WO1998058246A2 - Improvements in and relating to compounds, sensors and extractants - Google Patents
Improvements in and relating to compounds, sensors and extractants Download PDFInfo
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- WO1998058246A2 WO1998058246A2 PCT/GB1998/001632 GB9801632W WO9858246A2 WO 1998058246 A2 WO1998058246 A2 WO 1998058246A2 GB 9801632 W GB9801632 W GB 9801632W WO 9858246 A2 WO9858246 A2 WO 9858246A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D497/04—Ortho-condensed systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/02—Five-membered rings
- C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Definitions
- This invention concerns improvements in and relating to compounds, sensors and extractants.
- the invention is particularly concerned, but not exclusively, with electrochemical sensors for environmental monitoring and extractants for removing cations from solution.
- the extraction of cations from solution in many applications is also desirable.
- the cations may be present in organic or aqueous phases, such as waste streams, and at a variety of concentration levels.
- the present invention aims to provide sensors, extractants and methods for producing and using these, together with compounds, suitable for use in such applications or their preparation, as well as a number of other objectives.
- T 1( T 2 , T 3 , T 4 independently comprise T E , T E T H , T E T S , T E T H T S where : -
- T E is -H, -OH, -CH 3 , -SH, -CH 2 SH, -CH(SH) 2 , -C(SH) 3I -CN, -SCOCH 3 , -SEt, -SPh, -S(CH 2 ) n Et, -S(CH 2 ) dislikePh -C(Hal) 3 , -CH(Hal) 2 , -CH 2 Hal, where Hal is any halogen; T s is -S-(CH 2 ) n S-;
- T m is -(CH 2 ) n -, -(CH) m (CH 2 ) n -, -CO-, -CO(CH 2 ) n -, -(CH 2 ) m CO-, -(CH 2 ) m CO(CH 2 ) n -, -C00-, -COO(CH 2 ) n -, -(CH 2 ) m COO-, - (CH 2 ) m COO(CH 2 ) n - , including halogen substituted forms thereof and where m is 1 to 15 and n is 1 to and where R 1# R 2 are independently chains of formulae :- -CH 3/ -(CH 2 ) p OH, -(CH 2 ) p CN, -(CH 2 ) p Me, -SCH 3 , -S(CH 2 ) p OH, -S(CH 2 ) p CN, -S (CH 2
- Compounds according to this formulation are useful as end products, or as intermediaries in the formation of such products, particularly where the products are intended for the sensor or extractant type applications with which this invention is concerned.
- the compound senses cations in aqueous or organic solution, most preferably metal cations.
- the compound is self-assembling to a substrate.
- the compound has both these properties.
- the compound is a metal ion sensor.
- the compound is according to formula A.
- X 1 is the same as X 2 .
- X x or X 2 is S, most preferably both are S.
- T ⁇ ; T 2 , T 3 or T 4 are -SH terminated. This offers a self-assembly function for the compound onto a suitable substrate.
- T , T 2 , T 3 , T 4 are independently selected from :- -H, -CF3, -(CH 2 ) n SH, -C00H, -C00CH 3 , -COH, -COCH 3 , -C00(CH 2 ) n Br, -COO(CH 2 ) n SH, -C0(CH 2 ) n SH, -S(CH 2 ) n CN, - SCH 3 , -S(CH 2 ) n SH, -SC00(CH 2 ) n SH, -SCO (CH 2 ) n SH.
- T ⁇ ; T 2 or T 1 and T 2 are selected therefrom and T 3 or T 4 and more preferably T 3 and T 4 are -H, -CF3 or -CH 3 .
- T and T 2 are the same with T x or T 2 being selected from the above with the other being -H, -CF3 or -CH 3 .
- n is 2 to 20, more preferably 5 to 15 and most preferably 8 to 12.
- m is 1 to 12, more preferably 1 to 8 and most preferably 2 to 4.
- m and n when taken together are less than 22.
- R x or R 2 independently are -(CH 2 ) 2 Me ; -(CH 2 ) 2 CN, -H, -CH 3 , -(CH 2 ) 2 OH, - (CH 2 ) 2 0(CH 2 ) 2 0H and most preferably are the same .
- p is 1 to 6, most preferably 2 to 4 and most preferably of all 2.
- t is 0 to 5 and preferably 0 to 2.
- R x and R 2 are joined by chain of formulae :- - [ (CH 2 ) 2 0] 4 CH 2 - or - (CH 2 ) 2 or - [ (CH 2 ) 2 S] 2 CH 2 2- or -CH 2 SCH 2 20CH 2 SCH 2 .
- v is 2 to 6, most preferably 2.
- w is 2 to 4, most preferably 2.
- y is 3 to 6, most preferably 4.
- a compound comprising a redox active group and a cation sensing group and / or a thiol terminated group.
- the redox group may be tetrathiafulvalene, ferrocene, dithiin or bipyridinium based.
- the redox active group is selected from formulae:
- X x and X 2 are independently S or Se. Most preferably X x and X 2 are the same . Preferably X x and/or X 2 are S .
- T 1# T 2 , T 3 , T 4 may independently by -H, -CF3, -CH 3 , a carbon based chain, including an alkyl, a thioalkyl, an ester, or a ketone chain and/or be -SH terminated.
- T x , T 2 , T 3 , T 4 is selected from :- -(CH 2 ) n SH, -C00(CH 2 ) n SH, -CO(CH 2 ) n SH, -S(CH 2 ) n SH, -SCOO(CH 2 ) n SH, -SCO(CH 2 ) n SH.
- T 3 or T 4 are -H, -CF3 or -CH
- R ⁇ and R 2 together are - [ (CH 2 ) 2 0] 4 CH 2 -
- a cation sensor and/or extractor incorporating a compound according to the first and / or second aspect of the invention.
- the sensor/extractant may be provided in solution, as a Langmuir-Blodgett layer, as a cast layer or as a self-assembled layer .
- the cation sensor/extractor is provided with the compound in a fixed state.
- the compound is fixed to a substrate.
- the substrate can be introduced to a liquid to be sensed.
- the substrate can readily be removed from the liquid following sensing.
- the compound is provided on substrate which can be introduced to the liquid and separated therefrom following extraction.
- the compound may be provided on beads, zeolites or the like.
- the compound is provided in conjunction with an electrode, most preferably in electrical contact with the electrode.
- the sensor may further provide a reference electrode. Both the compound bearing electrode and reference electrode, in use, being in contact with the fluid to be sensed.
- the compound is fixedly mounted on an electrode.
- the compound may be present on the electrode or extractor as a mono-layer.
- the compound may be provided on the electrode or extractor as a cast film.
- the compound may be provided on the electrode or extractor as a self-assembly layer.
- Gold or platinum electrodes may be provided.
- the electrode may be in the form of a coil, wire, strip or the like.
- the metal electrode may be applied to a glass substrate, electrically non-conducting substrate, silicon substrate, single crystal silica substrate or the like.
- the compound may be employed in the sensor or extractor as a solution.
- the compound may be employed in the sensor or extractor as a Langmuir-Blodgett layer.
- the sensor may be qualitative or quantitative.
- the fluid to which the sensor or excractor is introduced in use is most preferably a liquid.
- the sensor or extractor may be introduced to an organic liquid and/or an aqueous liquid during use .
- the metal ions may include Ag, Zn, Na, Ba for instance.
- the sensors detection of the cations may be determined by an electrochemical response, a change in the compounds response to incident radiation thereon, such as fluorescence or a combination of such techniques .
- the senor's or extractor's reaction with the cation is reversible.
- a fourth aspect of the invention we provide a method of producing a sensor comprising attachment of a compound according to the first or second aspect of the invention to an electrically conducting material .
- the electrically conducting material may comprise an electrode or an electrically conducting material contacting an electrode.
- the compound may be attached to the electrically conducting material by means of film casting.
- the compound may be attached to the electrically conducted material by self assembly.
- the compound is provided in the electrically conducted material from an organic solution containing the compound.
- Acetonitrile or acetonitrile / benzene solvents may be employed for this purpose.
- the electrode may be provided on a substrate prior to attachment of the compound.
- a non-conducting substrate such as a glass or silica substrate is preferred.
- the electrode may be applied by electro-deposition, screen printing or may be formed by etching or physical removal of part of a layer on a substrate to give an electrode of the desired configuration.
- the substrate preferably supports a reference electrode.
- the compound is provided according to the first and/or second aspect of the invention.
- a fifth aspect of the invention we provide a method of sensing comprising contacting a liquid to be sensed with a compound according to the first and / or second aspect of the invention, with a sensor according to the third or produced according to the fourth aspect of the invention in which the component to be detected (if present) alters a property of the sensor, the charged property being detected.
- a sixth aspect of the invention we provide a method of removing cations from a liquid comprising contacting the liquid with a compound according to the first aspect of the invention and/or a compound according to the second aspect of the invention and/or an extractor according to the third aspect of the invention and separating the compound/extractant or extractor from the liquid.
- Figure 1 illustrates one configuration of a molecule according to the inven ion
- Figure 2a illustrates a synthesis route for oxone , •
- Figure 2b illustrates a synthesis route for thione
- Figure 3 illustrates synthesis 1, 2 and 3 for compounds la, lb and lc;
- Figure 4 illustrates a further configuration of a molecule according to the invention
- FIG. 5 illustrates synthesis 4 for compounds 9 and 10
- Figure 6 illustrates a still further configuration of a molecule according to the invention
- Figure 7 illustrates two alternative synthesis routes for starting materials for synthesis 5;
- Figure 8 illustrates synthesis 5, 6, 7, 8 and 9 for compounds 13, 21, 22, 23 and 24;
- Figure 9 illustrates synthesis 10 and 11 for compounds 25, 26, 27, 28 and 29;
- Figure 10 illustrates synthesis 12, 13 and 14 for compounds 30, 33, 34 and 35;
- Figure 11 illustrates synthesis for compounds 39, 40 and 24;
- Figure 12 illustrates synthesis for compounds 42, 37, 43 and 44;
- Figure 13 illustrates synthesis for compounds 45 and 46
- Figure 14 illustrates synthesis for compounds 48, 47a, 47b, 49a and 49b;
- Figure 15 illustrates synthesis for compounds 51, 52 and 53;
- Figure 16 illustrates synthesis for compounds 56, 57, 58 and 54;
- Figure 17 illustrates synthesis for compounds 60, 61, 62 and 57
- Figure 18 illustrates synthesis for compounds 63, 64, 66, 68 and 70;
- Figure 19 illustrates synthesis for compounds 72, 73, 74 and 75;
- Figure 20 illustrates synthesis for compounds 57 and 54
- Figure 21a illustrates synthesis for compounds 77, 78 and 79
- Figure 21b illustrates synthesis for compounds 82, 83, 84, 85, 86 and 87;
- Figure 22 illustrates synthesis for compounds 88, 89, 90, 91, 92, 93 and 94;
- Figure 23 illustrates a yet further configuration of a molecule according to the invention.
- Figure 24 illustrates a still further configuration of a molecule according to the invention.
- Figure 25 illustrates FT-RAIRS spectra for compound la on an Au surface
- Figure 26 illustrates smooth data according to Figure 25
- Figure 27 illustrates cyclic voltametry for compound la
- Figure 28 illustrates cyclic voltametry for compound lb
- Figure 29 illustrates cyclic voltametry for compound 46
- Figure 30a illustrates cyclic voltametry for compound la with BuNBF. as electrolyte and with NaPF 6 as salt
- Figure 30b illustrates cyclic voltametry for compound la in Bu 4 NBF 4 as electrolyte and with AgBF 4 as salt;
- Figure 31a illustrates the change of voltametric response for compound la in differential pulse voltametry
- Figure 31b illustrates the change in voltametric response for compound la in square wave voltametry
- Figure 32 shows cyclic voltametry results for compound 16 with Ag + ;
- Figure 33a illustrates cyclic voltametry results for a self assembly monolayer of compound 44 on an Au electrode in 0.5M LiC10 4 /acetonitrile ;
- Figure 33b illustrates cyclic voltametry results for a self assembly monolayer of compound 44 on a Au electrode in 0.5M HC10 4 ;
- Figure 34a illustrates equivalent results to 33a, but for compound 46;
- Figure 34b illustrates equivalent results to 33b, but for compound 46;
- Figure 35 illustrates the change in voltametric response for compound 46 self assembled on a platinum electrode in solution of 0.2M Bu 4 NC10 4 /acetonitrile after addition of 0.012M of AgC10 4 solution (-line);
- Figure 36 illustrates the change of voltametric response for compound 71 in acetonitrile, 0.2 Bu 4 NC10 4 , dotted line saturated AgC10 4 ;
- Figure 37 illustrates results for compound 75 in an equivalent system to that of Figure 36; and Figure 38 illustrates the change of voltametric response for compound 24 in acetonitrile/water, 0.2M Bu 4 NC10 4 , acidified to pH 2 by HC10 4 , dotted line 5.85 x 10 "2 MOL L -1 AgC10 4 .
- the basic three part structure of the present invention is illustrated in one configuration in Figure 1.
- the molecule consists of a crown ring A, a tetrathiafulvalene link B and terminal thiol group C .
- the terminal thiol group and tetrathiafulvalene are linked by a carbon chain spacer unit D.
- the overall assembly works in terms of the macro cycle providing a cation, particularly metal ion, accepting site.
- the acceptance of the metal ion results in a change in the oxidation of the redox active tetrathiafulvalene group.
- This change can be detected in a number of ways and from a number of results.
- the system may be chromophoric so resulting in a colour change which is detectable either to the eye or more normally to a colour sensitive technique such as a UV-VIS spectrophotometry or surface plasma resonance.
- the change in oxidation can give rise to a potential or current. If the compound is provided in electrical contact with a substrate which can act as an electrode this too can be determined .
- the thiol termination to the carbon chain provides the structure with a self-assembly function facilitating the attachment of the compound to a substrate such as an electrode.
- the carbon chain acts to space the attachment from the redox group and metal sensing component.
- the chain normally facilitates alignment of separate molecules in the assembled form, the tails being attached to the substrate, the metal sensing groups being exposed to the solution.
- the synthesis started from oxone and thione.
- the oxone was obtained using the sequence set out in Figure 2a with thione being obtained using the sequence set out in Figure 2b.
- the material was subsequently thiolated and hydrolysed to give the target compound lb .
- Figure 6 illustrates a further variation on the basic structure, in which the crown ring is replaced by a pair of chains .
- compound 39 was generated by reduction of compound 6 in dichloromethane at -78°C using diisobutylaluminium hydride . Higher temperature reactions gave a complex mixture.
- Figure 16 illustrates the production scheme for compound 54 from compounds 55 and 4. Triethyl phosphite mediated cross coupling of compounds 4 and 55 afforded compound 56 (44% yield after chromatographic separation from symmetrically coupled products) following a reaction at 120°C for three hours.
- Compound 54 is produced from compound 58 by reduction of the thioester using LiAlH 4 upon aqueous hydrolysis, 88% yield.
- Compound 54 is an air stable orange oil .
- saponification of the thioester using sodium hydroxide in dioxane or transesterification using sodium ethoxide in ethanol and tetrahydrofuran afforded after hydrolysis compound 54 also.
- Figure 17 shows the production scheme for compound 57 from compound 59.
- the cyanoethyl protected thiolate was deprotected using cesium hydroxide in methanol followed by in si tu trapping with either 3- bromopropanol or 6-bromohexanol to produce compounds 60a and b accordingly, 90 and 88% yields respectively.
- t-butyldiphenylsilyl protected alcohol compound 64a and b and 65a and b could be deprotected using tetrabutylammonium fluoride in tetrahydrofuran to give alcohol 66a and b and 67a and b respectively with yields of between 85 and 95%. Modification of the alcohol to thiol using the 2 step synthesis discussed above is possible.
- Compound 94 illustrated in Figure 22 and comparable compound to compound 54 was synthesised using the illustrated reaction route.
- Compound 94 has an hexyl chain that was designed to fill the void generated by the methyl group in compound 54 and as analysed by molecular modelling.
- Compound 94 was prepared in 2 steps, 74% overall yield, as an orange oil, using the 2 stage synthesis detailed earlier. Aswell as these examples other compound types are suitable for use in the present invention. These include the type of compound illustrated in Figure 23 which has a similar structure to that set out in Figure 1 but employs selenium as the conjugated lone pairs. In this case they are provided at the TTF to crown ring junction, but their use with open chains is also possible.
- the compound illustrated in Figure 24 provides a further variation in which the crown is provided as a bridge, but between the sulphurs positioned on different ends of the THF group .
- the compounds are, however, particularly suitable for provision as self-assembly layers and this is desirable because it offers a simple and cheap technique and the chemical attachment results in a more robust assembly .
- the gold substrate was cleaned prior to dipping into the self assembled solution by immersion for 20 seconds in chromic solution (5 gram K 2 Cr 2 0 7 ) dissolved in lOcc water with slow addition of 50cc concentrated sulphuric acid; followed by rinsing in distilled water; followed by 20 seconds in dilute aqua regia; followed by rinsing with copuois water; followed by rinsing with methanol followed by drying in a current of nitrogen.
- chromic solution 5 gram K 2 Cr 2 0 7
- lOcc water with slow addition of 50cc concentrated sulphuric acid
- This self assembled solution was obtained by dissolving the solid compound in 5cc if HPLC grade acetonitrile in a sonic bath for 15 minutes. The resulting light orange solution/suspension was then transferred into the Teflon dipping container and a gold substrate dipped immediately following its cleaning.
- the monolayers are applied to the substrates by contact with the compound in question in a solution of acetonitrile or acetonitrile-benzene . Layer thicknesses of around 2.2nm have been determined.
- Figure 27 and Figure 28 show cyclic voltametry results for compounds la and lb on 1.6mm diameter Pt electrode against an Ag / Ag + reference electrode. The result for compound lb in particular is close to that shown in the equivalent solution system.
- Figure 29 shows cyclic voltametry results for compound 46 on 0.076mm working diameter Pt electrode. The response is measured in a solution of 0.2M Bu 4 NPF 6 /acetonitrile in saturated Ba(C10 4 ) 2 solution (dashed line). Electrochemical recognition behaviour was thus demonstrated for this compound with a typical shift in E x of circa 70mV.
- the compound was used in conjunction with an Fc/Fc+ couple as the internal reference to test that the reference electrode did not change potential at high salt concentrations .
- Table 2 below provides details of the shift in oxidation potential with solutions of the different salts listed. As can be seen a response to all the cations results, increasing in strength from Lithium through Sodium to the strongest response for Silver ions .
- Figures 34a and 34b indicate equivalent results for compound 46 in equivalent systems .
- Compound 54 exhibited electro chemical recognition behaviour for Ag+ ions in acetonitrile solution and as a self assembly monolayer in acetonitrile .
- Figures 36 and 37 illustrate changes in voltametric response for compounds 71a and 75 respectively in acetonitrile with 0.2M Bu 4 NC10 4 using a 0.5mm diameter electrode, dotted line saturated Pb(C10 4 ) 2 .
- Figure 5 shows the response to Ag-i- ions in a mixed acetonitrile/water medium using compound 24.
- the CV response for different ratios Ag + to the compound 24 are shown in Figure 38.
- tetrathiafulvalene group as the basis for the compound is beneficial over many other groups, including ferrocene for instance, as it is capable of undergoing two separate oxidations .
- the second oxidation can therefore be used as an internal reference to confirm the results detected and the detection of the first oxidation.
- the geometry of the tetrathiafulvalene group, particularly in combination with a relatively straight chain is also beneficial to the invention.
- the more planar structure of the molecule, for instance, compared with the ferrocene for instance, renders self-assembly easier and allows closer packing of the molecules on the substrate.
Abstract
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU82215/98A AU8221598A (en) | 1997-06-18 | 1998-06-18 | Improvements in and relating to compounds, sensors and extractants |
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Application Number | Priority Date | Filing Date | Title |
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GB9712694A GB9712694D0 (en) | 1997-06-18 | 1997-06-18 | Improvements in and relating to compounds,sensors and extractants |
GB9712694.0 | 1997-06-18 |
Publications (2)
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WO1998058246A2 true WO1998058246A2 (en) | 1998-12-23 |
WO1998058246A3 WO1998058246A3 (en) | 1999-03-18 |
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PCT/GB1998/001632 WO1998058246A2 (en) | 1997-06-18 | 1998-06-18 | Improvements in and relating to compounds, sensors and extractants |
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AU (1) | AU8221598A (en) |
GB (1) | GB9712694D0 (en) |
WO (1) | WO1998058246A2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006113440A2 (en) * | 2005-04-15 | 2006-10-26 | Worcester Polytechnic Institute | Multi-transduction mechanism based microfluidic analyte sensors |
JP2008222639A (en) * | 2007-03-13 | 2008-09-25 | Showa Shell Sekiyu Kk | New compound and lubricating oil composition containing the same |
CN103936761A (en) * | 2014-03-28 | 2014-07-23 | 宁波工程学院 | 3-pyridyl containing tetrathiafulvalene compound as well as preparation method and application thereof in specific recognition of Cu<2+> |
CN106831510A (en) * | 2017-01-16 | 2017-06-13 | 黄河三角洲京博化工研究院有限公司 | Thio hendecane of 1,11 dihydroxy 3,6,9 3 and preparation method thereof |
US9933385B2 (en) | 2007-12-10 | 2018-04-03 | Ascensia Diabetes Care Holdings Ag | Method of using an electrochemical test sensor |
US10067082B2 (en) | 2004-02-06 | 2018-09-04 | Ascensia Diabetes Care Holdings Ag | Biosensor for determining an analyte concentration |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BRPI0613592A2 (en) | 2005-07-20 | 2011-01-18 | Bayer Healthcare Llc | port-connected amperometry |
Citations (1)
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EP0590539A2 (en) * | 1992-09-30 | 1994-04-06 | Sumitomo Electric Industries, Ltd | Tetrathiafulvalene derivative precursors, tetrathiafulvalene derivatives, and processes for producing them |
-
1997
- 1997-06-18 GB GB9712694A patent/GB9712694D0/en active Pending
-
1998
- 1998-06-18 AU AU82215/98A patent/AU8221598A/en not_active Abandoned
- 1998-06-18 WO PCT/GB1998/001632 patent/WO1998058246A2/en active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0590539A2 (en) * | 1992-09-30 | 1994-04-06 | Sumitomo Electric Industries, Ltd | Tetrathiafulvalene derivative precursors, tetrathiafulvalene derivatives, and processes for producing them |
Non-Patent Citations (5)
Title |
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A.J.MOORE ET AL.: "CATION RECOGNITION BY SELF-ASSEMBLED LAYERS OF CROWN-ANNELATED TETRATHIAFULVALENES." ADVANCED MATERIALS., vol. 10, no. 5, 23 March 1998, pages 395-398, XP000739184 WEINHEIM DE * |
M.MIZUNO ET AL.: "ORGANIC METALS:ALKYLTHIO SUBSTITUTION EFFECTS IN TETRATHIAFULVALENE" JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS.,1978, pages 18-19, XP002080371 LETCHWORTH GB * |
P.HUDHOMME ET AL.: "STUDIES OF THE 1ST S-POSITION ISOMER OF BIS(ETHYLENEDITHIO)TETRATHIAFULVALENE" ANGEWANDTE CHEMIE. INTERNATIONAL EDITION., vol. 36, no. 8, 2 May 1997, pages 878-880, XP002080370 WEINHEIM DE * |
R.DIEING ET AL.: "CROWN-ANNELATED TETRATHIAFULVALENES" JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 2.,1996, pages 1587-1593, XP002080369 LETCHWORTH GB * |
TH. HANSEN ET AL.: "CROWN ETHERS DERIVATIVES OF TETRATHIAFULVALENE.1" JOURNAL OF ORGANIC CHEMISTRY., vol. 57, 1992, pages 6403-6409, XP002080368 EASTON US * |
Cited By (11)
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US10067082B2 (en) | 2004-02-06 | 2018-09-04 | Ascensia Diabetes Care Holdings Ag | Biosensor for determining an analyte concentration |
WO2006113440A2 (en) * | 2005-04-15 | 2006-10-26 | Worcester Polytechnic Institute | Multi-transduction mechanism based microfluidic analyte sensors |
WO2006113440A3 (en) * | 2005-04-15 | 2007-01-18 | Worcester Polytech Inst | Multi-transduction mechanism based microfluidic analyte sensors |
US7935309B2 (en) | 2005-04-15 | 2011-05-03 | Worcester Polytechnic Institute | Multi-transduction mechanism based microfluidic analyte sensors |
JP2008222639A (en) * | 2007-03-13 | 2008-09-25 | Showa Shell Sekiyu Kk | New compound and lubricating oil composition containing the same |
US9933385B2 (en) | 2007-12-10 | 2018-04-03 | Ascensia Diabetes Care Holdings Ag | Method of using an electrochemical test sensor |
US10690614B2 (en) | 2007-12-10 | 2020-06-23 | Ascensia Diabetes Care Holdings Ag | Method of using an electrochemical test sensor |
CN103936761A (en) * | 2014-03-28 | 2014-07-23 | 宁波工程学院 | 3-pyridyl containing tetrathiafulvalene compound as well as preparation method and application thereof in specific recognition of Cu<2+> |
CN103936761B (en) * | 2014-03-28 | 2018-04-10 | 宁波工程学院 | Tetrathiafulvalene compound containing 3 pyridine radicals and preparation method thereof and to Cu2+Single-minded identification purposes |
CN106831510A (en) * | 2017-01-16 | 2017-06-13 | 黄河三角洲京博化工研究院有限公司 | Thio hendecane of 1,11 dihydroxy 3,6,9 3 and preparation method thereof |
CN106831510B (en) * | 2017-01-16 | 2018-10-19 | 黄河三角洲京博化工研究院有限公司 | Three thio hendecanes of 1,11- dihydroxy -3,6,9- and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
WO1998058246A3 (en) | 1999-03-18 |
AU8221598A (en) | 1999-01-04 |
GB9712694D0 (en) | 1997-08-20 |
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