EP2212266A1 - Deutération de substances de marquage - Google Patents

Deutération de substances de marquage

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Publication number
EP2212266A1
EP2212266A1 EP08851727A EP08851727A EP2212266A1 EP 2212266 A1 EP2212266 A1 EP 2212266A1 EP 08851727 A EP08851727 A EP 08851727A EP 08851727 A EP08851727 A EP 08851727A EP 2212266 A1 EP2212266 A1 EP 2212266A1
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EP
European Patent Office
Prior art keywords
markers
liquid
liquids
deuterating
fluorescence
Prior art date
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.)
Withdrawn
Application number
EP08851727A
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German (de)
English (en)
Inventor
Rüdiger Sens
Christos Vamvakaris
Wolfgang Ahlers
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP08851727A priority Critical patent/EP2212266A1/fr
Publication of EP2212266A1 publication Critical patent/EP2212266A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/003—Marking, e.g. coloration by addition of pigments

Definitions

  • the present invention relates to a method for the detection of markers in liquids using deuterating agents.
  • the invention further relates to methods for labeling liquids and to the use of deuterating agents to improve the detectability of markers in liquids.
  • EP 0 818 674 describes methods for identifying an analyte in a sample by treating a sample with a deuterating reagent using the Raman signal emitted after irradiation.
  • markers in liquids are often used in very low concentrations in the ppm or ppb range.
  • low concentrations of the markers are advantageous if the liquids are to be marked invisible or largely unnoticed.
  • the liquids are often contaminated by substances that make it difficult or even impossible to reliably detect the markers in the often used low concentrations.
  • the object of the present invention was to provide methods which reliably enable the detection of markers in liquids even in extremely low concentrations.
  • a sub-task of the present invention was to allow the detection of markers in low concentrations even in contaminated liquids.
  • the liquids to be marked are basically of any nature and may be pure liquids or mixtures of liquids.
  • Non-polar liquids are preferably used in the context of the process according to the invention.
  • non-polar liquids are liquids or mixtures of liquids having a dielectric constant (18 ° C., 50 Hz) less than 4.
  • the fluids are generally available commercially.
  • the non-polar liquids preferably contain oils, particularly preferably mineral oils, in particular diesel fuels. Most preferably, the non-polar liquid is a mineral oil, in particular a diesel fuel.
  • the liquid contains impurities.
  • impurities of the liquid are to be understood as meaning substances which interfere or make impossible the detection of the markers in step (c) of the above-stated process.
  • Terms of the form C 3 -Cb in the context of this invention designate chemical compounds or substituents with a certain number of carbon atoms.
  • the number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
  • Further specification of the chemical compounds or substituents is made by terms of the form C 3 -Cb-V.
  • V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
  • Heteroatoms are preferably oxygen, nitrogen, sulfur or phosphorus.
  • C 1 -C 20 -alkyl straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl, ethyl, propyl , Isopropyl, or C 4 -C 6 -alkyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2,2 -Dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethyl
  • Trimethylpropyl 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C 7 0 CI -alkyl, such as heptyl, octyl, 2-ethyl-hexyl, 2, 4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl and their isomers.
  • C 1 -C 20 -alkoxy denotes a straight-chain or branched alkyl group having 1 to 20
  • Carbon atoms (as mentioned above) which are attached via an oxygen atom (-O-), for example Ci-Cio-alkoxy or Cn-C2o-alkoxy, preferably C1-C10alkyloxy, particularly preferably Ci-C3-alkoxy, such as methoxy , Ethoxy, propoxy.
  • oxygen atom for example Ci-Cio-alkoxy or Cn-C2o-alkoxy, preferably C1-C10alkyloxy, particularly preferably Ci-C3-alkoxy, such as methoxy , Ethoxy, propoxy.
  • C3-C15-cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as. B. norbornyl or norbenyl.
  • Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
  • Aryloxy is a mono- to trinuclear aromatic ring system (as mentioned above), which is attached via an oxygen atom (-O-), preferably a mononuclear to dinuclear, more preferably a mononuclear aromatic ring system.
  • Heterocycles five- to twelve-membered, preferably five- to nine-membered, particularly preferably five- to six-membered, oxygen, nitrogen and / or sulfur atoms, ring rings optionally containing several rings such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, Dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, di- methylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or part.
  • the heterocycles can be attached in any desired manner chemically to the compounds of the general formula (I), for example via a bond to a carbon atom of the heterocycle or a bond to one of the heteroatoms.
  • five- or six-membered saturated nitrogen-containing ring systems which are attached via a ring nitrogen atom and which may contain one or two further nitrogen atoms or another oxygen or sulfur atom.
  • C 1 -C 20 -alkylamino means an amine group which is substituted by one, straight-chain or branched alkyl groups having 1 to 20 carbon atoms (as mentioned above), for example C 1 -C 2 -dialkylamino or C 3 -C 4 -dialkylamino, preferably C 1 -C 2 -cycloalkyl Dialkylamino attached via the nitrogen.
  • C 1 -C 20 -dialkylamino means a substituted amine group with two, identical or different, straight-chain or branched alkyl groups having 1 to 20 carbon atoms (as mentioned above), for example C 1 -C 2 -dialkylamino or C 3 -C 4 -dialkylamino, preferably C 1 -C 2 -cycloalkyl Dialkylamino attached via the nitrogen.
  • markers which can be detected in liquids with the aid of fluorescence spectroscopic methods are suitable as markers. Preferred are markers which can be detected in low concentrations in the ppb or ppm range.
  • concentration units ppm and ppb in the context of this invention refer to the ratio of weight units unless stated otherwise.
  • markers which allow a marking of the liquids invisible to the human eye. Frequently, such markers have no or only a very small absorption in the visible range of the electromagnetic spectrum (wavelength of 380 to 750 nm) or are not visible to the human eye due to the low concentration in the ppb or ppm range. Therefore, marking in the context of this invention does not mean the coloring of the liquids by means of dyes.
  • the hydrogen atoms of the markers can be easily replaced by deuterium.
  • These hydrogen atoms are referred to in the context of this invention as H / D-labile hydrogen atoms.
  • H / D-labile hydrogen atoms XH
  • the labels have substituents containing H / D labile hydrogens (deuteratable substituents).
  • these substituents contain NH or OH groups.
  • Preferred deuterable substituents are substituted or unsubstituted amino, hydroxy, carboxyl, or amide groups.
  • the deuterable substituents are chemically attached to the chromophore of the markers.
  • the markers are chemical compounds from the classes of compounds of phthalocyanines, naphthalocyanines, nickel-dithiolene complexes, aminium compounds of aromatic amines, methine dyes, azulenesquaric acid dyes, anthraquinones, rylenes (eg quaterrylene, terrylene, perylene dyes) , Naphthalene tetracarboxylic diimides, dibenzanthrones, isodibenzanthrones or electroneutral merocyanine dyes. These compounds particularly preferably have their absorption maximum in the range from 600 to 1200 nm. Most preferably, these markers have H / D labile hydrogens.
  • PCT / EP2007 / 052122 European application 07105776.4, PCT application PCT / EP2007 / 051745 and WO 2006/097434 A2.
  • phthalocyanines page (p. 1), line (Z.) 37 - p. 3, Z.9), naphthalocyanines (p. 3, Z.11 - p. 4, Z.20), nickel-dithiolene complexes (S.4, Z. 22 - P. 4, Z. 46), aminium compounds of aromatic amines (S. 5, Z. 1 - Z. 31), methine dyes ( P. 5, Z. 33 - p. 6, line 29), azulenesquaric acid dyes (p. 6, p. 31 - p. 7, line 16).
  • the markers can be prepared by methods known to those skilled in the art or known per se. Most preferably, the markers are given by anthraquinones of the general formulas (I) to
  • the variables R, R 1 and R 2 independently of one another are C 1 -C 20 -alkyl, preferably C 1 -C 6 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, or aryl which is optionally substituted by one or more C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function.
  • X in the formulas (I) to (III) assumes either the meaning of two hydrogen atoms, two cyano groups in the 2,3- or 6,7-position or two identical groups CH (R 9 ) (R 10 ) in 2,3- or 6,7-position of Anthrachinongerüstes.
  • the latter two groups CH (R 9 ) (R 10 ) are either two groups CH (COOR ') 2, CH (CN) COOR' or CH (CN) 2, where the radicals R 'are preferably Ci-C 2 o-alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, or aryl, which is optionally substituted by one or more Ci-C2o-alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, mean.
  • the selection of the variables R, R 1 and R 2 is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, Undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetradecyl, penta-dec
  • the selection of the variables R, R 1 and R 2 is preferably carried out from the group consisting of unsubstituted phenyl simply in the 2-, 3- and 4-positions, the double in the 2,3-, 2,4- and 3,4-position and the triple in 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-substituted phenyl, which are substituted with the previously exemplarily enumerated, optionally interrupted with oxygen in ether function Ci-C2O alkyl radicals.
  • Anthraquinone derivatives of the compounds of the formulas IV to VII shown below are also to be mentioned as markers to be used according to the invention:
  • W is hydrogen or NHR ", p is 1, 2, 3 or 4, wherein for p greater than 1 the radicals are identical, and
  • Heterocycle optionally substituted with one or more C 1 -C 20 -alkyl groups optionally interrupted by 1 to 4 oxygen atoms in ether function;
  • Aryl which is optionally substituted by one or more C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20 -alkoxy, C 1 -C 20 -alkylamino or C 1 -C 20 -di- alkylamino;
  • Phenyl-C 1 -C 4 -alkyl which is optionally interrupted in the phenyl radical by one or more C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20 -alkoxy, C 1 -C 20 -alkylamino or C 1 -C 20 -cycloalkyl
  • Dialkylamino is substituted.
  • R "in the formulas IV to VII is particularly preferably C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, or aryl which is optionally substituted by one or more C 1 -C 20 -alkyl which is optionally substituted by 1 to 4 Oxygen atoms in ether function is interrupted.
  • R "in the formulas IV to VII is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethyl-nonyl, isotridecyl, Tetradecyl, pentadecyl, methoxymethyl, 2-ethyl-hexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propyl
  • the markers are most preferably given by Anthrachinondicarbonklareimide of the general formulas (VIII):
  • R 11 , R 12 , R 13 , R 14 are independently, identical or different H, Ci-C 2 o-alkyl, aryl, heterocycles
  • R 16 , R 17 , R 18 , R 19 independently of one another, identical or different, are H, C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, aryl, aryloxy, NR 11 R 12 , halogen, CN, NO 2 ,
  • substituents R 11 to R 19 may each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms being not more than 10, preferably not more than 8, very particularly preferably not more than 5 and in particular not more than 3 is, and / or in any position, but not more than five times, preferably not more than four times and more preferably not more than three times, by NR 11 R 12 , CONR 11 R 12 , COOR 11 , SO 3 R 11 , CN, NO 2 , C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, aryl, aryloxy, heterocycles or halogen may be substituted, which may also be substituted at most twice, preferably at most once with said groups.
  • radicals R 21 , R 22 , R 23 and R 24 and R 26 , R 27 , R 28 and R 29 each represent a heterocyclic radical or an aryloxy.
  • the aryloxy substituents may themselves be substituted with up to four, preferably with two, Ci-C4-alkyl groups.
  • M is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AICI, AIOH, AlOCOCH 3 , AIOCOCF3, or SiR 29 R 30 .
  • R 29 and R 30 are independently, the same or different, H, OH, Cl, C 1 -C 20 -alkyl, aryl, C 1 -C 20 -alkoxy or aryloxy.
  • phthalocyanines are known per se and can be prepared by methods known per se, such as those used in the preparation of phthalocyanines or naphtha-locyanines and as described, for example, in F. H. Moser, A.L. Thomas “The Phthalocyanines", CRC Press, Boca Rota, Florida, 1983, or J. Am.
  • synthesis of the phthalocyanines is carried out, for example, according to the methods described in WO 2005/070935.
  • phthalocyanines of the formulas (IX) or (X) in which all R 21 to R 28 are heterocyclic radicals and in each case pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl or morpholine 4-yl, where these radicals may be monosubstituted to trisubstituted, preferably monosubstituted, by C 1 -C 4 -alkyl, benzyl, phenylethyl or phenyl.
  • the markers are preferably given by naphthalocyanines of the general formula (XI):
  • Y 1 to Y 8 are each independently hydrogen, hydroxy, C 1 -C 20 -alkyl or C 1 -C 20 -alkoxy, where the alkyl groups may each be interrupted by 1 to 4 oxygen atoms in ether function and are optionally substituted by phenyl, and
  • Y 9 to Y 12 independently of one another are each hydrogen, C 1 -C 20 -alkyl or C 1 -C 20 -alkoxy, where the alkyl groups may each be interrupted by 1 to 4 oxygen atoms in ether function, halogen, hydroxysulfonyl or C 1 -C 4 -dialkylsulfamoyl.
  • R 29 and R 30 independently of one another, identical or different, are H, OH, Cl, C 1 -C 20 -alkyl, aryl, C 1 -C 20 -alkoxy or aryloxy.
  • naphthalocyanines of the formula (XI) in which at least one of the radicals Y 1 to Y 8 is different from hydrogen.
  • naphthalocyanines are known per se and can be obtained according to the methods of the above-mentioned prior art (Moser, J. Am. Chem. Soc.).
  • RSI 1 R ⁇ R 3 S 1 R 34 independently of one another, identically or differently H, C 1 -C 20 -alkyl, aryl, heterocycles, NR 35 R 36 ,
  • R 3 S 1 R 36 independently of one another, identical or different, are H, C 1 -C 20 -alkyl, aryl, heterocycles,
  • substituents R 31 to R 36 can each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms not exceeding 10, preferably not more than 8, very particularly preferably not more than 5 and in particular not more than 3 is, and / or in any position, but not more than five times, preferably not more than four times and more preferably not more than three times, by C 1 -C 20 alkyl, C 1 -C 20 alkoxy, aryl, aryloxy or heterocycles may be substituted These may likewise be substituted at most twice, preferably at most once, with the abovementioned groups.
  • the provision of the liquids containing markers according to step (a) of the process according to the invention can be carried out in any desired manner.
  • the markers are used in the form of solutions, but may also have been added as solids to the liquids to be marked.
  • Suitable solvents are preferably aromatic hydrocarbons such as toluene or xylene.
  • a concentration of markers of from 2 to 50% by weight, based on the solution, is generally selected.
  • step (a) of the process according to the invention are referred to as labeled liquids.
  • step (b) of the process according to the invention the liquid is brought into contact with a deuterating agent.
  • deuterating agents which bring about H / D exchange of H / D-labile hydrogen atoms. While deuteration is generally preferred, the process of the invention can also be carried out with higher hydrogen isotopes such as tritium.
  • deuterating agents which are liquids can be used within the scope of the invention.
  • Deuterated alcohols are preferably used as deuterating agents, such as monodeuterated methanol (MeOD) or monodeuterated ethanol (EtOD). Most preferred is EtOD.
  • D 2 O is used as deuterating agent.
  • lithium aluminum deuteride is used as deuterating agent.
  • D3PO4 BF3 is used as deuterating agent.
  • DsPO 4 BFs can be prepared according to the method described in US 3,475,507.
  • the labeled liquids are brought into contact with the deuterating agent.
  • the contact can be made by any method. For example, both can be mixed together as liquids, optionally after the solution of the deuterating agent in a liquid. Whether in this case the deuterating agent is added to the liquid or vice versa is generally insignificant. Often, the deuterating agent is added to the liquid and mixing is accomplished by, for example, shaking or stirring. Preferably, the deuterating agent dissolves either as a solid, as a liquid or in a solvent in the labeled liquid.
  • the duration of contact between labeled liquid and deuterating agent in step (b) of the process according to the invention can vary over a wide range, for example, depending on the particular marker.
  • the duration of the contact is in the range of 10 seconds to 24 hours. More preferably, the duration of the contact is less than 1 hour. Most preferably, the duration of the contact is less than 10 minutes.
  • the amount of deuterating agent used in the context of the process according to the invention, based on the labeled liquid can vary within a wide range, depending on the chemical nature of the deuterating agents and the markers.
  • the weight ratio of deuterating agent to labeled liquid is selected from the range of 20: 1 to 1:20. The selected range is preferably from 10: 1 to 1:10, in particular from 4: 1 to 1: 4.
  • the amounts of deuterating agents and labeled liquids used in the process of the invention may vary over a wide range. In most cases, for example in the case of spectroscopic detection in step (c), a few milligrams or milliliters of the substances are sufficient. Preferably, less than 10 mg or 10 ml are used.
  • step (c) The detection of the markers in step (c) is in principle carried out by means of the generally known methods of fluorescence spectroscopy, as described, for example, in WO
  • the proof can be qualitative or quantitative.
  • An important parameter for the detection of the markers is the signal / noise ratio of the respective method. In order to reliably detect a marker, the signal-to-noise ratio should generally be better than 10/1. For quantitative detection, a signal-to-noise ratio better than 30/1 is preferred.
  • the method according to the invention makes it possible to reliably detect even extremely low concentrations of markers by fluorescence-spectroscopic detection.
  • step (b) an H / D exchange of labile hydrogens of the marker takes place, which leads to an increased quantum yield of the fluorescence.
  • the intensities of the fluorescence signals are increased many times after being brought into contact with deuterating agents.
  • the intensity of the fluorescence signal here is the signal of the sample without the treatment with deuterating agent, but optionally with appropriate dilution.
  • the intensity of the fluorescence signal is preferably increased by the factor of at least two by the method according to the invention. Particularly preferred is a factor of at least four. Most preferably, the intensity of the fluorescence signal increases by at least a factor of five.
  • the concentration of marker can be by a factor of at least two, more preferably at least 4 and especially at least five decrease.
  • the use of the deuterating agent in step (b) does not amplify the background fluorescence occurring during the fluorescence spectroscopic detection (c) to the same extent as the intensity of the fluorescence signal of the marker and thus the signal / Improved noise ratio.
  • the signal / noise ratio preferably improves by a factor of at least two, more preferably at least 4 and in particular at least 5.
  • step (c) contacting the deuterating agent in step (b) also improves the signal-to-noise ratio in a contaminated liquid for detection in step (c). Therefore, in a preferred embodiment of the method according to the invention, the detection in step (c) is carried out on a contaminated liquid.
  • the H / D exchange takes place primarily in the marker and only subordinate in the substances that cause the contamination.
  • the detection of the markers is performed time-dependent.
  • the fluorescence intensity of the markers is determined at different times.
  • the time course of the fluorescence intensity is a characteristic feature of the markers used and can be used for the detection and identification of the markers.
  • Another object of the invention is a method for labeling liquids, wherein the detection of the markers is carried out according to one of the embodiments of the method according to the invention.
  • Another object of the invention is the use of deuterating agents to improve the detectability of markers in liquids.
  • markers in liquids even in extremely low concentrations, can be reliably detected even without separation and preparation.
  • Excitation wavelength 670 nm - long-pass filter: two times 695 nm
  • a quantity of 8.7 mg marker MS2 was dissolved in 100 ml toluene (concentration 100 ppm). Subsequently, the sample was dispersed in an ultrasonic bath for 15 minutes. The total release time was 30 minutes. The sample was diluted with toluene until a concentration of 100 ppb was reached. This sample was measured in the fluorescence detection apparatus (diesel tester) (see Example 1). The excitation wavelength of the laser was 760 nm (longpass filter: 776 nm). A portion of the 100 ppb solution was further diluted (33 ppb) with 2 parts (by weight) of toluene and also measured in the fluorescence detection device (diesel tester).
  • diesel was diluted with ethanol 1: 2 (by weight) and measured.
  • diesel was diluted with ethanol D1 (EtOD) and measured.
  • the dyes were dissolved in toluene and adjusted to an absorbance of 1.0 at the absorption maximum. Then one part of ethanol (EtOH) or ethanol D1 (EtOD) was added to two parts (always parts by weight) of the solutions thus prepared. These solutions were excited at a wavelength near their absorption maxima (lambda ex) at which the toluene solutions to be compared diluted with ethanol or ethanol D1 had equal absorptions. The following fluorescence intensities (scale parts) in the respective fluorescence maximum (FL) were obtained:
  • MS2 was adjusted in toluene to an extinction of 0.5 at the absorption maximum of 750 nm and diluted with ethanol D1 (EtOD) 1: 1 (weight). Subsequently, the kinetics of the fluorescence of MS2 was measured with the fluorescence spectrometer Cary Eclipse at 820 nm. After waiting for 20 minutes, the maximum intensity is reached.
  • Solvent Violet 59 (CAS # 6408-72-6) was adjusted to an absorbance of 0.16 in the absorption maximum of 542 nm in toluene and diluted with ethanol D1 1: 1 (weight). Subsequently, the kinetics of the fluorescence were measured with the fluorescence spectrometer Cary Eclipse in the fluorescence maximum at 607 nm (toluene) or 616 nm (1: 1 dilution with ethanol D1). After waiting for 20 minutes, the maximum intensity is reached.
  • Marker MS2 was adjusted to an absorbance of 0.2 at 746 nm in ethanol and monodeuterated ethanol (EtOD).
  • EtOD monodeuterated ethanol
  • the fluorescence signal observed in deuterated ethanol is about a factor of 3 higher than in non-deuterated ethanol.
  • a quantity of 8.7 mg of MS10 was dissolved in 100 ml of toluene (concentration 100 ppm). Subsequently, the sample was dispersed in an ultrasonic bath for 15 minutes. The total dissolution time was 30 minutes. The sample was diluted with toluene until a concentration of 10 ppb was reached. This sample was measured in the fluorescence detection apparatus (diesel tester) (see Example 1). The excitation wavelength of the laser was 660 nm (long-pass filter: 695 nm). A portion of the marker solution was further diluted with 2 parts of toluene (3 ppb) and also measured in the fluorescence detection device (diesel tester). Another part was diluted ( ⁇ 3ppb) with 2.3 parts ethanol D1 (EtOD) and measured. Another part was diluted (3 ppb) with 2 parts of ethanol D1 and measured.

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Abstract

L'invention concerne un procédé de détection de substances de marquage dans des liquides, selon lequel (a) une ou plusieurs substances de marquage identiques ou différentes sont présentes dans le liquide, (b) un agent de deutération est mis en contact avec le liquide et (c) la substance de marquage présente dans le liquide est détectée par spectroscopie en fluorescence. L'invention concerne également un procédé de marquage de liquides non polaires contaminés ainsi que l'utilisation d'agents de deutération en vue de l'amélioration de la détection de substances de marquage dans des liquides.
EP08851727A 2007-11-21 2008-11-17 Deutération de substances de marquage Withdrawn EP2212266A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08851727A EP2212266A1 (fr) 2007-11-21 2008-11-17 Deutération de substances de marquage

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07121213 2007-11-21
PCT/EP2008/065631 WO2009065789A1 (fr) 2007-11-21 2008-11-17 Deutération de substances de marquage
EP08851727A EP2212266A1 (fr) 2007-11-21 2008-11-17 Deutération de substances de marquage

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WO (1) WO2009065789A1 (fr)

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CN107434797B (zh) * 2016-05-26 2019-09-24 上海市计量测试技术研究院 一种氘标记玉米赤霉烯酮及其衍生物的合成方法

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DE19818176A1 (de) * 1998-04-23 1999-10-28 Basf Ag Verfahren zur Markierung von Flüssigkeiten mit mindestens zwei Markierstoffen und Verfahren zu deren Detektion
US5474937A (en) * 1993-01-25 1995-12-12 Isotag, L.L.C. Method of identifying chemicals by use of non-radioactive isotopes
US6040906A (en) * 1996-07-11 2000-03-21 Harhay; Gregory P. Resonance raman spectroscopy for identifying and quantitating biomatter, organic, and inorganic analytes
DE102004035948A1 (de) * 2004-07-23 2006-03-16 Basf Ag Verfahren zur Bestimmung der Identität oder Nicht-Identität mindestens einer in einem Medium homogen verteilten chemischen Verbindung

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WO2009065789A1 (fr) 2009-05-28
PE20091298A1 (es) 2009-09-30
RU2010125011A (ru) 2011-12-27
BRPI0819284A2 (pt) 2015-05-19
CN101868433A (zh) 2010-10-20

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