AU604681B2 - Protection of food against oxidation - Google Patents

Description

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AU-Arl 70235/87 OROA STON NBPDOEDE A' PR ETJWELTUELLE DEMANDE INTERNATIONALE PU3LIEE EN U TR ITE5E COOPERATION F' MATIERE DE BREVETS (PCT) (51) Classification internationale des brevets 4 (11) Numnro de publication internationale: WO 87/ 04904 A23L 3/36 A2 (43) Date de publication internationale: 27 aodit 1987 (27.08.87) (21) Numno de la demnande internationale: PCT/CH87/00020 (74) Repr~sentant commun: SOCIETE DES PRODUITS NESTLE Case postale 353, CH-1800 Vevey (22) Date dle d~p6t international: 16 f~vrier 1987 (16,02.87) (CH).

(31) Numnro de la demnande prioritaire: 666/86-2 (81) Etats disignks: AU, JP, US.

(32) Date de prioriti: 19 f~vrier 1986 (19,02.86) Publi~e (33) Pays de priorit6: CH Sans rapport de rechierche internationale, sera republige d~s r~ception de ce rapport.

(71) D61posant (pour bous les Elats d~sign~s sauf US): SO- CIETE DES PRODUITS NESTLE S.A. (CR/CR]; Case postale 353, CH-1800 Vevey (CR).

(72) Inventeurs; et3 Robert Chemin du Lacuez 38 A, CHR1807 Blonay LOLIGER, Jijrg Chemin de1 Pierre AX Fleur 6, CH-1802 Corseaux F AUSTRALIAN K socument contins the -9 SEP 1987 aniendments made urder PATENT oFFICE Section 49 and is correct for printing.

(54) Title: PROTECTION OF FOOD AGAINST OXIDATION (54) Tltre: PROTECTION DYUN ALIMENT CONTRE L OXYDATION (57) Abstract Uric acid is added to the food in a proportion of 5-10000 [ig or uric acid per g of dry rood material.

(57) Abr~g6 On ajoute de 1'acide urique ft ['aliment, AX raison de 5. 10000 .tg d'acide urique par g de mati~re sLche de 'aliment,.

A1 Protection of a food against oxidation 1 This invention relates to a process for the protection of a food against oxidation, to a food protected against oxidation and to the use. of uric acid in a food. I it is known that synthetic antioxidants; such as for example butyl hydroxytoluene (BHT) butyl hydroxyanisole (BHA) or propyl gallate (GPE) may be u-,ed to protect foods against oxidation.

suchIt is also known that so-called natural antioxidants, suhas extracts of spices, particularly rosemary, may be a 0 10 used to protect foods against oxidation. However, these antioxidants may be considered as chemical agents foreign ~.to the human organism.

In addition, it is known that uric acid present in the oa form of urate in human plasma probably plays an important par~t in the defence of the organism against reactions caused by oxidation phenomena.

However, it has never been proposed to use uric acid as 0 06 0such for the protection of foods against oxidation. This is because uric acid shows a certain solubility in water, but sees: 20 hardly any solu,bil:1ty in fats. Now, it is precisely the fatty component of foods which is susceptible to degradation by oxidation. It would appear that uric acid could only be used as an antioxidant for the protection of foods against oxidation in combination with an emulsifier. it would~ also appear necessary to synthesize a derivative of nucleic acid which would be soluble in fats. However, such a derivative might be in danger of incorporation within the human body.

The object of the present invention is to provide a process for the effective protection of a food against oxidation using a substance, which is neither a synthetic product nor a chemical agent foreign to the human organism arid from which the organism, is in hardly any danger of harm.

-2- 1 To this end, the process according to the invention is characterized in that uric acid is added to the food in a quantity of from 5 to 10,000 jig uric acid per g food dry matter. Similarly, the food protected against oxidat~.on by the process according, to the invention is characterized in that it contains from 5 to 10, 000 Lg of added uric acid per g dry matter.Finally, the presenlt invertioi also relates to the use of uric acid in a f ood, preferably in a quantity of from 5 to 10,000 'u.g uric a ,d per g dry matter, to protect it against oxidation.

It has been found that, surprisingly, uric acid lends itself as such to use as an antioxidant in foods and that it provides as such for the effective protection of foods against oxidation if used in the concentrations indicated.

This surprising effect is all the more valuable insofar as the ingestion of uric acid as such apparently has no effect on the urate level in humnan plasma, in contrast to the ingestion of nucleic aci :s which causes a rise in that level.

In the context of the present invention, the term 'foodtl is intended to be understood in a broad sense covering both food products intended for human consumption and fjods prepared on an industrial scale for consumption by animals, such as for example dogs, cats, poultry or cattle. Indeed, if uric acid is a useful, effective and harmless antioxidant 25 in the food products mentioned, it is all the more so in the foods mentioned for animals in view of its low cost and the ease with which it may be used in accordance with the present invention.

in the process or the use according to the invention, therefore, uric acid is added to a food or is preferably used in the foo5d in a qtuantity of from 5 to 10,000 vtg per-g food dry matter. If less than 5 4.g/g is used, the food is in danger of not being significantly protected against oxidation. If more than 10,000 i'g/g are added or used, the level of protection obtained may not be significantly S S

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-3 1 greater than that obtained by adding quantities within the range indicated. To carry out the process according to the invention, the uric acid may be used in the form of a fine powder or an aqneous solution. It is preferably used in the form of a salt in aqueous solution, more particularlY in the form of the sodium, po'v.assium or ammonium sa _lt. For use in this preferred form, a few percent uric acid may be dispersed in an aqueous solution of potassium, sodium or ammnonium hydroxide sufficiently concentrated to solubilize all the 10 uric acid dispersed.

The uric acid may be added to the food by thorough mixing with the food during or after its production. This presupposes that the food or its constituents are preferably in sub-divided, pasty or liquid form during or after 15 production.

Similarly, the food according to the present invention may be obtained by a process comprising a step in which uric acid in the form of a powder or solution is thoroughly mixed with a food product in sub-divided, pasty or liquid 20 form.

The food according to the invention preferably contains the uric acid in the form of its sodium, potassium or ammonium salt.

The above-mentioned thorough mixing step may take place, 25 for example, before or during t,-he extrusion phase of an extrusion cooking process of a food product in the form of a paste, for example to produce cocktail snacks, before drying during the cylinder drying of an aqueous suspension of food product, for example to produce dehydrated flakes, or during the homogenization phase of a process for the preparation of an emulsion, for example for parenteral use..

The following Examples are intended to illustrate the process, the product and the use according to the invention.

In the Examples, percentages or ratios are by weight, unless otherwise indicated.

S- 4 4 1 EXAMPLE 1 To prepare precooked dehydrated cereal flakes, grains of whole wheat are ground in a hammer mill the day before.

Three batches of an aqueous dispersion of 5 kg wheat flour in 20 kg water are prepared. One batch is kept additivefree for comparison. 1000 i.g uric acid per g flour are added with thorough stirring to the second batch and 2000 ig uric acid per g flour to the third batch after having formed a 5% dispersion of the uric acid in an approximately 10% potassium hydroxide solution and having waited for all the uric acid to be solubilized.

S• Each batch is heat-treated for 60 s at 130°C in a scraped-surface heat exchanger and then immediately dried for approximately 10 s on a dryer comprising two cylinders :9 15 heated with steam at 4 bar to a residual moisture content of 3.4 3.8%.

Three batches of cereal flakes are obtained and are subjected to an oxidation test carried out as follows: Oxidation test S" The cereal flakes are placed in lacquered sterilized 400 ml tinplate cans in a quantity of 40 g flakes per batch per can. The hermetically sealed cans are stored at 30 0

C.

I. 25 The head space of the cans containing samples of flakes of the three batches is analyzed after 1, 2 and 3 months by determining the pentane content, as the product of degradation of linoleic acid by oxidation, and the residual oxygen content. The pentane content is determined by gas-phase chromatography and the oxygen content by measurement of the paramagnetic susceptibility.

The results of this test are set out in the following Table: ~i 5 1 Strage time 1 month 2 months 3 months ne 0 2 pentane 02 pentane 02 -9 -9 -9 Samples 10 M 10 M 10 M Without uric 6.5 18 13 17 21.6 16 acid (comparison) With 1000 ug/g 5.9 19 13 19 18 18 uric acid With 2000 ug/g 4.3 19 8.3 18 14 18 uric acid 0

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i- It can be seen that, after storage for 1 month at the difference between the comparison sample and the samples containing uric acid is not significant. By contrast, after 2 and 3 months, the reduction in the production of pentane and in the consumption of oxygen as a result of the addition 20 of uric acid is very clear.

EXAMPLE 2 To prepare an emulsion of the parenteral emulsion type, 10% sunflower oil, 1% soya lecithin, 4% glucose and 25 85% water are mixed. The mixture is divided into several batches. One batch is kept additive-free for comparison.

200 4g propyl gallate (GPE) per g oil in the emulsion are added to a second batch, again for comparison. 1000 ug, 5000 yg and 10,000 ug uric acid per g oil in the emulsion 30 are added to third, fourth and fifth batches, respectively, after having formed a 5% dispersion of the uric acid in an appropximately 10% potassium hydroxide solution and having waited for all the uric acid to be solubilized.

Each batch is passed 15 times through a nozzle homogenizer. Five batches of emulsion are obtained and are 6- 1 subjected to an oxidation test carried out as follows: Oxidation test The emulsions are introduced into lacquered, sterilized 250 ml aluminium cans in .a quantity of 20 ml emulsion per batch per can. The hermetically sealed can's are stored at

C.

The head space of the cans containing emulsion samples of the five batches are analyzed after 10, 14, 28, 38 and 42 days by determining the pentane content and the ethane S' content, as respective degradation products of linoleic and e linolenic acids by oxidation, and the residual oxygen content.

I The pentane and ethane contents are determined by gas-phase chromatography and the oxygen content by measurement of the paramagnetic susceptibility.

The results of this test are shown in the following Tables:

ETHANE

l0-9 M Samples after days: 14 28 38 42 25 Without additive 4.54 6.05 19.4 23.1 25.3 (comparison) 200 ug/g GPE 1.73 2.16 2.27 2.27 2.59 (comparison) 1000 ug/g uric 4.54 4.87 5.40 5.83 5.83 acid 5000 ug/g uric 3.46 3.l8 4.11 4.21 4.32 acid 10,000 ug/g uric 2.16 2.59 2.80 2.80 4.54 acid 'p a uw& A/ty -7-

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Without additive (qcomparison) 200 v'Lg/g GPE 1o (comparison) 1000 lig/g uric acid 5000 jiig/g uric acid 10,000 ug/g uric acid 0.48 0.48 0.97 1.30 0.48 3.06 2.74 1.77 1.77 2.42 8.05 3.86 4.50 4.67 3.76 12 .4 6.77 8.06 9.10 6.36 17 .4 9.03 9.35 8.86 8.40 Samples after days: 14 28 381 42 Without additive 19.6 15.3 1.02 1.02 1.02 (comp a riso n) 200 GPE "d"0 .5 20.3 20.2 20.0 19.8 (comparison) 1000 4~g/g uric 19.8 19.8 19.5 19.2 19.0 acid 5000 14g/g uric 20.1 19.5 19.8 19.6 19.5 acid 10,000 jig/g uric 20.5 20.3 19.5 19.8 19.7 acid t -8 1 It can be seen that the production of ethane is virtually stopped from the 14th day of storage by the addition of uric acid and by the addition of GPE. The eduction in the production of ethane is already significant for a concentration of 1000 ug/g uric acid and makes relatively little progress for distinctly higher uric acid concentrations of 5000 and 10,000 ug/g.

The production of pentane is also significantly limited by the addition of uric acid.

10 Finally, the consumption of oxygen is suddenly interr *rupted between the 14th day and the 28th day by the addition of uric acid and by the addition of GPE.

EXAMPLE 3 S 15 To prepare a cat food, a dry mixture based on corn, wheat, soya flour, fish meal, chicken meal, salt, vitamins and trace elements is prepared. An aqueous dispersion based on fish pieces and liver is prepared.

:::The dry mixture is divided into four batches. 11 ug/g 0 of a dry mixture of antioxidants based on GPE and BHT is Sadded to the first batch for comparison. Uric acid is added to the second, third and fourth batches in quantities of 11 g/g, 33 ug/g and 99 ig/g, respectively.

ul/ml of a liquid preparation of antioxidants based S 25 on GPE and citric acid is added to the aqueous dispersion.

*eb 06 Each of tne four batches of dry mixture is moistened by addition of 4his aqueous dispersion, after which each of the four moistened mixtures is subjected to an extrusion cooking process. After cutting up into small pieces, the expanded products obtained are dried on issuing from the extruder. Four batches of dehydrated cat food are obtained.

Food samples of these four batches are stored at 36*C.

Using 18 cats, comparative feeding tests are carried out in pairs for 2 days after storage of the samples for 30, and 90 days at 36°C. The result of these tests shows that 11,A4/u~ 1--

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-9- 1 the cats have a distinct preference for the samples based on the dry mixture to which 33 4ig/g uric acid was added over the comparison samples based on th6 dry mixture to which 11 4g/g antioxidants based on GPE and BHT was added, By contrast, the samples -containing 11. vg/g and 99 4ig/g uric acid are enjoyed to the same extent as the 6omparison samples.

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Claims (5)

1. A process for t'a protection of a food against oxidation, characterized in that uric acid is added to the food in a quantity of from 5 to 10,000 pg uric acid per q food dry matter.

2. A process as claimed in Claim 1, characterized in o that the uric acid is added to the food in the form of the sodium, potassium or ammonium salt.

3. A food protected against oxidation, characterized in that it contains from 5 to 10,000 pg of added uric acid per g dry matter.

4. A food as claimed in Claim 3, characterized in that it contains uric acid in the form of the sodium, potassium or ammonium salt. A process for the protection of a food against oxidation as defined in Claim 1 and substantially as herein described with reference to any one of Examples 1 4 to 3. DATED this 19th day of SEPTEMBER 1990 SOCIETE DES PRODUITS NESTLE S.A. Attorney: WILLIAM S. LLOYD Fellow Institute of Patent Attorneys of Australia of SHELSTON WATERS i VH '"i ~r I INTERNATIONAL SEARCH REPORT I, PCT/CH87/00020 International Application No I. CLASSIFICATION OF SUBJECT MATTER (if several classlficton symbols apply, indicate all) According to International Patent Classification (IPC) or to both National Classincatlon and IPC Int.C. 4 A 23 L 3/34; A 23 K 1/16; A 23 K 3/00; A 61 K 47/00 II, FIELD SEARCHED Minimum Documentation Searched I Classification System Classification Symbols 4 Int.Cl1. A 23 L Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched 6 II., DOCUMENTS CONSIDERED TO BE RELEVANT Category I Citation of Document, 11 with Indication, where appropriate, of the relevant passages 2 I Relevant to Claim No, 13 X,Y FR, A, 2004476 (RALSTON P CO.) 28 November r1969, see claims 1,12,13,19; page 9, lines 10-25; page 21 table 6; example 6; age 5, lines 10-30 1-7 Y FSTA Journal no. 446, 1971, P.T. Gamage et al.: "Effects of linoleic acid hydroperodixdeS and their secondary products on the growth of tscherichia Coli",see abstract 71053340 IAgricultural and Biological Chemista-y, vol. no. 1, p. 33-39, 1971 1 CAhemical Abstracts vol. 68, 1968, (Columbus, Ohio, US), L. Poka et al. "The effect of iparenteral feeding on the postoperative protein metabolism see page 1912, abstract t 20054c, Nutr. Dieta 9 161-76 (1967) SSpecial categrles of cited documents: to I.ter document published alter the International fillin date op" A tiority date and not In conflict with the application but considefel'to be el particular relevance Invention earll t document but published on or after the International document of particular relevance; the claimed Invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority clalm(s) or Involve an Inventive step whichs ited t establish the publication da o anther Y" document of particular relevance' the claimed invention citation or other special reason (as specified) cannot be considered to Involve an inventive step when the document referring to an oral disclosure, use, exhibition or document Is combined with one or rMore other such docu- other means monts, such combination being obvltcus to a person skilled document published prior to the Internnai l fli lng date but In the art. later than the priority date claimed document nmember of the same patent family IV, CERTIFICATION Date of the Actual Completion of the international Search Date of Mailing of thl' International Search Repurt 28 July 1987 (28.07.87) 12 August 1987 (12.08.87) Internatlonal Searching Authority Slgnatle of Authorized Officer European Patent Office Iorm PCT/ISAi210 (second sheet) (January 1985) i -c _i L I~ -e dl INTERNATIONAL APPLICATION NO. PCT/QH 87/00020 (SA 16126) 1 This Annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 04/08/87 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Pacent document Publication Patent family Publication cited in search date member(s) date report FR-A- 2004476 28/11/69 NL-A- 6902727 24/09/69 DE-A- 1914418 23/10/69 GB-A- 1200583 29/07/70 GB-A- 1200582 29/07/70 CH-A- 527225 31/08/72 BE-A- 730276 01/09/69 US-A- 3830798 20/08/74 For more details about this annex see Official Journal of the European Patent Office, No. 12/82 44~ RAPPORT DE RECHERCHE INTERNATIONALE Demands Internationl@ N1 -P T rT g j o 1. CLASSEMENT DE LINVENTION (ai pluslours symboles de classification sont applicablei, leticldquer lous)? Solon Is cloasfication Internationale des brovet& (CIB) Cu A as foil solon lo classificationl nationa~l* of Ia CIE, CIB 4 :A 23 L 3/34; A 23 K 1/16;. A 23 K 3/00; A 61 K 47/00

11. DOMAINES SUN LESQUELS LA RECHERCHE A PORTE Documentaltion minimal. consult~oa Systime do clasllcolion ISymbole. do classification Document ationi consull~e autre ttue la documentat ion minlimal@ dans as mesure otO do lola documents font parfie des domalnes our loaquels In recherche a poril Ill, DOCUMENTS CONSIDitS COMME PERTINENTS t0 CtgreIdentification des documents citlisti1 avec Indication, at N, doevroyendlcatimna Caf~orledes passages per inertsa to ses 13 X,Y FR, A, 2004476 (RALSTON PURINA CO-) 28 novembre 1969, voir revendications 1-7 1,2,3,11,12,13,19; page 9, lignes 10-25; page 21, tableau 6; exemple 6; page 5, lignes 10-30 Y FSTA Journal, no. 446, 1971 P.T. Gamage et al.: "Effects of linoleic acid hydroperodixdes and their secondary products on the growth of Escherichia Coli"l, voir resunm6 710533401 Agricultural and Biological Chemistry, vol. 35, no. 1, p. 33-39, 1971 A Chemical Abstracts, volume 68, 1968, (Columbus, Ohio, US), L. Poka et al.: "The effect of parenteral feeding on the postoperative prqtein metabolism", voir page 1912, abr6g6 20054c, Nutr. -Dieta 161-76 (l 96 p *Cotigorios aAiclales do documernts cdIt 1 *To documenrt ullirieur publi# Poaldiauiomenth Alodale d* d~p6t 4x A* dcumnt dfinstat I* atg~nraldo s tehniuenonInternatiortal ou A Is date do Priorife of n-apparlonant pas *dcon dinla pantiu f6a VOWa oIatcnqe o 68 do Ia tachique Pertinet, mats cit16 pour comp dre conld~A cmmapallclirement pertinent II prIncips ou In tlitoris contituant Is base do linvnion E a docu ment antirlour, maia pul4liA A Is dale do d6p6t Interns. o ouetpriclheot ofnnf ivnlnrvni floral o ap~s cllo alequite no pout hitf conidile Comma nouvollo ou comma Lai documnn pouvanl lt un doute Sur Una revondicallon do Impliquant unto aclivitt Inventive prioiA ou cilk pour diforminer an data do publication d'une ev a document particulillromont Pertinent; l'invention revert. autr citation ou pour Una raison apilcials (follo qu'Indiqude) dluen otArocni1A omoIoiun n 00 0 document to rilirant A Uno divulgatlon orale, A un usage, Aactivitt Inventive loroque Is document est ass=6i A Uni ou Unaexositlion Cu tout autres moyons plusioursoautros documents do mime nature, cotta combi- a PP document p0b1i4 avent Is dale do dip~t Internationtal, prais nation 4tant hOldonlo Pour Un. porsonno du mtIler, postdriouremont A Is dale do prioritO revondiqu~e.o document Cut fall partle do Ia milmo famillo dos brevets IV, CERTIFICATION Dale b laquello Io recheorchre Internaltonal. a Wl electivement Dale deoxpidliort du preent rapport do recherchte Internationale achevde1 A S M 28 juillet 1987 12AUf Admirtistration chargie do Is rechierche Internatiortale Signature du lonctionnle rsl OFFICE EtJROPZEN DES BREVETS M. VAN MOL Formulalre PCTIISA12I0 (douslime feullo) (Jonve 1905) V ANNEXE AU RAPPORT DE RECHERCHE INTERNATIONALE RELATIF A LA DEMANDE INTERNATIONALE NO. PCT/CH 87/00020 (SA 16126) La pr~sente annexe indique les membres de l~a famille de brevets relatifs aux documents brevets cit6s dans le rapport de recherche international vis6 ci-dessus. Lesdits rnembres sont ceux contenus au fichier inforrnatique de l.'0ff4ice europ~en des brevets A la diate du 04/08/87 Les renseignements fournis sont donnv s iL titre in icatif et n'engagent pas l~a responsabilit6 de l'Office rop$en des brevets. Document brevet cit6 au rapport de recherche Date de publication Membre(s) de l~a famille de brevets Date de publication FR-A- 2004476 28/11/69 NL-A- 6902727 24/09/69 DE-A- 1914418 23/10/69 GB-A- 1200583 29/07/70 GB-A- 1200582 29/07/70 CU-A- 527225 31/08/72 BE-A- 730276 01/09/69 US-A- 3830798 20/08/74 Pour tout renseignement concernant cette annexe voir Journal Officiel de l'Office europeen des brevets, No. 12/82