WO2000002845A1 - Quaternary ammonium salts, polymeric film containing them and colorimetric device - Google Patents
Quaternary ammonium salts, polymeric film containing them and colorimetric device Download PDFInfo
- Publication number
- WO2000002845A1 WO2000002845A1 PCT/GB1999/002080 GB9902080W WO0002845A1 WO 2000002845 A1 WO2000002845 A1 WO 2000002845A1 GB 9902080 W GB9902080 W GB 9902080W WO 0002845 A1 WO0002845 A1 WO 0002845A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- forming polymer
- alkyl ammonium
- sensor device
- quaternary alkyl
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
- G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
Definitions
- This invention relates to oxygen substituted quaternary alkyl ammonium cations, and salts thereof, for incorporation in colorimetric film sensors particularly for the detection of carbon dioxide.
- Carbon dioxide sensors are known which incorporate quaternary alkyl ammonium salts of pH indicator dye acids and carbonic acid within transparent polymer membrane. They act as rapidly responding, reversible and non-consumpting detectors of carbon dioxide in the gas phase. Such sensors respond by changing colour on exposure to carbon dioxide. Furthermore, the response may be made quantitative by monitoring optical absorbance, e.g. using monochromatic light. Colour change occurs through the reversible protonation of the indicator dye anion by carbonic acid formed by the reversible reaction of carbon dioxide with water bound within the film.
- Such sensor films have applications in medicine, horticulture, air conditioning systems, environmental monitoring and industrial health and safety.
- an oxygen substituted quaternary alkyl ammonium cation or salts thereof provide an indicator dye which has improved compatibility with organic polymers, widening the choice of polymers available for sensor film formulation.
- R,, R 2 and R 3 which may be the same or different are each alkyl Cl to 20; and m and n, which may be the same or different, are each an integer from 1 to 19.
- v ues of m and n which may be the same or different, are each from 5 to 10, more preferably m and n together should have a total in the range offrom 4 to 10.
- the salts of the cations of formula I may be selected from the group halide, e.g. fluoride, chloride, bromide or iodide; hydroxide; carbonate and tetrafluoroborate.
- halide e.g. fluoride, chloride, bromide or iodide
- hydroxide e.g. carbonate and tetrafluoroborate.
- bromide salts are preferred, but especially preferred are the hydroxide salts.
- Particularly preferred salts are N,N,N-tripentyl-N-ethyl ethyl ether ammonium bromide and N,N,N-tripentyl-N-ethyl ethyl ammonium hydroxide.
- the cations of formula I, and salts thereof, are advantageous in that they produce an improved pH indicator dye with a greater compatibility with polymers therefore allowing a wider choice of polymers for sensor film formulation.
- a film formulation comprising a cation of formula I, or a salt thereof, in intimate mixture with a transparent film-forming polymer vehicle.
- the transparent vehicle may be a film forming oligomer.
- the transparent film-forming polymer vehicle should be compatible with the indicator material, such that the latter does not exude or otherwise undergo phase separation over a prolonged period (the intended lifetime of the sensor).
- the film-forming polymer should be volatile, e.g. at room temperature and the quaternary alkyl ammonium cation, or a salt thereof should be soluble in the polymer.
- the film- forming polymer vehicle should preferably be hydrolytically stable in order to avoid unwanted changes in the pH in the absence of carbon dioxide.
- the polymer should furthermore preferably be substantially permeable to carbon dioxide.
- the hydrolytically stable film-forming polymer may be water-soluble or organic solvent-soluble. It is preferred that the film-forming polymer is organic solvent soluble.
- suitable organic solvent soluble film-forming polymers include polyvinyl butyral, polyvinyl methyl ether, polymethyl methacrylate, ethyl cellulose and polystyrene.
- water-soluble film-forming polymers which also have good resistance to hydrolysis, include hydroxypropyl cellulose, carboxymethyl cellulose, polyethylene glycol, polyvinyl alcohol (100% hydrolised) and polypropylene glycol.
- polymers include polydimethyl silicone, and polyurethane.
- Such a device may generally comprise;
- Any conventionally known pH sensitive dyes may be used, including thymol blue, m-cresol purple, xylenol blue and/or cresol-red.
- the volatile polymer or oligomer may be any such material which is conventionally known in the art, for example, such as is described in PCT patent application no. WO96/24054 which describes that the film forming component is preferably a water- insoluble low volatility organic substance, which is not susceptible to alkaline hydrolysis and is liquid at temperatures below 100°C, e.g. at room temperature, or is semi-solid e.g. of waxy structure, at room temperature.
- Compounds which are "susceptible to alkaline hydrolysis” includes compounds such as those containing ester groups which are subjected to alkaline hydrolysis in the presence of a basic component.
- the film forming component may be selected from the group consisting of alcohols, phenols and alkoxylated derivatives of such substances, e.g. having at least one linear or branched polyether.
- the film forming component may have be a compound having one of the following structures:
- R 9 and R 12 each represents H or a linear or branched hydrocarbon residue of 1 to 50 carbon atoms, optionally containing one or more double bonds, triple bonds and/or ring structures
- R 10 , R n and R 13 each represents a linear or branched hydrocarbon residue of 1 to 10 carbon atoms
- x and y are equal or different integers from 0 to 100
- p is an integer from 1 to 6
- q and r are equal or different integers from 0 to 4.
- Polyalkylene glycols such as polymethylene glycols, polyethylene glycols, polypropylene glycols, polybutylene glycols .and copolymers of ethylene oxide, propylene oxide and/or butylene oxide.
- Other linear polyethers such as polytetrahydrofurans.
- Alkoxylated alcohols or phenols such as ethoxylated, propoxylated or butoxylated alcohols derived from fatty alcohols (straight or branched, saturated or unsaturated, etc), alkyl phenols, dialkyl phenols, alkyl naphthalenes, bisphenol A, alkyne diols, lanolin, cholesterol, phytosterol, sitosterol, glucose ethers and silicones; and mixed ethoxylated/propoxylated .alcohols.
- Branched polyethers for instance products obtained by ethoxylating and/or propoxylating trimethylol propane or pentaerythritol.
- Alkoxylated amines such as ethoxylated and/or propoxylated primary or secondary amines or dia ines.
- Dialkyl ethers e.g. dioctyl ether.
- Silicone oligomers or polymers may also be used since they have the advantage that, inter alia, they are highly permeable to carbon dioxide.
- a typical silicone polymer has permeability (that is, the gas transmission rate of a film of the polymer of thickness 0.001 inch, expressed as cubic centimetres of gas transmitted through 1 mm of film per 24 hours per square inch of film with one atmosphere differential across the film) is typically as follows:
- the silicone oligomers and polymers are, easy to handle and to apply to a suitable substrate using an organic solvent such as a hydrocarbon type solvent (such as hexane), a chlorinated solvent (for example, chloroform or dichloromethane), an ether solvent (such as tetrahydrofuran), or a low molecular weight oligomeric silicone (such as a cyclic dimethyl silicone).
- a hydrocarbon type solvent such as hexane
- a chlorinated solvent for example, chloroform or dichloromethane
- an ether solvent such as tetrahydrofuran
- a low molecular weight oligomeric silicone such as a cyclic dimethyl silicone
- silicone oligomers or polymers are substantially non-curable they have good storage stability and can be stored indefinitely in the solvent.
- the silicone oligomers or polymers are also readily compatible with the pH sensitive dye and the basic substance, and can be applied in the form of a film on a preformed substrate (such as a plastics, paper or glass substrate).
- a preformed substrate such as a plastics, paper or glass substrate.
- the silicone may be applied as an impregnation throughout a porous carrier medium, for example, of glass fibre, paper, plastics, textile fabric or the like. It is particularly preferred to use such materials which have been provided with a hydrophobic surface treatment, for example, by silanisation.
- the silicone oligomers or polymers are preferably substantially linear and substantially free of hydrophilic groups; preferred substituents for the silicone chain are methyl groups (although other low molecular weight hydrophobic groups may be employed, such as ethyl or trifiuoromethyl groups).
- the silicone oligomer or polymer is a linear polydimethylsiloxane.
- the sihcone preferably has a molecular weight in the range of 200 to 200000, and is preferably optically transparent.
- higher molecular weight silicone polymers are used they are very good binders and have a low glass transition temperature such that they maintain their physical properties over a wide range of temperatures. They are furthermore non-toxic and non-volatile, and hydrolytically stable.
- the silicone oligomers or polymers are furthermore compatible with the indicator ingredients (the dye and the basic substrate), and can be free of migratable low molecular weight materials such as plasticisers or the like.
- the device will be in the form of film sensor and the film may therefore require a support such as polypropylene sheet, a cellulose layer or a plastics foil material.
- the sensors of the invention may comprise a silanised paper support which is preferably non-translucent i.e. is reflective, such as a white film which aids in visual indication.
- the support may be a transparent film on a glass substrate which permits quantitative interrogation with, e.g. monochromatic light.
- the sensor device of the invention functions by the reaction of carbon dioxide with traces of water bound within the sensor film to form carbonic acid (H 2 CO 3 ).
- carbonic acid H 2 CO 3
- dissociation of H 2 CO 3 to H + and HCO 3 " produces a fall in sensor pH which in turn produces an optical absorbance change through the reversible protonation of the pH indicator dye.
- a method of carbon dioxide detection which comprises placing a sensor according to the invention in situ and observing a colour change.
- the sensors of the invention have particul.ar utility in determining the proper placement of the tracheal tube of an endotracheal intubation device in a patient.
- a further feature of the invention is to provide an endotracheal apparatus comprising a sensor as hereinbefore described.
- a method for determining the proper placement of an endotracheal tube which comprises inserting an endotracheal tube comprising a sensor according to the invention, into a patient and observing a colour change.
- TPA Tri Pentyl Amine
- BEE Bromoethyl Ethyl Ether
- the chemical structure of the new ammonium salt is shown below: Ri I R 3 -N + -(CH 2 ) n -O-(CH 2 ) m -CH 3 . Br '
- R réelle R 2 and R 3 are pentyl and n and m are each 2.
- TEEAB was dissolved in 17.6g (22.3ml) of methanol. 4g of Ag 2 O was added to the solution and stirred for one hour. The resulting 20% w/w methanolic solution of the hydroxide salt, TEEAOH was collected by decantation.
- pH indicator dye m-cresol purple, Thymol blue or xylenol blue
- Methanol was evaporated using a rotary evaporator and 7.9g of tetrahydrofuran was added to form a 20:1 base:dye solution.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99931364A EP1097124A1 (en) | 1998-07-11 | 1999-07-12 | Quaternary ammonium salts, polymeric film containing them and colorimetric device |
AU47902/99A AU4790299A (en) | 1998-07-11 | 1999-07-12 | Quaternary ammonium salts, polymeric film containing them and colorimetric device |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9815002.2A GB9815002D0 (en) | 1998-07-11 | 1998-07-11 | Formulations |
GB9815002.2 | 1998-07-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000002845A1 true WO2000002845A1 (en) | 2000-01-20 |
Family
ID=10835305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1999/002080 WO2000002845A1 (en) | 1998-07-11 | 1999-07-12 | Quaternary ammonium salts, polymeric film containing them and colorimetric device |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1097124A1 (en) |
AU (1) | AU4790299A (en) |
GB (1) | GB9815002D0 (en) |
WO (1) | WO2000002845A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007050463A1 (en) * | 2005-10-26 | 2007-05-03 | General Electric Company | Material compositions for sensors for determination of chemical species at trace concentrations and method of using sensors |
US7863459B2 (en) | 2005-12-16 | 2011-01-04 | Sun Chemical Corporation | Process for preparing onium salts |
US7883898B2 (en) | 2007-05-07 | 2011-02-08 | General Electric Company | Method and apparatus for measuring pH of low alkalinity solutions |
CN104897663A (en) * | 2015-05-21 | 2015-09-09 | 北京大学深圳研究生院 | Thin film sensor for detecting carbon dioxide and application of thin film sensor |
US10175254B2 (en) | 2013-07-16 | 2019-01-08 | Palo Alto Health Sciences, Inc. | Methods and systems for quantitative colorimetric capnometry |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2087132A (en) * | 1933-04-13 | 1937-07-13 | Alba Pharmaceutical Company In | Quaternary ammonium compounds |
DE682393C (en) * | 1933-04-14 | 1939-10-13 | I G Farbenindustrie Akt Ges | Process for the production of quaternary nitrogen compounds |
EP0324494A1 (en) * | 1988-01-14 | 1989-07-19 | W.R. Grace & Co.-Conn. | Permanent antistatic acid copolymer/quaternary amine mixtures and permanent antistatic polymeric films made therefrom |
WO1989007957A1 (en) * | 1988-02-26 | 1989-09-08 | Brigham And Women's Hospital | Co2 indicator for placement of tracheal tubes |
US5005572A (en) * | 1988-02-26 | 1991-04-09 | Brigham & Women's Hospital | CO2 indicator and the use thereof to evaluate placement of tracheal tubes |
WO1991005252A1 (en) * | 1989-09-29 | 1991-04-18 | Abbey Biosystems Limited | Carbon dioxide monitor |
WO1996024054A1 (en) * | 1995-02-03 | 1996-08-08 | Icor Ab | A colorimetric device for indicating carbon dioxide |
-
1998
- 1998-07-11 GB GBGB9815002.2A patent/GB9815002D0/en not_active Ceased
-
1999
- 1999-07-12 EP EP99931364A patent/EP1097124A1/en not_active Withdrawn
- 1999-07-12 AU AU47902/99A patent/AU4790299A/en not_active Abandoned
- 1999-07-12 WO PCT/GB1999/002080 patent/WO2000002845A1/en not_active Application Discontinuation
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2087132A (en) * | 1933-04-13 | 1937-07-13 | Alba Pharmaceutical Company In | Quaternary ammonium compounds |
DE682393C (en) * | 1933-04-14 | 1939-10-13 | I G Farbenindustrie Akt Ges | Process for the production of quaternary nitrogen compounds |
EP0324494A1 (en) * | 1988-01-14 | 1989-07-19 | W.R. Grace & Co.-Conn. | Permanent antistatic acid copolymer/quaternary amine mixtures and permanent antistatic polymeric films made therefrom |
WO1989007957A1 (en) * | 1988-02-26 | 1989-09-08 | Brigham And Women's Hospital | Co2 indicator for placement of tracheal tubes |
US5005572A (en) * | 1988-02-26 | 1991-04-09 | Brigham & Women's Hospital | CO2 indicator and the use thereof to evaluate placement of tracheal tubes |
WO1991005252A1 (en) * | 1989-09-29 | 1991-04-18 | Abbey Biosystems Limited | Carbon dioxide monitor |
EP0509998A1 (en) * | 1989-09-29 | 1992-10-28 | Abbey Biosystems Ltd | Carbon dioxide monitor. |
WO1996024054A1 (en) * | 1995-02-03 | 1996-08-08 | Icor Ab | A colorimetric device for indicating carbon dioxide |
Non-Patent Citations (3)
Title |
---|
ARTHUR JAMES EWINS: "Some new physiologically active derivatives of choline", BIOCHEM. J., vol. 8, 1914, pages 366 - 373, XP002120126 * |
KATSUHIKO AKAGI ET AL.: "Reactivities of several omega-substituted primary alkyl bromides with tertiary amines", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY., vol. 79, no. 12, 26 June 1957 (1957-06-26), DC US, pages 3118 - 3120, XP002120128 * |
RALPH B. FEARING ET AL.: "Some strongly basic derivatives of (+)- and (-)-1-hydroxy-2-aminobutane", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY., vol. 76, no. 17, 9 September 1954 (1954-09-09), DC US, pages 4382 - 4385, XP002120127 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007050463A1 (en) * | 2005-10-26 | 2007-05-03 | General Electric Company | Material compositions for sensors for determination of chemical species at trace concentrations and method of using sensors |
US7807473B2 (en) | 2005-10-26 | 2010-10-05 | General Electric Company | Material compositions for sensors for determination of chemical species at trace concentrations and method of using sensors |
US8647883B2 (en) | 2005-10-26 | 2014-02-11 | General Electric Company | Material compositions for sensors for determination of chemical species at trace concentrations |
US7863459B2 (en) | 2005-12-16 | 2011-01-04 | Sun Chemical Corporation | Process for preparing onium salts |
US7883898B2 (en) | 2007-05-07 | 2011-02-08 | General Electric Company | Method and apparatus for measuring pH of low alkalinity solutions |
US8076153B2 (en) | 2007-05-07 | 2011-12-13 | General Electric Company | Method and apparatus for measuring pH of low alkalinity solutions |
US8148166B2 (en) | 2007-05-07 | 2012-04-03 | General Electric Company | Method and apparatus for measuring pH of low alkalinity solutions |
US10175254B2 (en) | 2013-07-16 | 2019-01-08 | Palo Alto Health Sciences, Inc. | Methods and systems for quantitative colorimetric capnometry |
US11538569B2 (en) | 2013-07-16 | 2022-12-27 | Freespira. Inc. | Methods and systems for quantitative colorimetric capnometry |
CN104897663A (en) * | 2015-05-21 | 2015-09-09 | 北京大学深圳研究生院 | Thin film sensor for detecting carbon dioxide and application of thin film sensor |
Also Published As
Publication number | Publication date |
---|---|
GB9815002D0 (en) | 1998-09-09 |
EP1097124A1 (en) | 2001-05-09 |
AU4790299A (en) | 2000-02-01 |
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