EP0524230A1 - Analyse de composes constitues d'aldehydes ou pouvant etre convertis en aldehydes - Google Patents

Analyse de composes constitues d'aldehydes ou pouvant etre convertis en aldehydes

Info

Publication number
EP0524230A1
EP0524230A1 EP19910907562 EP91907562A EP0524230A1 EP 0524230 A1 EP0524230 A1 EP 0524230A1 EP 19910907562 EP19910907562 EP 19910907562 EP 91907562 A EP91907562 A EP 91907562A EP 0524230 A1 EP0524230 A1 EP 0524230A1
Authority
EP
European Patent Office
Prior art keywords
aldehyde
compound
sample
complex
reagent
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Withdrawn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
EP19910907562
Other languages
German (de)
English (en)
Inventor
Martyn William Hill
Dennis Frank Sharman
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.)
CTS Biocides Ltd
Original Assignee
CTS Biocides Ltd
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 GB909008100A external-priority patent/GB9008100D0/en
Priority claimed from GB909010278A external-priority patent/GB9010278D0/en
Priority claimed from GB909026054A external-priority patent/GB9026054D0/en
Application filed by CTS Biocides Ltd filed Critical CTS Biocides Ltd
Publication of EP0524230A1 publication Critical patent/EP0524230A1/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Withdrawn legal-status Critical Current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

Definitions

  • This invention relates to an assay for compounds which are, or can be converted to, aldehydes.
  • Known aldehyde tests include the Sawicki and Purpald reactions. Both these known reactions, and especially the latter, are good for assaying formaldehyde. They are less sensitive, to varying degrees, to other aldehydes. Moreover, the Purpald reaction requires alkali, and may therefore be experimentally-undesirable.
  • Known biocides include glutaraldehyde and methylene- bisthiocyanate (MBTC) . They are used in cooling towers, in order to control organisms such as Le ⁇ ionella. in paper- making and in other aqueous environments. It is an object behind this invention to monitor the level ' of such compounds in the water.
  • the invention is based, at least in part, on the realisation that MBTC releases formaldehyde under alkaline conditions such as those that prevail in cooling towers.
  • the Purpald reaction is clearly unsuitable in these circumstances, since it cannot distinguish between MBTC and any free formaldehyde with which such a compound may be in equilibrium or with any formaldehyde from another source.
  • a compound capable of releasing an aldehyde under alkaline or other given conditions (described herein as an aldehyde-releaser) , and free aldehyde in an aqueous sample are distinguished.
  • One aspect of the invention is a method which comprises: in a first sample, converting the aldehyde-releaser to aldehyde; in a second sample, separating the aldehyde-releaser and aldehyde; and determining the difference between the respective amounts of aldehyde obtained from the first and second samples.
  • the amount of aldehyde obtained from the first sample corresponds to the total amount of aldehyde-releaser and free aldehyde (which may include any aldehyde already present in the sample) .
  • the amount of aldehyde obtained from the second sample corresponds to free aldehyde only, and the difference between the two amounts therefore corresponds to the amount of aldehyde- releaser.
  • a second aspect of the invention is a method which comprises: separating the aldehyde-releaser and aldehyde; converting the aldehyde-free aldehyde-releaser to aldehyde; and determining the amount of aldehyde obtained by conversion.
  • the aldehyde is formaldehyde, it can be determined by the Purpald or Sawicki reaction. This is less satisfactory for an aldehyde having at least 2, 3 or more carbon atoms, e.g. glutaraldehyde.
  • such an aldehyde is assayed by reacting an aqueous sample containing the aldehyde with an agent with which the aldehyde reacts to form a water- insoluble complex, adding a reagent that gives a colour on reaction with the complex, and determining the colour.
  • complexing agent provides one means of separating aldehyde from aldehyde-releaser. Alternatively, they may be separated by contacting the appropriate sample with an anion-exchange resin, bisulphite or other immobilised medium that retards either the aldehyde or the aldehyde-releaser; if it is then necessary or desired to assay the bound aldehyde or bound aldehyde- releaser, the bound species may be eluted. If a complexing agent is used, it should be added in an amount sufficient to precipitate all free aldehyde, e.g.
  • the utility of the novel method is based on the realisation that the aldehyde, but not the releaser, will form a water-insoluble complex with compounds such as substituted 1,2-diaminoethane ⁇ which themselves are readily assayed by reaction with a suitable reagent, specifically a diazo compound, to give a characteristic colour.
  • a suitable reagent specifically a diazo compound
  • Specific complexing agents that can be used are 1,2-dianilino-l,2-diphenylethane and 1,2- dianilinoethane (Wanzlick's reagent).
  • the assay can suitably be conducted by - forming the complex, filtering the system, e.g. through a syringe filter, washing the complex residue, solubilising the complex, and adding a suitable diazo compound (of which many are known) . Thorough washing of the residue is desirable; it is preferred to use dilute acetic acid.
  • the solubilising agent may be IM HC1, optionally in admixture with methanol.
  • the formation/physical properties of the complex may be enhanced by salting out or another procedure such as adding a polymer that reduces its adherent tendencies, thus facilitating precipitation and recovery.
  • the complexing agent serves to concentrate aldehyde in the sample under test. An aldehyde that would give a reaction of low sensitivity to, say, Purpald reagent in the original sample may, after concentration, be so assayed.
  • the most preferred procedure is to separate the aldehyde-releaser and the aldehyde by bringing the sample into contact with a suitably immobilised reagent, e.g. an anion-exchange resin which binds/retards the aldehyde- releaser.
  • a suitably immobilised reagent e.g. an anion-exchange resin which binds/retards the aldehyde- releaser.
  • the bound species can subsequently be released by elution: for example, aqueous NaCl will serve to elute MBTC from an anion-exchange resin.
  • the releaser can then be assayed.
  • the aldehyde that is not immobilised may be compared with total aldehyde that can be generated by the sample. Formaldehyde that is released can of course be assayed by the Sawicki or Purpald reaction.
  • Example 1 Glutaraldehyde Assay
  • STEP 1 Close syringe and filter by means of the 3 way tap and pipette into syringe 6ml water to be tested for its glutaraldehyde content (or 6ml RO water to which appropriate quantities of glutaraldehyde have been added) .
  • STEP 2. Add 0.4ml Wanzlick's reagent (22 g/ml 4M acetic acid) . Mix well, wait 20 minutes.
  • STEP 3. Add 1ml 3M NaCl solution, mix well, wait 30 seconds.
  • STEP 4. Open tap on bottom of syringe and allow liquid to pass through the Whatman O.lum Puradisc filter in the filter unit; discard filtrate.
  • STEP 5. Wash precipitate (glutaraldehyde-Wanzlick's complex) on the filter disc with 7.5ml 0.25M acetic acid. Discard filtrate.
  • step 5 Close tap on bottom of syringe.
  • STEP 7 Add 3 ml IM HCl to the syringe and shake for 1 minute to dissolve any of the complex stuck to the wall of the syringe. Open the tap. The acid is then pushed slowly through the filter. The crystalline glutaraldehyde-Wanzlick's complex on the filter dissolves. Collect the filtrate in a test tube.
  • STEP 8. Adjust pH of filtrate to pH 3.5 by titration with 3.75M NaOH.
  • STEP 9 Add 0.4ml 4M acetic acid and mix.
  • STEP 10. Add 0.15ml Polymer (0.1% in RO water). Mix.
  • STEP 11. Add 0.2ml Fast Scarlet GG solution (lOmg/ml in RO water) :mix and wait for 5 minutes.
  • STEP 12. Take out 1.5ml into test tube.
  • STEP 13 Add 1.5ml cone. HCl;mix;wait for 2 minutes.
  • STEP 14 Read light absorption in colorimeter at 490nm.
  • Colorimeter WPA CO 210, or equivalent, with cuvettes (Polystyrene or silica) .
  • Test tubes plastic, 8 ml; obtainable from Sarsted, West
  • volumetric flasks, glass 10 ml; 100 ml.
  • Step 1 pipette into plastic test tube de-ionised water followed by the required volume of MBTC "working solution"; final volume: 1ml. (If a test on a water sample is to be carried out, use 1 ml of the water to be tested for its MBTC content) .
  • Step 2 add 1 ml of 5 M NaOH, mix well by flicking the tube with finger and thumb (or shaking) and wait 5 in.
  • Step 3 add 0.5 ml Purpald reagent (10 mg/ml in 0.5 M HC1) , mix and allow 5 min for the formation of the first purple colour complex (see BASIS OF REACTION FOR ANALYSIS) .
  • SUBSTITUTESHEET Step 4 add 0.3 ml of NaI0 4 solution (21.4 mg/ml water) ; mix, wait 1-5 min.
  • Step 5 read optical density (O.D.) of the deep purple solution at 550 nm in a colorimeter; use silica or polystyrene cuvettes.
  • Fig. I shows the absorption spectrum of the colour complex formed by different amounts of MBTC with the Purpald reagent after oxidation with NaI0 4 .
  • Table 1 and Fig. II. show values for a typical calibration curve for MBTC obtained by the above method. Table 1.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Echantillon aqueux contenant du bisthiocyanate de méthylène ou un autre composé capable de libérer un aldéhyde, analysé par détermination de la quantité d'aldéhyde libérée par conversion, par rapport, par exemple, à un échantillon dont on a séparé les aldéhydes existants. Echantillon aqueux contenant du glutaraldéhyde ou un autre aldéhyde possédant au moins 2 atomes C, analysé par addition d'un agent produisant un complexe insoluble dans l'eau et détermination de la quantité de complexe ou d'aldéhyde, après régénération.
EP19910907562 1990-04-10 1991-04-09 Analyse de composes constitues d'aldehydes ou pouvant etre convertis en aldehydes Withdrawn EP0524230A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB9008100 1990-04-10
GB909008100A GB9008100D0 (en) 1990-04-10 1990-04-10 Assay
GB909010278A GB9010278D0 (en) 1990-05-08 1990-05-08 Assay
GB9010278 1990-05-08
GB9026054 1990-11-30
GB909026054A GB9026054D0 (en) 1990-11-30 1990-11-30 Assay

Publications (1)

Publication Number Publication Date
EP0524230A1 true EP0524230A1 (fr) 1993-01-27

Family

ID=27265040

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910907562 Withdrawn EP0524230A1 (fr) 1990-04-10 1991-04-09 Analyse de composes constitues d'aldehydes ou pouvant etre convertis en aldehydes

Country Status (5)

Country Link
EP (1) EP0524230A1 (fr)
JP (1) JPH05506307A (fr)
AU (1) AU657906B2 (fr)
CA (1) CA2080374A1 (fr)
WO (1) WO1991015761A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0610302A1 (fr) * 1991-10-30 1994-08-17 Cts Biocides Ltd. Methode d'analyse

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA801052B (en) * 1979-03-10 1981-09-30 British Petroleum Co Apparatus and method for the determination of biocide concentration in aqueous systems

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9115761A1 *

Also Published As

Publication number Publication date
AU7663091A (en) 1991-10-30
JPH05506307A (ja) 1993-09-16
AU657906B2 (en) 1995-03-30
CA2080374A1 (fr) 1991-10-11
WO1991015761A1 (fr) 1991-10-17

Similar Documents

Publication Publication Date Title
US6323036B1 (en) Reagents and methods for releasing and measuring lead ions from biological matrices
KR950019732A (ko) 뇨 단백질 및 크레아티닌의 측정방법
JPS6339871B2 (fr)
Scheurer et al. Colorimetric submicromethod for determination of ammonia
AU657906B2 (en) Assay for compounds which are, or can be converted to, aldehydes
CA2254357A1 (fr) Dosage de reactifs diazoiques et methodes d'utilisation
US5183762A (en) Copper containing reagent for the detection and determination of bilirubin in the urine
US5372947A (en) Assay for an aldehyde or a compound capable of releasing an aldehyde
Margel et al. Reduction of organic mercury in water, urine, and blood by sodium borohydride for direct determination of total mercury content.
US3542649A (en) Color developing composition consisting of an enzyme,a salicylate and a hypochlorite donor
JPH02503599A (ja) 固相タンパク質アッセイ
US5552297A (en) Lead detection method and reggents utilizing aminolevulinic acid dehydratase and tertiary phosphines
Gaugush et al. A rapid manual method for nitrate determination in small volumes by a modification of the cadmium reduction method
CA1186200A (fr) Systeme et methode pour la preparation d'une solution temoin utile au dosage des cetones
Nelson et al. Simplified automated method for determination of urinary or serum uric acid, based on reduction of ferric-phenanthroline complex
Arakawa et al. Chemiluminescent assay for catecholamines by the generation of hydrogen peroxide in basic solution and the use of isoluminol-microperoxidase
RU2000373C1 (ru) Способ получени реактивной индикаторной бумаги
US5821074A (en) Method and compositions for enhancing aminolevulinic acid dehydratase assay
JP3308289B2 (ja) 尿中蛋白質検出方法及び試験片
JPH09203735A (ja) 非特異反応の抑制方法
SU1105814A1 (ru) Способ экстракционно-фотометрического определени меди,кобальта и кадми
RU2056634C1 (ru) Способ определения микроколичеств арсина в газах
RU2183017C1 (ru) Индикаторный состав для определения рения (vii) в водных растворах
SU1647401A1 (ru) Способ определени цинка и кадми
AU662162B2 (en) Colorimetric determination of magnesium ions in fluids

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19921023

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19950116

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19950527