EP1466169A2 - Procede de detection de substances de nucleation de metaux - Google Patents

Procede de detection de substances de nucleation de metaux

Info

Publication number
EP1466169A2
EP1466169A2 EP02719896A EP02719896A EP1466169A2 EP 1466169 A2 EP1466169 A2 EP 1466169A2 EP 02719896 A EP02719896 A EP 02719896A EP 02719896 A EP02719896 A EP 02719896A EP 1466169 A2 EP1466169 A2 EP 1466169A2
Authority
EP
European Patent Office
Prior art keywords
metal
substance
metal salt
carrier
nucleating
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Withdrawn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
EP02719896A
Other languages
German (de)
English (en)
Inventor
Walther Dr. Ensslin
Johannes Kupka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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
Priority claimed from DE2001108359 external-priority patent/DE10108359B4/de
Application filed by Individual filed Critical Individual
Publication of EP1466169A2 publication Critical patent/EP1466169A2/fr
Withdrawn legal-status Critical Current

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
    • G01N31/005—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods investigating the presence of an element by oxidation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1813—Specific cations in water, e.g. heavy metals

Definitions

  • the invention relates to a method for the extremely sensitive detection of metal nucleating substances such as metal and non-metal hydrides, metal salts such as iron (II), chromium (II) or tin (II) salts, mercury (I) and (II) salts , Fine dust of base metals, aldehydes, phenols, microorganisms and reducing sugars.
  • metal salts such as iron (II), chromium (II) or tin (II) salts, mercury (I) and (II) salts , Fine dust of base metals, aldehydes, phenols, microorganisms and reducing sugars.
  • the filter tip is colored yellow to form an arsenic-silver compound, blackish brown when water is added to separate elemental silver. This method is simple and can be carried out without any great expenditure on equipment, but is far from sensitive enough to detect arsenic in drinking water.
  • the object of the present invention is to provide a precise and reproducible method for the detection of metal nucleating substances, such as metal and non-metal hydrides, the detection limit of which can be reduced almost as desired and can be carried out simply, inexpensively and without major outlay on equipment.
  • a metal nucleating substance in particular a reducing substance (for example arsenic or antimony hydrogen) is brought into contact with a carrier which contains metal salt (for example silver bromide).
  • the metal salt reacts with the substance to be detected to form at least one metal seed.
  • the metal nuclei produced are then chemically developed in the manner customary for photographic purposes. If, for example, a photographic film containing silver salt is used as the support and this is brought into contact with a reducing substance, a number of nuclei are generated which is a measure of the concentration of the reducing substance to be detected.
  • the invention takes advantage of the fact that even the slightest metal nuclei, for example those formed by reduction, are converted into visible metal by the subsequent chemical development of the metal salt-containing carrier.
  • Photographic material such as commercially available films, contain silver salt in the form of uniformly distributed crystal grains, for example silver bromide grains.
  • a silver bromide grain of the photographic layer consists of approximately 10 8 to 10 12 silver ions.
  • the method according to the invention enables the detection of metal nucleating substances in the ppb range and far below, down to the atomic or molecular range. This makes it possible, for example, to detect arsenic in drinking water in the lowest concentrations as arsenic hydrogen in the lowest concentrations without sample preparation, even below the drinking water limit of 10 ⁇ g / 1.
  • a photographic material with a correspondingly high sensitivity (coarse grain) and by selecting an appropriate development process it is possible to shift the detection limit into the desired range as required.
  • the method according to the invention can therefore be used, for example, in semiconductor technology wherever extremely precise detection methods for doping are important.
  • the inventive method allows ⁇ after calibration with a standard sample (a sample having a known content of the metal nucleating substance), an exact quantitative determination. Since the amount of reducing substance contained in the sample can be found in the blackened or yellowed or at high concentrations still differently colored area of the developed photographic material, this can be determined by simply measuring the corresponding blackened or colored areas. This evaluation can be automated through the use of commercially available scanners and evaluation programs.
  • An advantage of the detection method according to the invention in addition to its extremely high sensitivity, which can be moved over a wide range, is that it enables cost-effective analysis of water and soil samples directly at the location of the sampling without any complex equipment. This prevents sample falsification due to storage and transport and the procedure can also be carried out without difficulty in places that are otherwise difficult to access.
  • Metal nucleating substances in the sense of this invention are understood to mean any substances which, when brought into contact with a metal salt, produce at least one metal nucleus.
  • Metal nucleating substances can, for example, be reducing substances which contain the metal salt Generation of one or more metal nuclei reduced.
  • metal nucleating substances can, for example, also be oxidizing substances which oxidize the metal salt to produce one or more metal nuclei.
  • the number of metal nuclei formed depends on the amount of the substance to be detected. If the substance to be detected is present in very small quantities - as is the case, for example, in very sensitive analytical detection methods - only a small number of metal nuclei are generated.
  • the reaction can go beyond the mere formation of metal nuclei to complete conversion (eg oxidation and / or reduction) of the metal salt.
  • reducing substance is generally understood to mean those substances which are less noble than the metal of the metal salt contained in the carrier and thus can reduce the metal salt to elemental metal.
  • Reducing substances are especially those that are less noble than gold, silver or palladium. Examples of such reducing substances are reducing hydrides, in particular arsenic hydrogen, germanium hydrogen, antimony hydrogen, hydrogen sulfide, selenium hydrogen, tellurium hydrogen, tin hydrogen and phosphines.
  • reducing substances in the sense of this invention are reducing metal salts such as iron (II), chromium (II) and tin salts as well as alkaline solutions of reducing Sugars or organic acids such as glucose, mannose, galactose, sorbose, ascorbic acid, glucosamines, milk sugars, maltose and fructose.
  • Acrolein, unsaturated hydrocarbons such as ethylene and acetylene and aldehydes, phenols and nitric oxide are used as reducing 'substances in question can be detected with the inventive method.
  • Fine dust (with a diameter of less than 0.1 ⁇ m down to the atomic range) of metals and mercury vapors, but also reducing sugars etc. can also be detected. This is of great importance in allergy research and job surveillance.
  • an oxidizing substance is generally understood to mean those substances which can oxidize the metal salt to elemental metal.
  • suitable oxidizing substances are ozone, chromates and dichromates, nitrous gases and / or peroxides.
  • metal salts such as telluride or selenide can be oxidized to elemental metal (e.g. tellurium or selenium).
  • metal nucleating substance to be detected with the method according to the invention does not itself have to have a direct metal nucleating effect. Rather, metal nucleating substances to be detected according to the invention also include reducing and / or oxidizing substances which generate a reducing and / or oxidizing agent via a mediator or by complex formation.
  • the metal nucleating substances also include metals and semiconductors themselves.
  • Metal nucleating substances in the sense of this invention can also be microorganisms. These can be, for example, reducing or oxidizing microorganisms. These can be fixed, for example, on the metal salt-containing carrier by means of a specific receptor. Metal nucleating substance can be released from the microorganisms, for example, by the action of an enzyme or surfactant.
  • Metal nucleating substances in the sense of this invention can also be biochemical substances. These can be fixed on the metal salt-containing support, for example, by specific receptors. The release of nucleating oxidizing and / or reducing agents can take place, for example, by a defined destruction of the complex.
  • the sample to be examined for a metal nucleating substance can be in a solid, liquid and gaseous state and can be applied to the metal salt-containing carrier.
  • gaseous substances such as heavy metal hydrides such as arsenic or antimony hydrogen
  • Atomic hydrogen can be produced, for example, by reacting acid and metal or by electrolysis of an aqueous solution.
  • Gaseous heavy metal hydride can be produced in a particularly simple manner at the location of the sampling, by mixing out the corresponding solution containing heavy metal salt with a mixture Magnesium and citric acid added.
  • the mixture of magnesium and citric acid preferably contains about five parts by weight of citric acid per part by weight of magnesium.
  • the reducing gas generated is brought into contact quantitatively, for example by introducing it into a closed reaction chamber, with the preferably moistened metal salt-containing carrier.
  • the selectivity of the process can also be achieved by selectively forming the seed at a specific pH or by introducing activating substances into the carrier.
  • Cobalt (II) salt for cyanide ions for example, can act as an activation substance. This produces a reducing cobalt (II) cyanide.
  • iron (II) ions can act as an activating substance for fluoride ions.
  • the iron fluoride complex (FeF 6 ) 4 ⁇ formed has a strong reducing effect.
  • an upstream immobile reducing agent such as magnesium powder can convert the substance to be detected into a reducing form (eg conversion of iron (III) or vanadium (V) or vanadium (III) into iron (II) or vanadium (II.) With a reducing effect) , Carbon monoxide, ethene, ethyne, propene, butene, butadiene and alkanes from three carbon atoms with palladium (II) salt can also be detected catalytically.
  • cyanide can be activated by activation with a sparingly soluble metal sulfide, the metal of which is easily a cyanide complex forms and thereby releases the nucleating sulfide ion.
  • the substance to be detected is brought into contact with a carrier containing metal salts.
  • Metal salts suitable according to the invention are any metal salts which form at least one metal seed due to the substance to be detected.
  • Suitable metal salts are, for example, silver, gold, copper, selenium, palladium and mercury salts and the silver salts of sulfur, selenium and tellurium.
  • Suitable metal salts are also tellurides and selenides, especially alkali tellurides and alkali selenides, which are particularly suitable for the detection of oxidizing substances.
  • Particularly suitable metal salts are silver, gold and / or palladium halides. Preferred halides are bromides. Silver bromide is particularly preferred.
  • the silver, gold and / or palladium halides are particularly suitable for the detection of reducing substances.
  • the metal salts are preferably in the form of crystals. Microencapsulated silver salt solutions or generally microencapsulated reducible metal salt solutions are also possible.
  • Any material that can serve as a medium for metal salts and that can be brought into contact with the substance to be detected can be used as a carrier.
  • Layer systems which contain metal salt in at least one layer are particularly suitable as supports. Papers or foils or grains or glass tubes coated with gelatin or similar thickeners are particularly suitable as supports.
  • Photographic materials in particular can be used as the metal salt-containing support. Any photographic plates, films and papers containing silver salt can be used as photographic material. These preferably contain silver halides, particularly preferably silver bromide, as the silver salt. Because of their availability and ease of handling, commercial black-and-white or color negative films and color reversal films are preferably used. Slide films or instant film can also be used.
  • the photographic materials can be used in any sensitivity level.
  • Relatively coarse-grained photographic materials with high sensitivity are preferably used. These preferably have a sensitivity class of 18 to 30 DIN, in particular 23 to 30 DIN or 100 to 3200 ASA.
  • Coarse-grained (3200 ASA) photographic materials can detect even the smallest amounts of substances to be detected in the ppt range. With microscopic evaluation of the developed film, detection down to the atomic range is even possible. Suitable photographic materials are described, for example, in Ullmann's Encyclopedia of Technical Chemistry, 4th edition, volume 18, page 474 ff., Verlag Chemie, Weinheim, 1979.
  • the metal salt-containing carrier for example silver salt-containing photographic material
  • the metal salt-containing carrier is brought into contact with the sample to be examined for the metal nucleating substance and / or is stored until development, essentially in the absence of light or under conditions which prevent exposure of the film, for example in one closed housing or for orthochromatic films using red light in a dark room.
  • the contacting of the substance to be detected with the photographic material is expediently carried out in a camera suitable for recording such materials.
  • the surface of the carrier is wetted with a suitable liquid before it is brought into contact with the sample.
  • the wetting mediates the contact of the substance to be detected with the metal salt contained in the carrier and enables the chemical reaction of the nucleation.
  • the carrier is preferably wetted with an aqueous solution. This preferably has a pH from 4.0 to 10.0, in particular from 5.0 to 8.0 and very particularly preferably from 7.0 to 8.0.
  • a buffered aqueous solution is also used as the wetting liquid. As such, approximately 0.1 to 5% by weight, in particular 0.5 to 1.5% by weight, aqueous
  • Sodium bicarbonate solution with a buffered pH around 7.0 can be used.
  • certain reducing substances such as sugars, e.g. glucose, mannose, galactose, milk sugar, maltose and fructose as well as organic acids such as ascorbic acid and glucosamines
  • an alkaline solution for example with a to wet ammoniacal solution (0.1% to 10.0% solution) or sodium hydroxide solution (0.1 to 10% solution).
  • the liquid used for wetting the carrier contains a substance which reduces the surface tension.
  • a substance that is particularly suitable for this purpose is alcohols such as methanol and ethanol.
  • a wetting liquid consisting of one part by volume of an approximately 1% sodium carbonate solution and approximately 9 parts by volume of methanol has also proven to be particularly advantageous.
  • the wetting of the carrier with the wetting liquid can be carried out with devices familiar to the person skilled in the art, for example with the aid of a wet sponge or felt which touches the film and, if appropriate, is continuously supplied with wetting liquid, or by spraying a defined amount of the wetting liquid through a spray head or via a device be carried out analogously to an inkjet cartridge. It is advantageous to measure the degree of humidification capacitively with a suitable sensor and / or a measuring device and thus to control it.
  • a photographic film is used as the support, it is expedient to dry the film after contacting the film with the substance to be detected, before transporting it into the film reel and developing it. This can be done, for example, by blowing air in or blowing it in. The completion of this drying and thus the termination of the nucleation in the film is preferably checked capacitively.
  • the substance to be detected is brought into contact with the metal salt-containing carrier, one or more metal nuclei are formed in the carrier by reaction with the metal salt depending on the amount of the substance to be detected, which is referred to in photography as a so-called latent image. These metal nuclei can be reinforced and made visible in the subsequent chemical development step.
  • the metal salt-containing carrier is chemically developed in the usual way after being brought into contact with the substance to be detected and optionally subsequently dried. Through the development, the metal salt in the carrier is selectively reduced to metal at the locations of the metal nuclei formed. The latent images created on the carrier by bringing them into contact with the substance to be detected are made visible.
  • Suitable developer substances are substances that. are able to selectively reduce the metal salt in the carrier material at the points where metal nuclei have been formed by contacting the substance to be detected.
  • Both organic and inorganic reducing agents can be used as developer substances. These are described, for example, in Ullmann's Encyklopadie der Technischen Chemie, 4th edition, volume 18, page 444-446, point 5.1 and page 455-456, point 6.3.2.1.
  • Particularly suitable developer substances are, for example, hydroquinone, N-methyl-p-aminophenol, 1-phenyl-3-pyrazolidone and N, N-dialkylated p-phenylenediamine derivatives.
  • Aqueous solutions of these substances can be used for development (so-called developer solutions), which in addition to the actual developer substance can also be used
  • Buffer substances and protective substances of various types can contain. Developer solutions that can be used according to the invention are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 446 to 448, point 5.2, pages 451 to 452, point 5.4, pages 454 to 463, point 6.3. If other metal salts are used instead of silver salts, the developers must be adjusted accordingly.
  • the development step carried out in the method according to the invention can furthermore be carried out for
  • a particularly high gain is achieved by post-development with a developer containing silver nitrate.
  • FIG. 1 shows a schematic representation of a device for carrying out the method according to the invention, in which a gaseous reducing substance is passed onto a photographic material and the photographic material is wetted by spraying with a liquid,
  • FIG. 2 shows a schematic representation of a device for carrying out the method according to the invention, in which a gaseous reducing substance is passed onto a photographic material and the photographic material is wetted with the aid of a wet sponge,
  • FIG. 3 shows a device according to FIG. 2, in which the gaseous reducing substance is produced by electrolysis and
  • FIG. 4 shows a device according to FIG. 1, in which the sample to be examined is placed on the film dissolved in a solvent.
  • a gaseous metal nucleating substance (5) is produced by reacting the liquid sample (5a) to be examined with a mixture of metal and acid in a reaction vessel (4) which is sealed airtight with a stopper (6).
  • the gaseous reducing substance (5) is injected into the interior of the reaction vessel (4) through a needle (7), a tube (8) and a needle (9) from above next to the lens (2) the inside of a closed camera housing (1) on an unexposed photographic film (3) through the outlet opening (10).
  • the film (3) was previously sprayed through a nozzle (11) with a solution of methanol and water in a ratio of 9: 1 buffered to pH neutral with sodium bicarbonate. Spraying is carried out by introducing about 40 ⁇ l of the methanol / water mixture into the line (14) via the microsyringe (13) and then actuating the 100 ml syringe (12) containing water to spray the wetting liquid.
  • the degree of moistening is determined capacitively by a metal frame (13a) forming a capacitor and a metal plate (13b) between which the moist film (3) is guided, and recorded and controlled by a measuring device (13c). The.
  • Lens (2) of the camera can be sealed light-tight with the help of a modeling clay (15) while opening the closure for further transport of the film.
  • the film (3) can be dried by blowing air or inert gas through a syringe (12a) with feed line (12b) before being transported on. This drying can also be recorded capacitively.
  • the reaction chamber (1) is flushed with air or inert gas from the reducing gas not converted on the film (3) for further measurements.
  • FIG. 2 shows a device which corresponds to the device shown in FIG. 1, with the exception that the wetting of the photographic material (3) takes place via a felt (16) impregnated with wetting liquid.
  • the felt (16) is supplied with wetting liquid by actuating a microsyringe (13).
  • FIG. 3 shows a device which corresponds to the device shown in FIG. 2, with the exception that the gaseous reducing substance (5) is produced by electrolysis of the liquid sample (5a) by means of electrodes (17) arranged in the reaction vessel (4) becomes.
  • the electrodes (17) are supplied with current via electrical lines (18).
  • Fig. 4 shows a device which corresponds to the device shown in Fig. 1, with the exception that the substance to be detected (5) as a liquid sample by means of a syringe (13) via an air flow generated by the syringe (12) via the line (14) and the nozzle (11) is injected.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

L'invention concerne un procédé de détection de substances de nucléation de métaux. Ce procédé consiste: (1) à mettre en contact un échantillon à examiner qui est placé dans une substance de nucléation de métaux, avec un substrat contenant du sel métallique pour obtenir au moins un germe métallique et (2) à développer chimiquement ce germe métallique. Une réduction catalytique du sel métallique se produit au moins à l'emplacement du germe métallique.
EP02719896A 2001-02-21 2002-02-21 Procede de detection de substances de nucleation de metaux Withdrawn EP1466169A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10108359 2001-02-21
DE2001108359 DE10108359B4 (de) 2001-02-21 2001-02-21 Nachweisverfahren für reduzierende Substanzen
DE10148869 2001-10-04
DE10148869 2001-10-04
PCT/EP2002/001869 WO2002066971A2 (fr) 2001-02-21 2002-02-21 Procede de detection de substances de nucleation de metaux

Publications (1)

Publication Number Publication Date
EP1466169A2 true EP1466169A2 (fr) 2004-10-13

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ID=26008589

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02719896A Withdrawn EP1466169A2 (fr) 2001-02-21 2002-02-21 Procede de detection de substances de nucleation de metaux

Country Status (3)

Country Link
EP (1) EP1466169A2 (fr)
AU (1) AU2002250994A1 (fr)
WO (1) WO2002066971A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4376768B2 (ja) 2004-01-14 2009-12-02 富士フイルム株式会社 ガス検出用材料及びガス検査方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2641559B2 (ja) * 1989-04-17 1997-08-13 理研計器株式会社 水素化物検出用紙、及び水素化物検出用紙調製溶液
US5171536A (en) * 1989-09-22 1992-12-15 Dragerwerk Aktiengesellschaft Colorimetric testing and measuring device for gases
JPH03242539A (ja) * 1990-02-20 1991-10-29 Terumo Corp 試験具およびその製造方法
US5665313A (en) * 1994-09-05 1997-09-09 Japan Pionics Co., Ltd. Detecting agent
JP3259949B2 (ja) * 1997-02-24 2002-02-25 理研計器株式会社 水素化物ガス検出紙

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02066971A3 *

Also Published As

Publication number Publication date
WO2002066971A3 (fr) 2004-07-29
AU2002250994A1 (en) 2002-09-04
WO2002066971A2 (fr) 2002-08-29

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