relaxation effect of the test chamber surface, Tb' can represent the effect of the hyperpolarized gas atoms colliding with 10 one another, and so on. Assuming that surface relaxation is the dominant relaxation effect, the relaxation rate can be described by adding the surface effects of the material sample and the test chamber. I Atli T A Y, _. - + c c (2.6) 15 where Am,, and Ym describes the area and relaxivity respectively of the material sample and Ac and Yc correspond to the area and relaxivity of the container or chamber. "V" is the free gas volume in the chamber. In this case, V= Ve - Vm, where "V"' is the volume of the chamber and "Vnm" is the volume of the container occupied by the material sample. In relaxivity studies for new materials (where the material sample is 20 small) the free volume "V" can be reasonably approximated as equal to V, i.e., V= Ve. Substituting back into (2.6): 1 A Y A Y,.____ C n M Te (2.7) T, V, VC Note that for a chamber without a material sample, this equation reduces to: 25 -19- WO 99/66255 PCTIUS99/13597 I A,.Y (2.8) T. V where TI, is the characteristic relaxation rate of the container or empty chamber. Substituting (2.8) into (2.7) yields: 1 _ A T "' + (2.9) 7, V, T 5 Solving equation (2.9) gives an expression for the relaxivity Tm associated with a specific material sample with a measured Ti in a chamber with known volume and observed Tic: T = , (I - 1 )(2.10) A,), T, T; 10 The relaxivity of a given material can easily be translated back into a more intuitive characteristic relaxation time. One method of comparison, in keeping with past surface relaxation rate studies, is to describe the relaxation rate as if there were a 1 cc spherical cell made of the material in question. Knowing the volume and surface area of such a cell (A=4tr 2 , V=47rr 3 /3, r=.62 cm) and substituting back into (2.8): 15 iee = 0.207cm (2.11) Ye Again, this container geometry is for illustration as it standardizes the relaxation term for comparison with past data. For reference, observed Ti values from 129Xe studies in the past showed ultra clean Pyrex with a Rb monolayer surface to have an associated Tcci= 30 minutes. 20 Experimental Determination of Relaxivity The hyperpolarized gas samples were used in a materials testing center known as the Spin Down Station. This apparatus was constructed to test various material samples in a controlled environment. The system consists of a materials testing -20- WO 99/66255 PCT/US99/13597 chamber, a Pulse-NMR Spectrometer, and a LabView user interface. The flexible system allows various chambers or bags to be cleaned and filled with polarized 129Xe or 3 He. The Pulse-NMR system then charts the deterioration of signal from these containers over time. 5 Equipment Layout Figure 1 is a schematic diagram of the Spin Down Station. This apparatus consists of a Helmholtz pair generating a stable Helmholtz magnetic field 151 around the glass test chamber labeled the Spin Down Chamber 152. The signal response 10 frequency (f) is proportional to the applied magnetic field (Bo) expressed by the equation f=yBo/2. This proportionality constant is known as the gyromagnetic ratio (YHe= 7 4 0 0 s-'G. yxe= 2 6 7 0 0 s 'G'). If the applied magnetic field remains constant, the coil must be tuned to switch between the two gases. As an alternative to retuning, the field strength was adjusted to result in the same frequency response for both gases. 15 A current of 1.0 A (7 G field) for 3He and 2.5 A (21 G field) for 129Xe was applied to the Helmholtz pair noted by the Helmholtz field shown in Figure 1. In the center of Helmholtz field 151 rested one of the two spin down chambers 152 used in these tests. Both chambers were valved to evacuate (base pressure -30 milliTorr) and fill the chamber with hyperpolarized gas. Each chamber could be 20 opened to insert polymer samples (typically 10mmx20mmxlmm). As shown, the NMR coil 153 rests beneath the chamber in the center of the Helmholtz field 151. The first spin down chamber was made of Pyrex TM coated with dimethyl dichlorosilane (DMDCS) and used a TeflonTM coated rubber O-ring as the vacuum seal. This chamber had a 110 minute characteristic T 1 suitable for observing the 25 surface relaxation effects of various polymer samples 154. Notably, after numerous tests, the TI, would often decrease. A thorough cleaning with high-purity ethanol restored the chamber to the baseline value. Unfortunately, the T 1 c for the PyrexTM chamber with 3 He was not long enough to distinguish good from bad materials for 3 He. Tests of various glasses in the Pyrex TM spin down chamber showed that a 30 chamber made of 1724 aluminosilicate glass would have a sufficiently long T 1 e for 3He. The 1724 3 He chamber was constructed with a ground seal requiring Apiezon TM vacuum grease. The chamber had a characteristic TIc of 12 hours on -21- WO 99/66255 PCT/US99/13597 average. The Apiezon
T
M grease used to seal both the chamber and the entry valve caused the chamber Tic to fluctuate significantly more than the Pyrex TM chamber. To restore the chamber to baseline TIc, the grease was removed by cleaning the chamber with high-purity Hexane. 5 Testing Procedure Using the Spin Down Station, seven polymer samples were tested using hyperpolarized 129Xe or 3 He. These polymers were purchased from Goodfellow, Inc., Berwyn, Pennsylvania. 10 Material Density Thickness Thickness (mm) (mm) (Sorption study) (Ti study) Polyamide 1.13 1 0.012* (Nylon 6) Silicone Elastomer 1.1-1.3 1 1 High Density Polyethylene 0.95 1 0.01 (HDPE) Low Density Polyethylene 0.92 1 0.05 (LDPE) Polyimide 1.42 1 0.025 (Kapton) Polypropylene 0.9 1 0.01 (PP) Polytetrafluoroethylene 2.2 1 0.01 (PTFE) I *Sample provided by DuPont. The particular polymers were chosen to represent a wide range of solubilities to ' 29 Xe and 3He gases. Each polymer sample was cleaned with ethanol and cut to a specific 15 size and shape to provide a known volume and surface area of the polymer sample (normally V=2 cm 3 , SA=42.6 cm 2 ) for each T, study. The following steps were taken for each material measurement: 1. Clean the testing chamber 2. Polarize 1 29 Xe or 3 He 20 3. Perform a Ti study to establish the chamber baseline (Tic) 4. Place polymer sample in chamber -22- WO 99/66255 PCT/US99/13597 5. Polarize 1 2 1Xe or 3 He 6. Perform a T, study of the chamber containing polymer sample (TI,) 7. Use TIc and T I, to find relaxation rate due to specific polymer 5 The Polymer Sorption Model The ability to measure and calculate relaxivity can result in an understanding of the physical characteristics that differentiate materials. An initial study of a wide range of materials confirmed conventional rigid containers of glass are much better than containers of materials containing paramagnetic or ferrous constituents such as 10 stainless steel. Notably, this test also showed a wide range of relaxivities within different material groups. In particular, different polymer materials were observed across the relaxivity spectrum. Manufacturing concerns such as durability and reliability make polymer materials an excellent alternative to the glass storage containers that are typically used for hyperpolarized gases, Scientifically, 15 substantially pure samples of these materials allow for relatively less complex models of surface relaxation. For discussion purposes, assume there is a polymer container of hyperpolarized gas in a homogeneous magnetic field. Since polymers are permeable materials, some quantity of gas dissolves in the container walls. The only dominant 20 relaxation mechanism in this system is that of the hyperpolarized gas atoms interacting with the protons or contaminants in the surface and bulk of the polymer container. Driehuys et al. demonstrated that relaxation of hyperpolarized 1 29 Xe in a specially coated glass sphere was dominated by the dipolar coupling between the protons in the surface and the 29 Xe nuclear spin. See Driehuys et al., "High-volume 25 production of laser-polarized 129 Xe," 69 App. Phys. Lett. (12), p. 1668 (1996). Since Xe-Xe collisions have a 56 hour Ti and typical conventional material T 1 times are 2 hours or less, the relaxation rate of the free gas can be neglected. Gas dissolved in the polymer surface relaxes quickly (
6 8 VS SHe=0.00 6 ). For this configuration, Ti is estimated at 36.8 minutes. Similarly, for the measured relaxivity for Nylon-6 of 0.0104 cm/min, predict T, is predicted to be about 148 min or about 2.4 hours. This value is close to what has been measured for the presently used Tedlarik bags. 10 EXAMPLE 3: Metal Film Surface In this example, metal film coatings are used as the contact surface. The 7″ x 7″ square bag described in Example 1 is employed but coated or formed with high purity aluminum on its internal contact surface (the surface in contact with the 15 hyperpolarized gas). The relaxivity of high purity aluminum for 129Xe has been recently measured to be about 0.00225 cm/min. (One readily available material suitable for use is Reynold’s T M heavy duty freezer foil). Doing the calculation, one can obtain a container with an extended T 1 for xenon of about 11.43 hours. This is a great improvement in T 1 for Xe. Similarly, the use of such metal film surfaces for 20 3He can generate Ti ‘s in the range of thousands of hours (the container no longer being a limiting factor as these Ti’s are above the theoretical collisional relaxation time described above). Metals other than aluminum which can be used include indium, gold, zinc, tin, copper, bismuth, silver, niobium, and oxides thereof. Preferably, “high purity” metals are employed (i.e., metals which are substantially 25 free of paramagnetic or ferrous impurities) because even minute amounts of undesirable materials or contaminants can degrade the surface. For example, another high purity aluminum sample tested had a relaxivity of about 0.049 cm/min, a full 22 times worse than the sample quoted above. This is most likely due to the presence of ferrous or paramagnetic impurities such as iron, nickel, cobalt, chromium and the like. 30 Preferably, the metal is chosen such that it is well below 1ppm in ferrous or paramagnetic impurity content. -60- WO 99/66255 PCT/US99/13597 EXAMPLE 4: Multiple Materials Using the bag configured as noted in Example 1, one can determine the effects of the addition of multiple materials. For example, a 5cm 2 silicone gasket positioned on the I liter deuterated HDPE bag (described in Example 1 (for 3He)) with a starting 5 T, of 132 hours will reduce the container’s associated relaxation time. As pointed out in Equations 2.5, 2.6, relaxation rates are additive. Thus, to properly determine the container or equipment relaxation time, the relaxivities and corresponding surface areas of all the materials adjacent the free volume should be evaluated. The hypothetical silicone gasket, with an exemplary area “A” of 5cm 2 , the measured 10 relaxivity of 0.0386cm/min (p. 47, table 4.3), and free volume still at 1000cc, gives a relaxation rate of about 1.9x 10-4/min. Adding the rate due to the bag itself (1.3×10 4 /min) yields a total rate of about 3.2×10~ 4 /min which is inverted to get a T, of about 52 hours. Therefore, it is apparent that adding a very small surface area of a poor material can drastically shorten the Ti despite the fact that most of the container 15 material is good. Indeed, many commercially used O-ring materials can have relaxivities an order of magnitude higher than the one described, making the situation even worse. Thus, it is important to use substantially pure (impurity free) materials. The relaxivity for an available “off the shelf’ silicone O-ring for 129Xe was measured at about 0.2-0.3 cm/min. For example, using the measured 129Xe relaxivity numbers 20 for the 3 He deuterated HDPE container will reduce the 132 hour bag down to just 15 hours (a full order of magnitude deterioration). The key is that every gasket, coupling, valve, tubing or other component that is added to the bag or container (especially those that are in fluid communication with the hyperpolarized gas) is preferably made of the friendliest possible material relative to the hyperpolarized 25 state. EXAMPLE 5: Measurement of Specific Material Properties Measurement of specific material properties such as the relaxivities of materials is described above. For example, as noted in equation 2.5, relaxation rates 30 attributed to various relaxation mechanisms are additive. Therefore, in order to measure the specific material property, a spin-down chamber such as that described herein can be used to determine two relaxation times for a hyperpolarized gas. Using the chamber consisting of two hemispheres sealed with an O-ring, the chamber is -61- WO 99/66255 PCT/US99/13597 closed, HP (“hyperpolarized gas”) is introduced therein, and the relaxation time Ti is measured. Then the chamber is opened, a sample of known surface area is inserted, and the process is repeated to measure a new T 1 . The new T, will be less than the old because a new relaxing surface has been added while keeping the free volume roughly the same. The difference between the two relaxation times is attributed to the relaxivity of the added material specimen. Thus, the difference can be used to calculate the material relaxivity using equation (2.10). EXAMPLE 6: Validation of the Sorption Model 10 Figures 4.1 and 4.2 show the calculated and experimental Ti values for 129Xe and 3 He, respectively, in a 1 cc sphere for different surface materials as plotted against the product of solubility (S) and the square root of the molar density of protons in the material matrix [1H] 5 . The 1cc sphere value incorporates both volume and surface area and is a useful Ti metric corresponding to conventional evaluations, and as such 15 is typically more readily descriptive than the relaxivity parameters described herein. The T, value according to equation (2.23c) depends on a number of fixed constants and then depends inversely on gas solubility and the square root of the proton concentration. Experimental values of the measured one cubic centimeter sphere Ti (Ticc) for all the polymers are plotted as well and show substantial agreement between 20 theory and experiment, thus validating the sorption model described herein. The foregoing is illustrative of the present invention and is not to be construed as limiting thereof. Although a few exemplary embodiments of this invention have been described, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the 25 novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the claims. In the claims, means-plus-function clause are intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Therefore, it is to be understood that the foregoing is 30 illustrative of the present invention and is not to be construed as limited to the specific embodiments disclosed, and that modifications to the disclosed embodiments, as well -62- WO 99/66255 PCT/US99/13597 as other embodiments. are intended to be included within the scope of the appended claims. The invention is defined by the following claims, with equivalents of the claims to be included therein. -63-
Claims (88)
1. A container for receiving a quantity of hyperpolarized gas therein, comprising: at least one resilient wall comprising inner and outer surfaces which defines an expandable chamber for holding a quantity of hyperpolarized gas 5 therein, said inner surface having a relaxivity value associated therewith; a quantity of non-toxic hyperpolarized fluid held in said expandable chamber, wherein the relaxivity value associated with said inner surface of said wall is low such that said inner surface inhibits contact-induced polarization loss of said hyperpolarized fluid, and wherein said wall defines an oxygen shield in 10 communication with said inner surface configured to inhibit the migration of oxygen into said expandable chamber; a port in fluid communication with said expandable chamber; and sealing means operably associated with said port for controlling the introduction and release of said quantity of hyperpolarized fluid into and out of 15 said expandable chamber; wherein the Ti for said hyperpolarized fluid held in said container resulting from one or more of contact-induced polarization loss and oxygen migration into said chamber is greater than about 6 hours.
2. A container according to Claim 1, wherein said wall inner surface is defined by a first material layer with a first thickness and said wall outer surface is defined by a second material layer with a second thickness, said second material layer configured to overlay and be secured to said first material layer, and wherein said second 5 material is different from said first material.
3. A container according to Claim 1, wherein said wall is configured to provide an oxygen permeability rate relative to said expandable chamber of less than about 1 x 10- amgt/min when measured at one atmosphere of pressure. -64- WO 99/66255 PCT/US99/13597
4. A container according to Claim 3, wherein said wall is configured as a unitary polymer material layer with a thickness which provides an oxygen permeability rate at one atm of less than about I x 10-7 amgt/min.
5. A container according to Claim 2, wherein said first material thickness is greater than the polarization decay length scale which is determined by the equation: L = 1, D, wherein LP is the polarization decay scale length, T, is the relaxation time of the noble gas in said first material, and Dp is the noble gas diffusion coefficient in said first material.
6. A container according to Claim 3, further comprising a quantity of hyperpolarized 3 He fluid held said expandable chamber, and wherein said inner layer thickness is at least 16 microns.
7. A container according to Claim 2, wherein said wall further comprises a third material layer overlaying and secured to said second material layer opposing said first material layer.
8. A container according to Claim 7, wherein said wall further comprises a fourth material layer overlaying and secured to said third material layer opposing said second material layer.
9. A container according to Claim 7, wherein said one of said second and third material layers is formed of an oxygen-shielding material, and wherein said first, second, and third material layers are formed of resilient materials such that said chamber has a first collapsed position and a second inflated position, corresponding respectively, 5 to said chamber being void or filled. -65- WO 99/66255 PCT/US99/13597
10. A container according to Claim 2. wherein said first material layer comprises a high purity metal which is substantially free of ferrous and paramagnetic impurities.
11. A container according to Claim 7, wherein at least one of said second and third material layers comprises a metal film configured to overlay the adjacently disposed layer.
12. A container according to Claim 2, wherein said first material layer comprises a material chosen from the group consisting of polyolefin, polystyrene, polymethacrylate, polyvinyl, polydiene, polyester, polycarbonate, polyamide, polyimide, polynitriles, cellulose and cellulose derivatives, and blends and mixtures thereof.
13. A container according to Claim 1, wherein said first layer material comprises a material chosen from the group consisting of high-density polyethylene, low density polyethylene, polypropylene having about 50% crystallinity, polyvinylfluoride, polyamide, polyimide, polynitriles, and cellulose, and blends and mixtures thereof.
14. A container according to Claim 1, said container having an internal volume (V) and an internal surface area (A), wherein said container is sized such that the ratio A/V is less than about .75 cm^ 1 .
15. A container according to Claim 13, wherein at least one of said O-rings is configured such that it is substantially non-depolarizing to the hyperpolarized gas held in said container.
16. A container according to Claim 13, wherein at least one of said O-rings is coated with a material which inhibits the contact-induced relaxation of said hyperpolarized gas.
17. A container according to Claim 15, wherein said O-rings are formed such that they are substantially free of depolarizing filler materials. -66- WO 99/66255 PCT/US99/13597
18. A container according to Claim 1, wherein said hyperpolarized fluid comprises 3He gas, and wherein said inner surface material has a relaxivity value of less than about .0013 cm/min.
19. A container according to Claim 1, wherein said hyperpolarized fluid comprises 129Xe gas, and wherein said inner surface material has a relaxivity value of less than about .012 cm/min.
20. A container according to Claim 1, wherein said hyperpolarized fluid is a gas.
21. A container according to Claim 20, wherein said hyperpolarized gas comprises hyperpolarized 3 He, and wherein said hyperpolarized 3 He gas in said container has a relaxation time longer than about 14 hours.
22. A container according to Claim 20, wherein said hyperpolarized gas comprises hyperpolarized 129Xe.
23. A container according to Claim 1, further comprising a capillary extension having opposing first and second end portions, wherein said second end portion is in fluid communication with said container port.
24. A container according to Claim 22, further comprising a valve in fluid communication with said container, wherein said capillary stem is positioned intermediate said port and said valve.
25. A container according to Claim 1, wherein said container includes a port isolation means operably associated with said expandable chamber for isolating said port from a major portion of said expandable chamber. -67- WO 99/66255 PCTIUS99/13597
26. A container according to Claim 25, wherein said container includes a perimeter, and wherein said port is disposed in said container such that it is proximate to a portion of said perimeter, and wherein said isolation means is positioned intermediate said port and a major portion of said expandable chamber.
27. A container according to Claim 26, wherein said isolation means is an externally applied clamp.
28. A container according to Claim 27, wherein said isolation means is defined by folding the perimeter portion of said container with said port toward the main volume of said expandable chamber.
29. A resilient container for holding hyperpolarized gas, comprising: a first layer of a first material configured to define an expandable chamber to hold a quantity of hyperpolarized gas therein; a second layer of a second material positioned such that said first layer is 5 between said second layer and said chamber; and a quantity of hyperpolarized gas positioned in said chamber.
30. A resilient container according to Claim 29, wherein one of said first and second materials is an oxygen shielding material such that the oxygen permeation into said chamber is less than about 1 x 10- 7 amgt/min, and wherein said first and second layers are concurrently responsive to the application of pressure.
31. A resilient container according to Claim 30, wherein said first layer has a surface material which has a low relaxivity value which inhibits contact-induced relaxation of the hyperpolarized gas held in said expandable chamber.
32. A resilient container according to Claim 31, wherein said first layer comprises a polymer material configured to face said expandable chamber and thereby form the gas-contacting surface. -68- WO 99/66255 PCT/US99/13597
33. A resilient container according to Claim 29. wherein said hyperpolarized gas is 3He and said first material is chosen from the group consisting of polyolefin, polystyrene, polymethacrylate, polyvinyl, polydiene, polyester. polycarbonate, polyamide, polyimide, polynitriles, cellulose and cellulose derivatives, and blends and 5 mixtures thereof.
34. A resilient container according to Claim 30. wherein said first material is perdeuterated or partially perdeuterated.
35. A resilient container according to Claim 30, wherein said first material comprises a copolymer.
36. A resilient container according to Claim 30, wherein said first layer material is chosen from the group consisting of high-density polyethylene, low-density polyethylene, polypropylene having about 50% crystallinity, polyvinylfluoride, polyamide, polyimide, polynitriles, and cellulose, and blends and mixtures thereof
37. A resilient container according to Claim 36, wherein said first material is perdeuterated or partially perdeuterated.
38. A resilient container according to Claim 30, wherein said first layer comprises a high purity metal.
39. A resilient container according to Claim 30, wherein said first layer comprises a material chosen from the group consisting of aluminum, indium, gold, zinc, tin, copper, bismuth, silver, niobium, and oxides thereof.
40. A resilient container according to Claim 30, wherein said hyperpolarized gas is 3 Helium, and wherein said first material has a relaxivity value of less than about .0013 cm/min. -69- WO 99/66255 PCT/US99/13597
41. A resilient container according to Claim 30, wherein said hyperpolarized gas is 1 29 Xe. and wherein said first material has a relaxivity value of less than about .012 cm/min.
42. A resilient container according to Claim 30, wherein said hyperpolarized gas is 3 He, and wherein said gas in said container has a relaxation time longer than about 6 hours.
43. A resilient container according to Claim 30, wherein said hyperpolarized gas is 3 He, and wherein said hyperpolarized gas in said container has a relaxation time longer than about 14 hours.
44. A resilient container according to Claim 30, wherein said hyperpolarized gas is 1 29 Xe, and wherein said hyperpolarized gas in said container has a relaxation time longer than about 4 hours.
45. A resilient container according to Claim 29, wherein said expandable chamber includes a port, and wherein said container further comprises a capillary stem in fluid communication with said port.
46. A resilient container according to Claim 29, wherein said expandable chamber includes a port, and wherein said container further comprises a releasably engageable port isolation means operably associated with said expandable chamber for substantially isolating said port from a major volume of said expandable chamber.
47. A resilient container comprising: at least one wall having opposing inner and outer surfaces; an expandable chamber defined by said wall inner surface, said chamber having a collapsible void position and an expandable inflated position, wherein 5 said chamber is configured to hold a quantity of hyperpolarized fluid therein: a valve operably associated with said expandable chamber; and -70- WO 99/66255 PCT/US99/13597 a capillary stem positioned intermediate said valve and said expandable chamber, wherein said chamber, said capillary stem and said valve are in fluid communication.
48. A resilient container according to Claim 47, wherein said inner surface is formed of a material having a low solubility for the hyperpolarized gas.
49. A resilient container according to Claim 47, wherein said wall is configured to inhibit the migration of oxygen into said chamber.
50. A resilient container according to Claim 47, wherein said capillary stem is formed onto a portion of said valve to define a continuous body.
51. A resilient container according to Claim 50, wherein said valve comprises a glass body.
52. A resilient container according to Claim 49, wherein said capillary stem is substantially rigid and has an internal surface which has a low solubility for said hyperpolarized fluid which inhibits contact induced depolarization of the hyperpolarized gas.
53. A resilient container according to Claim 49, wherein said valve has a first open position and a second closed position, and wherein said capillary stem has a length and inner width which is sized and configured to inhibit the passage of hyperpolarized gas from said container chamber toward said valve body when said valve is in the closed 5 position.
54. A resilient container according to Claim 49, wherein said container wall comprises a polymer.
55. A resilient container according to Claim 47, wherein said container wall inner surface comprises a deuterated polymer. -71- WO 99/66255 PCTIUS99/13597
56. A resilient container according to Claim 47, wherein said container wall comprises multiple layers of materials secured theretogether such that the container multiple layers are concurrently responsive to the application of pressure.
57. A resilient container according to Claim 50, wherein at least one of said multiple layers comprises a metallic material.
58. A resilient container according to Claim 50, wherein at least one of said multiple layers is formed of a different material from the other layers.
59. A resilient container according to Claim 52, said container further comprising a quantity of hyperpolarized 3 He, wherein said container is configured to provide a Ti resulting from contact-induced polarization and oxygen exposure which is greater than about 6 hours.
60. A resilient container according to Claim 53, wherein the T, is greater than about 14 hours.
61. A resilient container according to Claim 54, said container further comprising a quantity of hyperpolarized 1 29 Xe, wherein said container is configured to provide a T, resulting from contact-induced polarization and oxygen exposure which is greater than about 4 hours.
62. A multi-layer resilient bag comprising: a quantity of hyperpolarized gas; and first and second opposing walls configured with a plurality of material layers, said first and second opposing walls attached together around a perimeter 5 portion thereof to define an expandable chamber therebetween for holding said quantity of hyperpolarized gas therein, said expandable chamber having a gas contacting surface and a port, wherein said gas-contacting surface is formed of a material which has a reduced solubility for a hyperpolarized gas, and wherein said -72- WO 99/66255 PCT/US99/13597 first and second walls are configured to inhibit the migration of oxygen and 10 moisture into said expandable chamber.
63. A multi-layer resilient bag according to Claim 62, further comprising means for sealing said port such that a major portion of said quantity of hyperpolarized fluid is captured within said chamber when said chamber is expanded, and wherein said sealing means is configured to allow the release of said hyperpolarized fluid and allow 5 said first and second walls to compress said chamber to expel the hyperpolarized gas from therein.
64. A multi-layer resilient bag according to Claim 63, wherein said sealing means is a valve.
65. A multi-layer resilient bag according to Claim 64, further comprising a capillary stem in fluid communication with said port and said valve.
66. A multi-layer resilient bag according to Claim 62, further comprising an isolation means releasably engageable with said expandable chamber for isolating said port from a major portion of said expandable chamber.
67. A container according to Claim 66, wherein said bag includes a perimeter. and wherein said port is disposed in said bag such that it is proximate to a portion of said perimeter, and wherein said isolation means extends intermediate said port and a major portion of said expandable chamber.
68. A container according to Claim 66, wherein said isolation means is an externally applied clamp.
69. A container according to Claim 66, wherein aid isolation means is defined by folding the perimeter portion of said container associated with said port toward the main volume of said expandable chamber. -73- WO 99/66255 PCTIUS99/13597
70. A multi-layer bag according to Claim 62, wherein said multiple layers are at least three layers, wherein each of said layers is formed of a different material from the others, such that said first and second walls are puncture resistant, moisture resistant, and oxygen resistant, and wherein said chamber gas contacting surface is resistant to contact 5 induced depolarization
71. A multi-layer bag according to Claim 70, wherein said hyperpolarized fluid comprises gaseous 3 He, and wherein the T, of said 3 He in said bag is greater than about 6 hours.
72. A multi-layer bag according to Claim 70, wherein said hyperpolarized fluid comprises gaseous 129Xe, and wherein the T, of said 129Xe in said container is greater than about 4 hours.
73. A method for storing, transporting, and delivering hyperpolarized gas to a target, comprising the steps of: hyperpolarizing a quantity of noble gas with spin exchange with an alkali metal; 5 introducing a quantity of hyperpolarized gas into an expandable multi layer container having opposing walls defined by multiple layers of materials, wherein the multiple layers of the container walls are securely attached together such that they are concurrently responsive to the application of pressure thereon, and wherein one of said layers is formed of a material resistant to the migration of 10 oxygen into the container, and also wherein the hyperpolarized gas is processed such that it is non-toxic and substantially free of alkali metal and thereby suitable for in vivo administration; sealing the container to retain the hyperpolarized gas therein; transporting the container to a site remote from the hyperpolarization 15 site; and compressing the container to collapse the chamber and force the hyperpolarized gas to exit therefrom, thereby delivering the hyperpolarized gas to a target. -74- WO 99/66255 PCT/US99/13597
74. A method according to Claim 73, further comprising the step of inhibiting a major portion of the gas held in the container from circulating toward the port opening in the container during storage and transport.
75. A method according to Claim 74, wherein said inhibiting step is performed by disposing a capillary flow passage in communication with the port of the container.
76. A method according to Claim 74, wherein said inhibiting step is performed by substantially isolating a minor portion of the container from the main volume of the container.
77. A method according to Claim 76, wherein said isolating step is performed by clamping a portion of the opposing walls of the container together.
78. A method according to Claim 76, wherein said isolating step is performed by folding the minor portion of the container toward the main volume of the container to pinch together the opposing wall segments therebetween.
79. A method according to Claim 73, wherein said hyperpolarized gas is ‘He and wherein said container includes a first layer with a surface which inhibits the depolarizing contact interaction of the hyperpolarized gas such that the hyperpolarized gas has a relaxation time longer than about 6 hours.
80. A method according to Claim 73, wherein the wall includes a first layer comprising a high purity metal.
81. A method according to Claim 74, wherein the wall includes a first layer comprising a polymer and a second layer comprising an metal configured to define an oxygen shield overlying the first layer.
82. A method according to Claim 74, further comprising the step of configuring the container to suppress the migration of oxygen into said chamber. -75- WO 99/66255 PCT/US99/13597
83. A method according to Claim 74, wherein said filling step and said delivering step are repeated.
84. A method according to Claim 73, wherein said container walls comprise at least three layers of three different materials.
85. A method for preparing an expandable storage container for receiving a quantity of hyperpolarized gas, comprising the steps of: providing a quantity of purge gas into the hyperpolarized gas container; expanding the hyperpolarized gas container by directing a quantity of 5 purge gas therein; collapsing the hyperpolarized gas container by removing purge gas therefrom; outgassing the oxygen in the container walls by decreasing the oxygen partial pressure in the container thereby causing a substantial amount of the 10 oxygen trapped in the walls of the container to migrate into the chamber of the container in the gas phase; filling a container with a quantity of storage nitrogen after said outgassing step to a pressure which minimizes the pressure differential across the walls of the container to minimize further outgassing of the container; 15 storing the container for future use; and removing the storage nitrogen and outgassed oxygen from the container before filling with a quantity of hyperpolarized gas.
86. A method for determining the hyperpolarized gas solubility in a material such as a polymer or fluid, comprising the steps of: introducing a first quantity of hyperpolarized gas into a container; measuring a first relaxation time of the hyperpolarized gas in the container; 5 positioning a sample of a desired material in the container; introducing a second quantity of the hyperpolarized noble gas into the container; -76- WO 99/66255 PCT/US99/13597 measuring a second relaxation time of the hyperpolarized gas in the container; and 10 determining the gas solubility of the sample based on the difference between the first and second relaxation times.
87. A method according to Claim 86, wherein said sample is a structurally fixed sample having a known geometric shape with a surface formed of the desired material.
88. A method according to Claim 86, wherein said sample is a quantity of fluid filling a portion Qf the free volume in the chamber. -77-
AU45722/99A
1998-06-17
1999-06-16
Resilient containers for hyperpolarized gases
Ceased
AU745398B2
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1998-06-17
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1998-06-17
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1998-07-30
1998-07-30
Containers for hyperpolarized gases and associated methods
US09/126448
1998-07-30
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WO1999066255A2
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1998-06-17
1999-06-16
Resilient containers for hyperpolarized gases
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Resilient containers for hyperpolarized gases
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ATE523776T1
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AU745398B2
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US6237363B1
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1998-09-30
2001-05-29
Medi-Physics, Inc.
Hyperpolarized noble gas extraction methods masking methods and associated transport containers
US6286319B1
(en)
*
1998-09-30
2001-09-11
Medi-Physics, Inc.
Meted hyperpolarized noble gas dispensing methods and associated devices
US6523356B2
(en)
1998-09-30
2003-02-25
Medi-Physics, Inc.
Meted hyperpolarized noble gas dispensing methods and associated devices
US6648130B1
(en)
1999-08-11
2003-11-18
Medi-Physics, Inc.
Hyperpolarized gas transport and storage devices and associated transport and storage methods using permanent magnets
EP1265527A2
(en)
2000-03-13
2002-12-18
Medi-Physics, Inc.
Diagnostic procedures using direct injection of gaseous hyperpolarized ?129 xe and associated systems and products
KR101095943B1
(en)
*
2006-02-21
2011-12-19
밀리켈빈 테크놀로지스 엘엘씨
Hyperpolarization methods, systems and compositions
CN107831094B
(en)
*
2017-10-30
2020-04-07
中国人民解放军国防科技大学
Method for measuring gas diffusion constant based on change of relaxation rate of alkali metal atom
CN108519312B
(en)
*
2018-03-30
2020-06-02
重庆山楂树科技有限公司
Device for detecting gas particles
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1967-09-15
1972-04-18
Us Army
Process for the deuteration of the hydroxyl position of organic alcohols
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Merck Sharp & Dohme (I.A.) Corporation
Deuteration of functional group-containing hydrocarbons
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*
1981-01-26
1984-07-18
Hinsaw Waldo Stephen
Investigation of samples by nmr techniques
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1988-06-23
1990-04-03
Hormoz Azizian
Deuteration of unsaturated polymers and copolymers
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1990-08-29
1991-12-24
Vecere William T
Fitting and tube apparatus for gas emission sample container
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*
1991-01-18
1992-12-29
Bgi Incorporated
Gas sampling apparatus
US5545396A
(en)
1994-04-08
1996-08-13
The Research Foundation Of State University Of New York
Magnetic resonance imaging using hyperpolarized noble gases
US5612103A
(en)
1995-06-07
1997-03-18
Princeton University
Coatings for production of hyperpolarized noble gases
AUPN538495A0
(en)
*
1995-09-12
1995-10-05
Esnouf, Philip Stuart
Disposable oxygenating device
US5809801A
(en)
1996-03-29
1998-09-22
The Trustees Of Princeton University
Cryogenic accumulator for spin-polarized xenon-129
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*
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Lawrence Berkeley National Laboratory
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(en)
*
1996-03-29
1997-07-01
The Trustees Of Princeton University
High volume hyperpolarizer for spin-polarized noble gas
1999
1999-06-16
CA
CA002335467A
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Expired – Fee Related
1999-06-16
CA
CA002637700A
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1999-06-16
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AT08019587T
patent/ATE523776T1/en
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1999-06-16
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AU45722/99A
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1999-06-16
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EP99928724A
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2001-04-11
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1999-12-23
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1999-12-23
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2002-11-28
AU745398B2
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2002-03-21
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1999-12-23
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2003-08-29
HU0103605A2
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2002-03-28
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2001-09-12
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2008-11-18
CN1117942C
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2003-08-13
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2011-09-07
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