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WO1992008130A1 - Temperature insensitive calibration system - Google Patents

Temperature insensitive calibration system Download PDF

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Publication number
WO1992008130A1
WO1992008130A1 PCT/US1991/007917 US9107917W WO9208130A1 WO 1992008130 A1 WO1992008130 A1 WO 1992008130A1 US 9107917 W US9107917 W US 9107917W WO 9208130 A1 WO9208130 A1 WO 9208130A1
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WO
WIPO (PCT)
Prior art keywords
calibration system
phase
calibration
partial pressure
amount
Prior art date
Application number
PCT/US1991/007917
Other languages
French (fr)
Inventor
David W. Deetz
Russell L. Morris
Original Assignee
Diametrics Medical, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Diametrics Medical, Inc. filed Critical Diametrics Medical, Inc.
Publication of WO1992008130A1 publication Critical patent/WO1992008130A1/en

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0006Calibrating gas analysers

Definitions

  • the present invention is directed generally to a multi-phase control or calibration system and, more particularly, to such a system exhibiting relatively constant partial pressures with respect to certain diverse dissolved gaseous species of interest in one or more liquid phases over a range of ambient temperatures.
  • the preferred fluid consists of a first non-aqueous liquid phase containing an amount of dissolved oxygen (0 2 ) in which the partial pressure of 0 2 is relatively temperature insensitive over an ambient temperature range of interest, a second, aqueous phase, immiscible with the first phase and containing an amount of dissolved carbon dioxide (C0 2 ) and one or more solute species that provide temperature stability with respect to the partial pressure of C0 2 over the ambient temperature range of interest.
  • the liquid phases are in equilibrium with a vapor phase.
  • perfluorocarbons are completely fluorinated organic compounds in which all the carbon-bound hydrogen atoms are replaced with fluorine atoms. These materials have an unique combination of properties.
  • the compounds are extremely non-polar and have essentially no solvent action. They are so chemically inert and have such high thermal stability that they can be mixed with almost any material without fear of any adverse reactive effect either upon other mixture components or upon the material itself.
  • the compounds also have a relatively high boiling points and low pour points giving them a relatively wide liquid range. Many of these perfluorocarbon materials also have a high, relatively stable, oxygen solubility.
  • Aqueous perfluorocarbon multi ⁇ phase emulsions have been proposed for applications which involve the need to carry or sense oxygen in the presence of carbon dioxide and/or where pH needs to be controlled or sensed.
  • One such emulsion system is illustrated and described in U.S. Patent 4 722 904 to Feil.
  • Other such systems are disclosed in Turner (U.S. Patent 4 001 142), Cormier, et al. (U.S. Patent Nos. 4 299 728 and 4 369 127) and Sorenson, et al. (U.S. Patent Nos. 4 116 336 and 4 151 108).
  • These fluids typically comprise an aqueous emulsion of the organic oxygen carrier. Certain of these emulsions may contain surfactant materials, pH buffers and preservative materials.
  • the aqueous phase and the perfluorocarbon phase are chemically compatible but completely immiscible. While the perfluorocarbon phase reversibly carries the oxygen of interest, the aqueous phase reversibly carries other constituents of interest such as carbon dioxide and hydrogen ions.
  • control system contains a known partial pressure of oxygen and a known partial pressure of carbon dioxide and be of a known pH. Accordingly, the control system must be supplied in gas-tight, sealed ampules, or the like containing known amounts of ' dissolved oxygen and carbon dioxide species so that equilibrium partial pressures remain constant.
  • a known or control substance can later be used to check the relative accuracy of an instrument utilized to measure 0 2 and C0 2 concentration and the pH of such substances as blood.
  • the temperature sensitivity of the partial pressures of dissolved gases of interest has been greatly reduced.
  • the accuracy of calibration system established at a filling temperature of 20°C, for example, will not be sacrificed by later removal at, for example, 30°C.
  • the oxygen carrying solution phase is a solution of oxygen in one or more perfluorocarbon materials.
  • the preferred perfluorocarbon materials include FC-43, FC-75, FC-77, and others, manufactured by and available from the 3M Company of St. Paul, Minnesota.
  • the aqueous solution phase contains a specific amount of C0 2 complexing agents such as ethylene diamine, HC0 3 " , Ca ++ and OH " or other compounds which buffer the partial pressure of carbon dioxide (C0 2 ) in the aqueous solution to changes in temperature.
  • An amount of a compatible pH buffer can also be employed to stabilize the solution with respect to acidity.
  • the multi-phase control/calibration system of the invention is prepared under tightly controlled conditions and transferred to containers designed to accommodate the desired amount.
  • the filled containers are provided with a sealed storage atmosphere which maintains the desired conditions in equilibrium during the shelf life of the system.
  • This atmosphere typically contains sufficient oxygen and carbon dioxide in a mixture with one or more other gases inert to the system to maintain the desired amount of 0 2 and C0 2 species in the liquid phases of the system.
  • the preferred range of 0 2 (p0 2 ) partial pressure with respect to the system is from about 10 to about 200 mm Hg and the preferred range of partial pressure for C0 2 (pC0 2 ) is from about 5 to 100 mm Hg.
  • the preferred temperature range of temperature relative partial pressure insensitivity is about 20°C to about 30°C. It is also contemplated that various phase components can be used, if desired, to expand the ambient temperature range of relative partial pressure insensitivity beyond the range of 20°C to 30°C, if desired.
  • the range 20° to 30°C represents the normal range of temperatures for an indoor conditioned space.
  • the solution of the calibration system of the invention consist of a single aqueous phase containing, in addition to a C0 2 binding component or components, one or more solutes which reversibly bind 0 2 , such as copper ions, hemoglobin, and transition metal macromolecular complexing agents.
  • solutes such as copper ions, hemoglobin, and transition metal macromolecular complexing agents.
  • Solutions formulated in accordance with the invention should exhibit stable overall solubilities of the gases of interest over a range of ambient temperatures between about 20°C and 30°C. This means that calibration/control systems in impermeable containers which are filled under strictly controlled conditions at one temperature may be removed from a storage atmosphere at a different temperature and used with complete confidence.
  • control solutions including those in which oxygen is carried by a perfluorocarbon in one phase and carbon dioxide is carried in a second aqueous solution phase of controlled pH which are used to calibrate biological sensors utilized to detect dissolved oxygen, carbon dioxide and acidity. Because of the inherent properties of these systems, it has always been assumed that the temperature limitation with respect to exposure was one which had to be accommodated and could not be overcome.
  • the solutions or liquid phases in accordance with the invention are prepared under controlled conditions. Known amounts of the dissolved gases 0 2 and C0 2 are present in the phases as prepared. However, it may be months or even years before the system is actually used so that long-term stability is required. To preserve the integrity of the system over the shelf life of the product, the calibration system is sealed in an impermeable fluid tight container together with an amount of storage atmosphere which contains sufficient p0 2 and pC0 2 to maintian the amount of dissolved species in the liquids over time.
  • the container may be a glass ampule, or the like, but is preferably a polymeric envelope or laminated pouch which may consist of several layers of metallic foil and polymeric materials which make the pouch impervious to atmosphere exchange with the environment.
  • the calibration system of the present invention maintains its known p0 2 , pC0 2 and pH for the relatively shorter time required to perform the control or calibration procedure, regardless of the ambient temperature at which the breach occurs as long as that temperature is in the range of relative stability for the system, e.g., 20°C-30°C.
  • the calibration system of the present invention can also function well as a control system for analytical instruments of the class normally employing such controls as periodic checks. Controls generally require somewhat less precision than calibration systems.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

A multi-phase control and/or calibration system consists of a first non-aqueous liquid phase containing an amount of dissolved oxygen (O2) in which the O2 partial pressure is made relatively temperature insensitive over an ambient temperature range of interest, a second, aqueous solution, immiscible with the first solution phase and containing an amount of dissolved carbon dioxide (CO2) and one or more solute species that provide temperature stability with respect to the partial pressure of CO2 over the ambient temperature range of interest. The liquid phases are in equilibrium with a vapor phase and the system may be sealed with a storage atmosphere.

Description

TEMPERATURE INSENSITIVE CALIBRATION SYSTEM
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed generally to a multi-phase control or calibration system and, more particularly, to such a system exhibiting relatively constant partial pressures with respect to certain diverse dissolved gaseous species of interest in one or more liquid phases over a range of ambient temperatures. The preferred fluid consists of a first non-aqueous liquid phase containing an amount of dissolved oxygen (02) in which the partial pressure of 02 is relatively temperature insensitive over an ambient temperature range of interest, a second, aqueous phase, immiscible with the first phase and containing an amount of dissolved carbon dioxide (C02) and one or more solute species that provide temperature stability with respect to the partial pressure of C02 over the ambient temperature range of interest. The liquid phases are in equilibrium with a vapor phase. 2. Description of the Related Art
Relatively inert fluids which have the ability to dissolve rather large amounts of oxygen and which are stable and do not affect biological media, for example, are known. The class of fluorinated organic compounds known as perfluorocarbons are the best known examples of such materials. Perfluorocarbon substances are completely fluorinated organic compounds in which all the carbon-bound hydrogen atoms are replaced with fluorine atoms. These materials have an unique combination of properties. The compounds are extremely non-polar and have essentially no solvent action. They are so chemically inert and have such high thermal stability that they can be mixed with almost any material without fear of any adverse reactive effect either upon other mixture components or upon the material itself. The compounds also have a relatively high boiling points and low pour points giving them a relatively wide liquid range. Many of these perfluorocarbon materials also have a high, relatively stable, oxygen solubility.
These properties have led to the use of perfluoroσarbon solutions as oxygen carriers and as controls for 02 sensors. Aqueous perfluorocarbon multi¬ phase emulsions have been proposed for applications which involve the need to carry or sense oxygen in the presence of carbon dioxide and/or where pH needs to be controlled or sensed. These include medical related technologies involving blood and synthetic blood materials and blood gas analysis controls and calibrators. One such emulsion system is illustrated and described in U.S. Patent 4 722 904 to Feil. Other such systems are disclosed in Turner (U.S. Patent 4 001 142), Cormier, et al. (U.S. Patent Nos. 4 299 728 and 4 369 127) and Sorenson, et al. (U.S. Patent Nos. 4 116 336 and 4 151 108).
These fluids typically comprise an aqueous emulsion of the organic oxygen carrier. Certain of these emulsions may contain surfactant materials, pH buffers and preservative materials. The aqueous phase and the perfluorocarbon phase are chemically compatible but completely immiscible. While the perfluorocarbon phase reversibly carries the oxygen of interest, the aqueous phase reversibly carries other constituents of interest such as carbon dioxide and hydrogen ions.
The use of such materials, particularly as quality controls for blood gas analyzers, for example, requires that the control system contain a known partial pressure of oxygen and a known partial pressure of carbon dioxide and be of a known pH. Accordingly, the control system must be supplied in gas-tight, sealed ampules, or the like containing known amounts of ' dissolved oxygen and carbon dioxide species so that equilibrium partial pressures remain constant. Such a known or control substance can later be used to check the relative accuracy of an instrument utilized to measure 02 and C02 concentration and the pH of such substances as blood. Although such prior approaches have been successful with respect to achieving proper quality control of such devices, the integrity of the partial pressure of the dissolved species used in control measurements depends on the complete isolation of the control system from the time it is prepared until the time of use. In addition, because of the variation in solubility of the gas species of interest with temperature, the opening and use of the control must occur at a specific temperature; and thus the results are also quite temperature dependent.
There remains a definite need to reduce the sensitivity of such control systems to fluctuating or uncertain ambient temperature conditions. This would lead to more versatile uses of the materials and to the development of accurate device calibration methods without the need for rigorous environmental control at the time of calibration. Accordingly, it is an object of the present invention to develop a calibration/control system which is less temperature sensitive than known fluids of the class including aqueous emulsions of perfluorocarbons.
SUMMARY OF THE INVENTION In accordance with the present invention, the temperature sensitivity of the partial pressures of dissolved gases of interest has been greatly reduced. The accuracy of calibration system established at a filling temperature of 20°C, for example, will not be sacrificed by later removal at, for example, 30°C.
In the preferred embodiment, the oxygen carrying solution phase is a solution of oxygen in one or more perfluorocarbon materials. The preferred perfluorocarbon materials include FC-43, FC-75, FC-77, and others, manufactured by and available from the 3M Company of St. Paul, Minnesota. The aqueous solution phase contains a specific amount of C02 complexing agents such as ethylene diamine, HC03 ", Ca++ and OH" or other compounds which buffer the partial pressure of carbon dioxide (C02) in the aqueous solution to changes in temperature. An amount of a compatible pH buffer can also be employed to stabilize the solution with respect to acidity.
The multi-phase control/calibration system of the invention is prepared under tightly controlled conditions and transferred to containers designed to accommodate the desired amount. The filled containers are provided with a sealed storage atmosphere which maintains the desired conditions in equilibrium during the shelf life of the system. This atmosphere typically contains sufficient oxygen and carbon dioxide in a mixture with one or more other gases inert to the system to maintain the desired amount of 02 and C02 species in the liquid phases of the system.
The preferred range of 02 (p02) partial pressure with respect to the system is from about 10 to about 200 mm Hg and the preferred range of partial pressure for C02 (pC02) is from about 5 to 100 mm Hg. The preferred temperature range of temperature relative partial pressure insensitivity is about 20°C to about 30°C. It is also contemplated that various phase components can be used, if desired, to expand the ambient temperature range of relative partial pressure insensitivity beyond the range of 20°C to 30°C, if desired. The range 20° to 30°C, however, represents the normal range of temperatures for an indoor conditioned space.
In addition, surfactants or other wetting agents can be added to emulsify the multiliquid phases, if desired. It is also contemplated that the solution of the calibration system of the invention consist of a single aqueous phase containing, in addition to a C02 binding component or components, one or more solutes which reversibly bind 02, such as copper ions, hemoglobin, and transition metal macromolecular complexing agents. These include meso-tetraphenyl porphorin complexes of Co(II), Co(III), Mn(III) and Fe(II) .
Solutions formulated in accordance with the invention should exhibit stable overall solubilities of the gases of interest over a range of ambient temperatures between about 20°C and 30°C. This means that calibration/control systems in impermeable containers which are filled under strictly controlled conditions at one temperature may be removed from a storage atmosphere at a different temperature and used with complete confidence.
DETAILED DESCRIPTION Although there are some exceptions, notably dilute solutions of hydrogen chloride in water, the solubility of most gases and liquids decreases with increases in temperature. It is further well known that the equilibrium solubility of any volatile constituent of a solution at a given temperature is related to the partial pressure of that constituent in the vapor phase above the liquid at any given temperature. It follows, then, that solutions of critical concentrations of dissolved gaseous species and liquids have an extreme sensitivity both to changes in the partial pressure of each such species above the solution and to changes in temperature of the solution. Prior to the present invention, it has heretofore been necessary to expose the calibration/control system to the ambient environment at a specific temperature to preserve the compositional integrity of the system.
This has heretofore always been the case with respect to control solutions, including those in which oxygen is carried by a perfluorocarbon in one phase and carbon dioxide is carried in a second aqueous solution phase of controlled pH which are used to calibrate biological sensors utilized to detect dissolved oxygen, carbon dioxide and acidity. Because of the inherent properties of these systems, it has always been assumed that the temperature limitation with respect to exposure was one which had to be accommodated and could not be overcome.
According to the present invention, however, it has been discovered that such multi-phase solutions can, indeed, be made less sensitive to variations in ambient temperature over the range of ambient temperatures normally encountered in indoor conditioned spaces, e.g., 20°C to 30°C.
While it has been found that a variety of perfluorocarbon substances exhibit rather stable properties with respect to dessolving amounts of oxygen in the range of 20°C-30°C and, in some instances, even beyond this range, the same cannot be said of the relative concentration of dissolved C02, which decreases with increasing temperature. In accordance with the invention, it has further been' discovered, however, that the use of a dissolved species, such as ethylene diamine in the aqueous phase of the multi¬ phase calibration solution, can stabilize the amount of carbon dioxide dissolved in the aqueous solution. In fact, the overall partial pressure C02 can be substantially linearized over a temperature range comparable to that of 02 in the perfluorocarbon. Compatible buffers can also be added to the aqueous solution to control acidity at the desired pH value.
The solutions or liquid phases in accordance with the invention are prepared under controlled conditions. Known amounts of the dissolved gases 02 and C02 are present in the phases as prepared. However, it may be months or even years before the system is actually used so that long-term stability is required. To preserve the integrity of the system over the shelf life of the product, the calibration system is sealed in an impermeable fluid tight container together with an amount of storage atmosphere which contains sufficient p02 and pC02 to maintian the amount of dissolved species in the liquids over time. The container may be a glass ampule, or the like, but is preferably a polymeric envelope or laminated pouch which may consist of several layers of metallic foil and polymeric materials which make the pouch impervious to atmosphere exchange with the environment. When the seal of the encapsulating container is breached, of course, the protective or storage atmosphere is lost. The calibration system of the present invention, however, maintains its known p02, pC02 and pH for the relatively shorter time required to perform the control or calibration procedure, regardless of the ambient temperature at which the breach occurs as long as that temperature is in the range of relative stability for the system, e.g., 20°C-30°C.
It is apparent that the calibration system of the present invention can also function well as a control system for analytical instruments of the class normally employing such controls as periodic checks. Controls generally require somewhat less precision than calibration systems.
This invention has been described in this application in considerable detail in order to comply with the Patent Statutes and to provide those skilled in the art with the information needed to apply the novel principles and to construct and use such specialized components as are required. However, it is to be further understood that the invention can be carried out by specifically different equipment and devices and that various modifications can be accomplished without departing from the scope of the invention itself.

Claims

CLAIMSWhat is claimed is:
1. A calibration system which is relatively temperature insensitive over an ambient temperature range of interest, comprising: a first calibration medium phase comprising a sufficient amount of a first solvent which has a capacity for dissolving (02) to render the amount of 02 dissolved in the calibration system relatively constant over the ambient temperature range of interest and an amount of 02 dissolved therein; a second calibration medium phase comprising an amount of a second solvent and a solute having a capacity for dissolving carbon dioxide (C02) and an amount of C02 dissolved therein; a vapor phase in contact with the first and second phases; wherein the partial pressure of both 02 and C02 in the phases remains substantially constant over the ambient temperature range of interest.
2. The calibration system of claim 1 wherein the first and second phases are liquid phases.
3. The calibration system of claim 1 further comprising: a fluid tight enclosure for containing the calibration system; and an amount of storage atmosphere of known composition hermetically sealed in the fluid tight enclosure comprising a vapor impermeable barrier in communication with the calibration system.
4. The calibration system of claim 3 wherein the system is insensitive to the relative volume occupied by the vapor phase in relation to that occupied by the first and second phases.
5. The calibration system of claim 3 wherein the first liquid phase comprises an aqueous solution of a solute which reversibly binds to 02.
6. The calibration system of claim 5 wherein the first liquid phase contains an amount of at least one species selected from a group consisting of copper ions, hemoglobin and transition metal complexes.
7. The calibration system of claim 2 wherein the second phase consists substantially of an aqueous solution containing at least one solute species which reversibly reacts with C02.
8. The calibration system of claim 7 wherein the aqueous solution of the second phase contains at least one solute species selected from the group consisting of ethylenediamine and OH" ions.
9. The temperature insensitive calibration system of claim 1 wherein the first solvent consists mainly of a perfluorocarbon material.
10. The temperature insensitive calibration system of claim 3 wherein the first solvent consists mainly of a perfluorocarbon material.
11. The temperature insensitive calibration system of claim 7 wherein the first solvent consists mainly of a perfluorocarbon material.
12. The temperature insensitive calibration system of claim 8 wherein the first solvent consists mainly of a perfluorocarbon material.
13. The calibration system of claim 3 wherein the partial pressure of 02 is in the range of about 10 to 200 mm Hg and wherein the partial pressure of C02 is in the range of about 5 to 100 mm Hg.
14. The calibration system of claim 12 wherein the partial pressure of 02 is in the range of about 10 to 200 mm Hg and wherein the partial pressure of C02 is in the range of about 5 to 100 mm Hg.
15. The temperature insensitive calibration fluid of claim 1 wherein the range of ambient temperatures of interest is from about 20°C to about 30°C.
16. The temperature insensitive calibration fluid of claim 3 wherein the range of ambient temperatures of interest is from about 20°C to about 30°C.
17. The temperature insensitive calibration fluid of claim 12 wherein the range of ambient temperatures of interest is from about 20°C to about 30°C.
18. The multi-phase calibration system of claim 12 wherein the system is insensitive to the relative volume of the vapor phase in equilibrium with the first and second phases.
19. A multi-phase calibration system having a plurality of non-vapor calibration specie containing medium phases in contact with a vapor phase characterized by a relatively temperature independent equilibrium with respect to the partial pressure of gaseous species of interest in each calibration specie containing medium phase over an ambient temperature range extending from about 20°C to about 30°C comprising: a first phase comprising an amount of 02 dissolved in a medium consisting mainly of a perfluorocarbon, wherein the partial pressure of 02 remains substantially constant with respect to changes in temperature in the ambient temperature range of interest; a second calibration specie containing medium phase comprising an amount of C02 dissolved in an aqueous solution containing an amount of at least one solute which reversibly reacts with C02 such that the partial pressure of C02 remains substantially constant with respect to changes in temperature in the ambient temperature range of interest; and a vapor phase in equilibrium with the first and second phases.
20. A multi-phase calibration system having a plurality of liquid phases in contact with a vapor phase characterized by a relatively temperature independent equilibrium with respect to the partial pressure of gaseous species of interest in each liquid phase over an ambient temperature range of interest from about 20°C to about 30°C comprising: a first liquid phase comprising an amount of 02 dissolved in a liquid perfluorocarbon, wherein the partial pressure of 02 remains substantially constant with respect to changes in temperature in the ambient temperature range of interest; a second liquid phase comprising an amount of C02 dissolved in an aqueous solution containing an amount of at least one solute which reversibly reacts with C02 such that the partial pressure of
C02 remains substantially constant with respect to changes in temperature in the ambient temperature range of interest; a vapor phase in equilibrium with the first and second phases; a fluid tight container for storing the calibration system; and an amount of storage atmosphere of known composition hermetically sealed in the fluid tight container with the calibration system.
21. The calibration fluid of claim 20 wherein the aqueous liquid phase further contains an amount of at least one buffer to control the pH.
22. The calibration system of claim 20 wherein the partial pressure of 02 is in the range of about 10 to 200 mm Hg and wherein the partial pressure of C02 is in the range of about 5 to 100 mm Hg.
23. The calibration system of claim 20 wherein the aqueous solution contains at least one solute species selected from the group consisting of ethylediamine and OH" ions.
24. The multi-phase calibration system of claim 20 wherein the system is insensitive to the relative amount of storage atmosphere with relation to the liquid sealed in the fluid-tight container.
25. The calibration system of claim 21 wherein the partial pressure of 02 is in the range of about 10 to 200 mm Hg and wherein the partial pressure of C02 is in the range of about 5 to 100 mm Hg.
26. The temperature insensitive calibration fluid of claim 21 wherein the aqueous solution contains at least one solute species selected from the group consisting of ethylediamine and OH" ions.
PCT/US1991/007917 1990-10-26 1991-10-25 Temperature insensitive calibration system WO1992008130A1 (en)

Applications Claiming Priority (2)

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US60466690A 1990-10-26 1990-10-26
US604,666 1990-10-26

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Citations (7)

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Publication number Priority date Publication date Assignee Title
US4126575A (en) * 1977-11-22 1978-11-21 Louderback Allan Lee Blood control standard
US4163734A (en) * 1975-05-30 1979-08-07 Radiometer A/S Reference liquid for blood gas equipment
US4279775A (en) * 1979-12-31 1981-07-21 Louderback Allan Lee Blood gas control
US4299728A (en) * 1980-07-21 1981-11-10 Instrumentation Laboratory Inc. Blood gas control
US4369127A (en) * 1980-07-21 1983-01-18 Instrumentation Laboratory Inc. Blood gas control
US4469792A (en) * 1980-12-31 1984-09-04 Allied Corporation Blood gas calibration and control fluid utilizing stroma-free hemoglobin
US4485174A (en) * 1982-09-29 1984-11-27 Instrumentation Laboratory Inc. Hemoglobin-based blood gas control

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163734A (en) * 1975-05-30 1979-08-07 Radiometer A/S Reference liquid for blood gas equipment
US4126575A (en) * 1977-11-22 1978-11-21 Louderback Allan Lee Blood control standard
US4279775A (en) * 1979-12-31 1981-07-21 Louderback Allan Lee Blood gas control
US4299728A (en) * 1980-07-21 1981-11-10 Instrumentation Laboratory Inc. Blood gas control
US4369127A (en) * 1980-07-21 1983-01-18 Instrumentation Laboratory Inc. Blood gas control
US4469792A (en) * 1980-12-31 1984-09-04 Allied Corporation Blood gas calibration and control fluid utilizing stroma-free hemoglobin
US4485174A (en) * 1982-09-29 1984-11-27 Instrumentation Laboratory Inc. Hemoglobin-based blood gas control

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. WINDHOLZ et al., "The Merck Index", Tenth Edition, published by, MERCK & CO. INC. (NEW JERSEY), 1983, p. 549. *

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AU9022191A (en) 1992-05-26

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