US3822189A - Enzymatic time-temperature indicating methods and devices - Google Patents

Enzymatic time-temperature indicating methods and devices Download PDF

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Publication number
US3822189A
US3822189A US00313316A US31331672A US3822189A US 3822189 A US3822189 A US 3822189A US 00313316 A US00313316 A US 00313316A US 31331672 A US31331672 A US 31331672A US 3822189 A US3822189 A US 3822189A
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temperature
reaction product
time
indicator
chamber
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US00313316A
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English (en)
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S Tornmarck
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Food Control AB
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Food Control AB
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01KMEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K3/00Thermometers giving results other than momentary value of temperature
    • G01K3/02Thermometers giving results other than momentary value of temperature giving means values; giving integrated values
    • G01K3/04Thermometers giving results other than momentary value of temperature giving means values; giving integrated values in respect of time

Definitions

  • the present invention relates to a method. and device for. time-temperature responsive indication.
  • theinterrelationobtained by means of such an enzymatic indicator is not always the desired one. For instance, if;a suitable interrelation exists between the change-overtime of the indicator at low temperatures, the change-overtime at high temperatures will frequently be too long. To some extent, this deviation of the time-temperature responsiveness of the indicator from the desired value is-corrected in that the enzymatic indicator at low .temperatures may exhibit a linear interrelation of temperatureaand g time which has a different, less negative coefficient :ofinclination than the linear interrelation at high temperatures. The inclination of these curves at low "temperaturesdsdetermined by the chemical mechanism and can be van'ed within rather narrow limits only.
  • Swedish Pat. 346,162 which relates to an enzymatic indication of the above-mentioned type
  • Swedish patent application 9,715/70 which relates to a time-temperature responsive indication, the substances adapted to react with one another being kept apart by a semi-permeable diaphragm, the permeability of which increases with an increase in temperature.
  • the present invention it has now been contrived to obtain a satisfactory adaptation of the time-temperature responsiveness of the indicator and thereby to eliminate the disadvantages of the prior indicators.
  • the present invention is based upon the utilisation of an enzymatic indicator, and to adapt the time-temperature responsiveness of the indicator, i.e. in order to obtain a more rapid change at high temperatures, the indicator is supplied with and additional amount of the reaction product that is being indicated.
  • the invention relates to a time-temperature responsive indication method in which an enzyme as a function of time and temperature in a reaction zone acts upon a sub strate, while forming a reaction product that is established by means of an indicating substance, said method being characterised in that there is introduced into the reaction zone an additional amount of the reaction product, increasing with an increase in temperature.
  • the invention also comprises a device for carrying the method into efiect, said device comprising two chambers interconnected by means of a temperature-controlled valve means, one of said chambers constituting a reaction zone containing a time-temperature responsive enzymatic indicator consisting of an enzyme, a substrate, a solvent, an indicator and, if desired, a butter, said device being characterised in that said second chamber contains a source of the reaction product that is generated by the enzymatic reaction within said first chamber.
  • the enzyme preferably is urease, the substrate urea, the reaction product ammonia, and the indicating substance is a pH indicator;
  • the above-mentioned source of reaction product may consist of the reaction product which is to be supplied to the reaction zone or of the same enzyme and substrate as in said reaction zone which, as a function of time and temperature, produce the reaction product which is then supplied to said reaction zone.
  • the temperature-controlled valve means preferably is a semi-permeable diaphragm, the permeability of which increases with an increase in temperature, or a bimetallic spring.
  • FIG. 1 shows indication characteristics of a known I enzymatic indicator
  • FIG. 2 shows the characteristic of an indicator according to the invention
  • FIGS 3-5- show different embodiments of the device according to the invention.
  • 'A generally is a characteristic of an indicator having a low buffer strength, i.e. it has no or but an insignificant addition of buffer
  • B is a characteristic of an indicator having a high buffer strength, i.e. it has a higher addition of buffer.
  • the indication characteristic is parallelly offset towards longer changeover times by the addition of a butter.
  • the figure also shows that the indication characteristic is composed of two curve branches which substantially correspond to straight lines, and for the characteristic A the portion a is the high temperature indication characteristic, whereas the portion a is the low temperature indication characteristic. The same applies to the characteristic B and the curve branches b and b", respectively.
  • the indication characteristic could previously only be affected by the addition of a buffer, i.e. by parallelly offsetting the characteristic.
  • the inclination of the curve branches a and b, respectively, could not be affected, whereas the inclination of curve branches a" and b", respectively, could be affected to a small degree only.
  • the enzymatic indicator is supplied as a function of the temperautre with an additional amount of reaction product from a source which is or generates such a reaction product.
  • the result is a composite indication characteristic which at low temperatures corresponds to the above-mentioned characteristic according to FIG. 1 but which at high temperatures, because of the additional amount of reaction product, obtains different inclination, as will appear from FIG. 2, curve B.
  • this new indication characteristic E is composed of the characteristic C of the main indicator according to FIG. 1, and of curve D for the additional amount of reaction product.
  • the appearance of curve D will depend upon the special design, described in the following, of the indicator according to the present invention, by which design an increasing addition of reaction product at increasing temperature is made possible. It will be appreciated that by changing the form of curve D the indication characteristic E can be changed in different ways so that the desired appearance will be obtained.
  • the indicator according to FIG. 3 is a container comprising two chambers 1 and 2 separated by a partition 3.
  • the chambers 1 and 2 are defined outwardly by outer walls 7 and 8 of impermeable material, such as a suitable plastics material.
  • the chamber 2 contains a capsule 6 with the reaction product, i.e. the substance that is formed by the reaction between the enzyme and the substrate in capsules 4 and 5.
  • the above-mentioned partition 3 is formed of a semi-permeable diaphragm material, such as low density polyethylene or cellulose acetate, the permeability of such diaphragm material increasing with an increase in temperature.
  • the function of the indicator according to FIG. 3, in which the enzyme is urease, the substrate is urea, the resulting reaction product is ammonia, and the indicating substance is a pH indicator, is as follows.
  • the indicator is activated by crushing the capsules 4, 5 and 6, whereby urease and urea are brought together within the chamber 1, and the enzymatic process starts by forming ammonia.
  • the enzymatic indication reaction within the chamber 1 has a characteristic corresponding to curve A, B or C in FIGS. 1 and 2, respectively.
  • the chamber 2 simultaneously contains ammonia that has been released by the crushing of the capsule 6, and this ammonia passes through the diaphragm 3 into the chamber 1 as a function of the temperature. If the time it takes for a given amount of ammonia to penetrate the diaphragm 3 into the chamber 1 is taken as a function of the temperature, a curve corresponding to D in FIG. 2 will be obtained.
  • FIG. 4 shows another embodiment of the indicator according to this invention.
  • the indicator of FIG. 4 largely corresponds to the one shown in FIG. 3, and like parts have been identified by like reference numerals.
  • the indicator according to FIG. 4 differs from the indicator according to FIG. 3 in that the source of reaction product within the chamber 2 is not directly a reaction product (ammonia), but the same enzyme and substrate as in the chamber 1, in this instance urease and urea.
  • the enzyme and the substrate within the chamber 2 are enclosed in capsules 9 and 10 which, uponactivation of the indicator, are crushed like the capsules 4 and 5 within the chamber 1.
  • the enzyme and the substrate within the chamber 2 will generate as a function of time and temperature the reaction product ammonia which passes through the diaphragm 3 into the chamber 1.
  • the indicator according to FIG. 4 thus corresponds to the indicator according to FIG. 3, except that the reaction product within the chamber 2 is not in its finished state, but is generated as the indication proceeds.
  • FIG. 5 shows a further embodiment of the indicator according to the present invention, and this indicator differs from the two devices previously described substantially in that the diaphragm 3 which acts as a timecontrolled valve means, has been replaced by a bimetallic spring 11.
  • the bimetallic spring 11 rests against the seat 12 and thus prevents communication between the chambers 1 and 2.
  • the bimetallic spring is bent more and more and rises from the seat 12, as is shown in FIG. 5.
  • a communication passage is established between the chamhers I and 2, the size of said passage increasing with an increase in temperature.
  • the additional amount of reaction product within the chamber 2 will be supplied to the chamber 1 as a function of the temperature, as in the devices according to FIGS. 3 and 4.
  • the source 6 of the reaction product within the chamber 2 actually may be a finished reaction product, as is shown in FIG. 5, or enzyme and substrate forming the reaction product.
  • valve means between the chambers 1 and 2 in the form of a semi-permeable diaphragm or in the form of a bimetallic spring, but also in this respect it will be obvious that any valve means can be employed which, as a function of the temperature, controls the communication between chambers 1 and 2.
  • the present invention has a wide field of use generally encompassing all kinds of sensitive substances and products, for instance the supervision and indication of food products, medicines, photographic film, storage-sensitive chemical substances, such as explosives, etc.
  • a device for time-temperature responsive indication said device having two chambers a temperature-controlled valve means connecting said chamber;
  • a time-temperature responsive enzymatic indicator including an enzyme and its substrate, a solvent, an indicating substance to indicate enzyme activity on the substrate and a buffer in one of said chambers, said first chamber constituting a reaction zone,
  • theimprovement comprises:
  • a device wherein the enzyme is urease, the substrate urea, the reaction product ammonia, and ⁇ the indicating substance is a pH indicator.
  • a device wherein said source consists of the reaction product which is to be supplied to the reaction zone.
  • a device wherein said source consists of the reaction product which is to be supplied to the reaction zone.
  • a device wherein said source consists of enzyme and substrate of the same kind as those in the reaction zone which, as a function of time and temperature, form the reaction product subsequently supplied to the reaction zone.
  • a device wherein said source (9, consists of enzyme and substrate of the same kind as those in the reaction zone which, as a function of time and temperature, form the reaction product subsequently supplied to the reaction zone.
  • valve means is a semi-permeable diaphragm whose permeability increases with increasing temperature.
  • valve means is a bimetallic spring.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
US00313316A 1971-12-10 1972-12-08 Enzymatic time-temperature indicating methods and devices Expired - Lifetime US3822189A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SE7115855A SE376657B (en, 2012) 1971-12-10 1971-12-10

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US3822189A true US3822189A (en) 1974-07-02

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US (1) US3822189A (en, 2012)
JP (1) JPS4866479A (en, 2012)
DE (1) DE2257838C3 (en, 2012)
GB (1) GB1366797A (en, 2012)
SE (1) SE376657B (en, 2012)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977945A (en) * 1974-02-21 1976-08-31 Food Control Ab Time and temperature-dependent enzymatic indicator
US4066403A (en) * 1975-06-20 1978-01-03 Eastman Kodak Company Multilayer analytical element
USRE30267E (en) * 1975-06-20 1980-05-06 Eastman Kodak Company Multilayer analytical element
US4284719A (en) * 1979-05-17 1981-08-18 Kockums Chemical Ab Substrate composition and use thereof
AU644935B2 (en) * 1991-01-31 1993-12-23 Oscar Mayer Foods Corporation Time temperature indicator with distinct end point
WO2000047964A1 (en) * 1999-02-10 2000-08-17 Temp-Tell Limited Thermal history indicators
EP1138777A3 (en) * 2000-03-23 2002-08-07 Konica Corporation Temperature history indicator
US6694913B2 (en) * 2001-08-10 2004-02-24 Isadore Cooperman Changed condition indicator
US20060130734A1 (en) * 2003-02-27 2006-06-22 Avantone Oy Printed TTI indicators
US20070151502A1 (en) * 2001-08-10 2007-07-05 Isadore Cooperman Changed condition indicator
US20130081566A1 (en) * 2011-10-04 2013-04-04 Sanko Tekstil Isletmeleri Sanayi Ve Ticaret A.S. Intelligent temperature indicator label and method
US20140311401A1 (en) * 2013-04-23 2014-10-23 Inditechkorea Co., Ltd. Freeze indicator
US20150153315A1 (en) * 2013-12-04 2015-06-04 Temptime Corporation Condition change labels
WO2017060676A1 (en) * 2015-10-05 2017-04-13 The Technology Partnership Plc Data logging device
CN106996930A (zh) * 2017-05-03 2017-08-01 中国标准化研究院 食品用时间温度指示器

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59124956A (ja) * 1982-12-29 1984-07-19 Sakata Shokai Ltd 熱履歴検知用の熱インジケ−タ−
US4826762A (en) * 1987-10-23 1989-05-02 Massachusetts Industry Of Technology Enzymatic temperature change indicator
FR2896311B1 (fr) * 2006-01-18 2008-03-21 Galdino Barbieri Detecteur de depassement d'une temperature limite
GB2552167A (en) 2016-07-11 2018-01-17 Intray Ltd Time temerature indicator label

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977945A (en) * 1974-02-21 1976-08-31 Food Control Ab Time and temperature-dependent enzymatic indicator
US4066403A (en) * 1975-06-20 1978-01-03 Eastman Kodak Company Multilayer analytical element
USRE30267E (en) * 1975-06-20 1980-05-06 Eastman Kodak Company Multilayer analytical element
US4284719A (en) * 1979-05-17 1981-08-18 Kockums Chemical Ab Substrate composition and use thereof
AU644935B2 (en) * 1991-01-31 1993-12-23 Oscar Mayer Foods Corporation Time temperature indicator with distinct end point
US7036452B1 (en) 1999-02-10 2006-05-02 Temp-Tell Limited Thermal history indicators
WO2000047964A1 (en) * 1999-02-10 2000-08-17 Temp-Tell Limited Thermal history indicators
EP1138777A3 (en) * 2000-03-23 2002-08-07 Konica Corporation Temperature history indicator
US20070151502A1 (en) * 2001-08-10 2007-07-05 Isadore Cooperman Changed condition indicator
US7011037B2 (en) 2001-08-10 2006-03-14 Isadore Cooperman Changed condition indicator
US20040182304A1 (en) * 2001-08-10 2004-09-23 Isadore Cooperman Changed condition indicator
US6694913B2 (en) * 2001-08-10 2004-02-24 Isadore Cooperman Changed condition indicator
US7770534B2 (en) 2001-08-10 2010-08-10 Isadore Cooperman Changed condition indicator
US20060130734A1 (en) * 2003-02-27 2006-06-22 Avantone Oy Printed TTI indicators
US7430982B2 (en) * 2003-02-27 2008-10-07 Avantone Oy Printed TTI indicators
US20130081566A1 (en) * 2011-10-04 2013-04-04 Sanko Tekstil Isletmeleri Sanayi Ve Ticaret A.S. Intelligent temperature indicator label and method
US8695528B2 (en) * 2011-10-04 2014-04-15 Sanko Tekstil Isletmeleri Sanayi Ve Ticaret A.S. Intelligent temperature indicator label and method
US20140311401A1 (en) * 2013-04-23 2014-10-23 Inditechkorea Co., Ltd. Freeze indicator
US9410852B2 (en) * 2013-04-23 2016-08-09 Intellectual Discovery Co., Ltd. Freeze indicator
US20150153315A1 (en) * 2013-12-04 2015-06-04 Temptime Corporation Condition change labels
US9739757B2 (en) * 2013-12-04 2017-08-22 Temptime Corporation Condition change labels
WO2017060676A1 (en) * 2015-10-05 2017-04-13 The Technology Partnership Plc Data logging device
GB2557812A (en) * 2015-10-05 2018-06-27 Ttp Plc Data logging device
CN106996930A (zh) * 2017-05-03 2017-08-01 中国标准化研究院 食品用时间温度指示器

Also Published As

Publication number Publication date
JPS4866479A (en, 2012) 1973-09-12
GB1366797A (en) 1974-09-11
DE2257838C3 (de) 1978-09-07
DE2257838A1 (de) 1973-06-20
SE376657B (en, 2012) 1975-06-02
DE2257838B2 (de) 1978-01-12

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