WO2009105375A1 - Procédé de détection - Google Patents

Procédé de détection Download PDF

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Publication number
WO2009105375A1
WO2009105375A1 PCT/US2009/033855 US2009033855W WO2009105375A1 WO 2009105375 A1 WO2009105375 A1 WO 2009105375A1 US 2009033855 W US2009033855 W US 2009033855W WO 2009105375 A1 WO2009105375 A1 WO 2009105375A1
Authority
WO
WIPO (PCT)
Prior art keywords
fungicide
paper
sample
fluorescence
thiabendazole
Prior art date
Application number
PCT/US2009/033855
Other languages
English (en)
Inventor
Paul Edward Bonnett
Nelson Alfred Johnson
Original Assignee
Syngenta Participations Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Publication of WO2009105375A1 publication Critical patent/WO2009105375A1/fr

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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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21G—CALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
    • D21G9/00—Other accessories for paper-making machines
    • D21G9/0009—Paper-making control systems

Definitions

  • the present invention relates to a method for detecting the presence of a fungicide in a sample which is generated during the manufacture of an industrial material.
  • the method according to the invention may be used to ensure that sufficient quantities of the fungicide are present in the industrial material.
  • a Liquid chromatographic based method for determining the presence of Thiabendazole (TBZ) residues on citrus fruits is known from J-AOAC-Int. 1996 Mar- Apr; 79(2): 579- 82.
  • This method uses fluorescence detection, however, it requires that the sample be subjected to a lengthy and complicated liquid chromatography technique prior to the fluorescence analysis.
  • the present invention provides a series of advantages over the prior art including the ability to rapidly analyse samples during the manufacturing process of industrial materials to check the presence of fungicide and the quantification thereof. The invention therefore provides significant improvements over the prior art.
  • a method for detecting the presence of a fungicide in a liquid sample extracted from a sample generated during manufacture of an industrial material comprising: (a) providing an aqueous and/or an organic/aqueous sample to be tested; (b) subjecting said sample to electromagnetic radiation of a wavelength sufficient to excite fluorophores comprised by said fungicide; (c) detecting fluorescence of said fluorophore in said sample.
  • the sample to be tested is an aqueous sample.
  • the sample to be tested is an organic/aqueous sample.
  • the sample to be tested is an organic sample.
  • the present invention further provides a method as described above wherein said material is cellulose of polymeric based such a paper and paper containing products.
  • industrial material includes those materials used in construction and the like.
  • industrial material may be structural timber, doors, cupboards, storage units, carpets, particularly natural fibre carpets such as wool and hessian, plastics, wood (including engineered wood) and wood plastic composite.
  • the industrial material is a coating.
  • Coating includes compositions applied to a substrate, for example, paints, stains, varnishes, lacquers, primers, semi gloss coatings, gloss coatings, flat coatings, topcoats, stain-blocking coatings, penetrating sealers for porous substrates, concrete, and marble, elastomeric coatings, mastics, caulks, and sealants, board and panelling coatings, transportation coatings, furniture coatings, and coil coatings, bridge and tank coatings and surface marking paints, leather coatings and treatments, floor care coatings, paper coatings, personal care coatings such as for hair, skin, nails, woven and nonwoven fabric coatings and pigment printing pastes, and adhesive coatings such as, for example, pressure sensitive adhesives and wet- and dry-laminating adhesives and plaster.
  • coating means paint; varnish; stain, lacquer or plaster.
  • said coating is a lacquer.
  • coating means paint. Paint can comprise, for example, a film former and a carrier (which carrier can be water and/or an organic solvent) and optionally a pigment.
  • industrial material includes adhesives, sealants, joining materials and joints and insulation material.
  • industrial material means structural timber.
  • industrial material means engineered wood.
  • industrial material means plastic.
  • Plastics includes plastic polymers and copolymers, including: acrylonitrile butadiene styrene, butyl rubber, epoxies, fluoropolymers, isoprene, nylons, polyethylene, polyurethane, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polyvinylidene fluoride, polyacrylate, polymethyl methacrylate, polyurethane, polybutylene, polybutylene terephthalate, polyether sulfone, polyphenyllenoxide, polyphenylene ether, polyphenylene sulfide, polyphtatamide, polysulphene, polyester, silicone, styrene butadiene rubber and combinations of polymers.
  • plastic polymers and copolymers including: acrylonitrile butadiene styrene, butyl rubber, epoxies, fluoropolymers, isoprene, nylons, poly
  • industrial material means polyvinyl chloride (PVC).
  • industrial material means polyurethane (PU).
  • industrial material means wood plastic composite (WPC). Wood plastic composite is a material that is well known in the art. A review of WPCs can be found in the following publication - Craig Clemons - Forrest Products Journal. June 2002 VoI 52. No. 6. pp 10- 18.
  • Wood is to be understood as meaning wood and wood products, for example: derived timber products, lumber, plywood, chipboard, flakeboard, laminated beams, oriented strandboard, hardboard, and particleboard, tropical wood, structural timber, wooden beams, railway sleepers, components of bridges, jetties, vehicles made of wood, boxes, pallets, containers, telegraph-poles, wooden fences, wooden lagging, windows and doors made of wood, plywood, chipboard, joinery, or wooden products which are used, quite generally, for building houses or decks, in building joinery or wood products that are generally used in house-building including engineered wood, construction and carpentry.
  • Industrial material also includes cooling lubricants and cooling and heating systems, ventilation and air conditioning systems and parts of production plants, for example cooling- water circuits.
  • Industrial material also includes wallboards such as gypsum based wallboards.
  • said industrial material is paper.
  • the sample for analysis may be taken from the paper product or from the process water used in the manufacture of the paper. If the sample is from the paper product then this sample is prepared for testing by mixing the paper with a solvent which may be water, a water/organic solvent mixture or an organic solvent.
  • organic solvents applicable to the present invention include acetonitrile, alcohols such as methanol, ethanol, propanol, ketones such as acetone, hydrocarbons such as hexane and aromatics such as toluene.
  • the present invention still further provides a method as described above wherein detection of said fluorescence allows the quantification of the fungicide in said sample.
  • the present invention still further provides a method as described above wherein the wavelength which excites the flouorophores comprised by said fungicide is about 305nm. In a particular embodiment said wavelength is 305nm. - -
  • the present invention still further provides a method as described above wherein the wavelength of the fluorescence signal emitted by the excited fluorophore is about 360nm. In a further embodiment said wavelength is 360nm.
  • the fungicide is Thiabendazole.
  • Thiabendazole (TBZ) is listed as entry 790 in The Pesticide Manual, Thirteenth Edition, published by The British Crop Protection Council, 2003.
  • TBZ is mainly known as a fungicide for use on crops.
  • fluorescence characteristics of TBZ can be used to calculate and quantify the presence and amount of TBZ containing fungicidal formulations during the manufacturing of industrial materials such as during paper production.
  • the present invention still further provides a method as described above wherein the fluorescence is detected via a fluorescence spectrometer.
  • the present invention still further provides a method as described above wherein said samples are analysed during the paper making process to ensure that the paper comprises sufficient quantities of the fungicide.
  • said samples are analysed after the paper making process to confirm that the paper comprises sufficient quantities of the fungicide.
  • the results of the analysis are used to control the amount of fungicide that is added to the pulp during the manufacturing process.
  • the present invention further provides a method for determining the amount of fungicide present in the paper comprising: (a) adding a desired level of fungicide to the pulp during the paper manufacturing process; and (b) generating paper from said pulp by extracting water from the pulp; (c) analysing the level of fungicide in said extracted water; and (d) deducing the level of fungicide in said paper based on the level of fungicide present in said extracted water.
  • the methods of the present invention may be used to ensure that appropriate levels of the fungicide are added to the industrial material such as the paper. For example, if the analysis yields that there is insufficient fungicide in the paper, further fungicide can be added to paper that is being generated. Likewise, if the analysis yields that there is too much fungicide in the paper, the amount added to the paper during manufacture can be reduced to ensure the appropriate levels in the end paper product are achieved. In both cases, the method may be repeated at multiple intervals to ensure that desired levels of the fungicide are present in the end paper product.
  • the fungicide may be applied to the industrial material via numerous means which are well known to the person skilled in the art including dipping, spraying, atomising, dusting, scattering, coating or pouring. More specifically and with respect to paper, the fungicide may be added via any of these means or via addition to the pulp which is subsequently processed into paper. Paper processing is well known to the person skilled in the art with early evidence dating back to ancient Egyptian times (where the material was a rather expensive commodity known as "papyrus").
  • an automated system can be provided wherein the system is programmed to deliver a desired level of fungicide in the product and the paper manufacturing machine samples the product at particular stages during the paper manufacturing. The results are then used to calculate the amount of fungicide that is added to the system to ensure that the desired quantity of fungicide is present in the end paper product. The system can then ensure that the appropriate amounts of fungicide are actually added to the system and monitored to ensure that the desired quantity of fungicide is present in the end paper product.
  • the present invention further provides an apparatus for manufacturing an industrial material which comprises a fungicide, which apparatus comprises a means for detecting the presence of a fungicide in an aqueous sample which is generated during manufacture of said material said apparatus comprising: (a) a means for providing an aqueous sample to be tested; (b) a means for subjecting said sample to electromagnetic radiation of a wavelength sufficient to excite fluorophores comprised by said fungicide; (c) a means for detecting fluorescence of said fluorophore in said sample.
  • said apparatus comprises a paper making apparatus.
  • said papermaking apparatus comprises a means for detecting the presence of a fungicide during the paper making process.
  • said means for detecting the presence of a fungicide is located within a part of the apparatus selected from the group consisting of the stock chest, flow box, pulp refiner, pulper, centri- cleaners, scalping screens, reverse cleaners, dump chest, refiners, machine chest, consistency stuff box, Whitewater chest, fan pump, headbox, tray water, broke tank, dissolved air flotation (daf) unit, primary clarifier, secondary clarifier, effluent outfall.
  • the present invention still further provides a papermaking apparatus as described above wherein said apparatus further comprises a means for performing the method of determining the amount of fungicide present in the paper as described above.
  • the present invention still further provides the use of a fluorescence detector in the detection of a fungicide in an aqueous sample which is generated during manufacture of an industrial material.
  • the detector is a quantitative one.
  • the fungicide is Thiabendazole and the industrial material is paper.
  • the present invention still further provides a method for the detection of a fungicide in the effluent generated during the manufacture of an industrial material comprising: (a) providing an aqueous sample of the effluent to be tested; (b) subjecting said sample to electromagnetic radiation of a wavelength sufficient to excite fluorophores comprised by said fungicide; (c) detecting fluorescence of said fluorophore in said sample.
  • the detection of said fluorescence allows the quantification of the fungicide in said sample.
  • the wavelength which excites the flouorophores comprised by said fungicide is about 305nm.
  • the wavelength of the fluorescence signal emitted by the excited fluorophore is about 360nm.
  • said fungicide is Thiabendazole.
  • the fluorescence is detected via a fluorescence spectrometer.
  • Pulp B (-1.0% cellulose fibers): 80 grams of Pulp A concentrate and 20 grams of Pulp B concentrate were mixed with 900 grams of tap water. The mixture was mixed via a propeller mixer (400-600 RPM) until homogeneous and thin (in this example the mixture was mixed for at least 1 A hr).
  • Paper slurry was then generated using the following ingredients:
  • Formulation A is a water based fungicidal formulation containing as fungicidal active ingredients - Azoxystrobin 19%; Thiabendazole 19% and Fludioxonil at 1.9% by weight.
  • Azoxystrobin is described as entry 47 in The Pesticide Manual, Thirteenth Edition, published by The British Crop Protection Council, 2003.
  • Fludioxonil is listed as entry 368. Both compounds are well known as fungicides for use on crops and also as seed treatment agents. - o -
  • the mixture was agitated to ensure homogenous condition before opening bottom valve on to hand-sheet former filter and collecting the effluent. Once the water was almost totally filtrated, a light vacuum was turned on for few seconds followed by full vacuum to completely drain the water. The filter was opened and the compacted paper was peeled off the filter onto a blotter paper. The paper disc was covered with another layer of blotter paper and pressed to dry the excess humidity. The paper disc was then placed on the pre-heated press-dryer (no temp adjustment, on-off button only) and dried for 3 minutes, until constant weight.
  • the concentration of thiabendazole in the paper slurry was determined from a thiabendazole standard curve by plotting the concentration (ppm) of thiabendazole in a pH 5.3 buffer solution vs the thiabendazole fluorescence signal at about 360 nm.
  • the concentration of thiabendazole in the standard calibration solutions ranged from 0.1 ppm to 1 ppm thiabendazole.
  • Paper Analysis About 1 gram of paper containing about 500 ppm of thiabendazole was cut into small strips, and added to a 20 ml vessel. 20 ml of acetonitrile:water mixture (50:50) was added and sonicated in a water bath at room temperature (between 25-7O 0 C) for about 20 minutes. About 0.2 ml of the organic or aqueous organic extract was added to 7 ml of pH 5.3 buffer and agitated several times. An aliquot of the diluted paper extract was then transferred to a cuvette and the fluorescence signal at about 360 nm measured.
  • the concentration of thiabendazole in the paper was determined from a thiabendazole standard curve by plotting the concentration (ppm) of thiabendazole in a pH 5.3 (pH 2-8) buffer solution vs the thiabendazole fluorescence signal at about 360 nm.
  • the concentration of thiabendazole in the standard calibration solutions ranges from 0.1 ppm to 1 ppm thiabendazole.
  • Table 1 presents the analytical results from the paper produced in Examples 1 & 2.
  • HPLC analysis was conducted along side the fluorescence measurement for comparison.
  • Table 2 shows that the ratios of the other fungicidal components in "Formulation A" are retained in the paper at a fixed ratio based and therefore the concentration of thiabendazole can be used to predict the level of other additives in the paper.

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  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne un procédé pour détecter la présence d’un fongicide dans un échantillon qui est généré par la fabrication d’une matière industrielle. En particulier, le procédé selon l’invention peut être utilisé pour garantir que des quantités suffisantes du fongicide sont présentes dans la matière industrielle. Dans un mode de réalisation en particulier, le fongicide est le thiabendazole et la matière est du papier.
PCT/US2009/033855 2008-02-19 2009-02-12 Procédé de détection WO2009105375A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2959408P 2008-02-19 2008-02-19
US61/029,594 2008-02-19

Publications (1)

Publication Number Publication Date
WO2009105375A1 true WO2009105375A1 (fr) 2009-08-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2430179A1 (fr) * 2009-02-27 2012-03-21 Syngenta Participations AG Procédé de détection
US9746425B2 (en) 2015-05-12 2017-08-29 Gojo Industries, Inc. Waste detection

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040033555A1 (en) * 2001-07-20 2004-02-19 Shawn Louise Anderson Methods using light emission for determining the effeciveness of plant treatment agents in controlling plant disease organisms
US20060270919A1 (en) * 2005-05-11 2006-11-30 Mytek, Llc Biomarkers sensing
US20070004046A1 (en) * 2005-07-01 2007-01-04 Platypus Technologies, Llc Detection of analytes
US20070160814A1 (en) * 2005-06-20 2007-07-12 Mercolino Thomas J Methods for quality control

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040033555A1 (en) * 2001-07-20 2004-02-19 Shawn Louise Anderson Methods using light emission for determining the effeciveness of plant treatment agents in controlling plant disease organisms
US20060270919A1 (en) * 2005-05-11 2006-11-30 Mytek, Llc Biomarkers sensing
US20070160814A1 (en) * 2005-06-20 2007-07-12 Mercolino Thomas J Methods for quality control
US20070004046A1 (en) * 2005-07-01 2007-01-04 Platypus Technologies, Llc Detection of analytes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2430179A1 (fr) * 2009-02-27 2012-03-21 Syngenta Participations AG Procédé de détection
EP2430179A4 (fr) * 2009-02-27 2014-01-08 Syngenta Participations Ag Procédé de détection
US9746425B2 (en) 2015-05-12 2017-08-29 Gojo Industries, Inc. Waste detection
US10126249B2 (en) 2015-05-12 2018-11-13 Gojo Industries, Inc. Waste detection
US10539513B2 (en) 2015-05-12 2020-01-21 Gojo Industries, Inc. Waste detection

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