DE2423076A1 - METHOD FOR PROTECTING FOOD AGAINST INVALIDATION BY MICRO-ORGANISMS AND MEANS OF CARRYING OUT THE PROCEDURE - Google Patents

Description

DIPL.-IN6. DR. IUR. DIPL.-INS.

VOLKER BUSSE DIETRICH BUSSE

45 OSNABRÜCK _j May 10th 1974

MDSERSTRASSE 2O / 24 L / Th

Ivar Harry SANICK Uppa'kra, Lund, Sweden

Process for the protection of food against Infestation by microorganisms and means for carrying out the process

The invention relates to a method and a means for protecting edible or drinkable products which are susceptible to it Fungal, in particular mold, infestation and / or infestation are caused by putrefactive bacteria. For the sake of simplicity, such products are used in the following description and referred to as "food" in the claims. Such products include, in particular, meat or Fish products and those products mentioned that contain meat or fish in raw, semi-treated or · pretreated or treated condition, e.g. B. meat-containing patties, pastes or masses such as liver patties, ready-to-use Meat dishes and the like, pasta in a semi-prepared or fully prepared state, e.g. B. Wheat or rye bread, fruit of different types, e.g. B. tomatoes, citrus fruits, and the like. Products.

409849/0 801

It has long been known that many different spices have an inhibiting or killing effect on a large number of Exercise bacterial and / or fungal species. In trying to put this fact into practice for food preservation however, a number of difficulties have arisen to implement. One of these difficulties is that the spice or the seasoning, in order to exert an effective preservative effect, must be used in such amounts that the dated The limit set in the taste result is considerably exceeded.

Although the literature often provides contradicting information about the antibacterial and / or antifungal effects of various spices - and sometimes even completely inaccurate information - there is agreement that cinnamon aldehyde, which is found in cinnamon oils, among other things, has a considerable inhibitory effect on a number different fungi and different types of bacteria (cf. PM Ramadan et al, "On the Anti-Bacterial Effects of some Essential Oils" in Chem. Mikrobiol. Technol. Lebensm., Volume 1 (1972), page 96, and Clifton P. acrylic acid, HinsiehüLch the corresponding cinnamic or phenyl.. - Lord, Jr. & WJ Husa "Antimolding Agents for syrups" in J. Am Pharm Ass, Volume XLIII, No. 7 (Mon 195 ¹ O, pages 438). and their salts, the presence of an antibacterial effect is also determined and their use is proposed for the preservation of particular types of fruit and vegetables (US Pat. Nos. 2,790,717, 2,819,972 and 2,819,973).

409849/0801

acid and its salts, however, have a significantly weaker one Acts as cinnamaldehyde,

In practice, however, the use of cinnamaldehyde-containing Products used as preservatives are severely impaired by the fact that the preservative effect is often rapid decreases, not only when the product is stored, but also after it has been added to the material to be preserved has been.

The invention is primarily based on the object indicated To avoid drawbacks and to be both an effective and practical method of protecting food using cinnamaldehyde as an anti-microbial agent to create without this (with direct addition of the antimicrobial agent to the food) an undesirable Aromabzw. Changes in the taste of the food are brought about.

The invention is also based on the object of providing a cinnamaldehyde To provide containing agent for the protection of food against Eefall by microorganisms, in which the cinnamaldehyde a has improved storage stability.

Further features and advantages of the subject matter of the invention result from the claims and the following description.

409849/0801

The method according to the invention is characterized in that the food and / or foci of infection for an infestation. of the food through microorganisms (? .. B. walls in rooms in which the food is treated or stored, people who handle the food, work tools and machines as well as packaging materials for the food, etc.) with a "liquid cinnamaldehyde" and a "liquid onion product" in an amount sufficient to achieve a protective effect.

The term "liquid cinnamaldehyde" in this context means cinnamaldehyde as such or a liquid product suitable for addition to food and as essential Contains component cinnamaldehyde, this cinnamaldehyde obtained from plants or produced synthetically can. As an example of such products are commercially available cinnamon oils, z. B. Cassia oil, which is usually 75 to 90 percent by weight Contains cinnamaldehyde, and Ceylon cinnamon oil, which normally contains 55 to 70 percent by weight cinnamaldehyde, as well as these manufactured solutions containing cinnamaldehyde, especially solutions in ethyl alcohol, and corresponding synthetic solutions Cinnamaldehyde or emulsions in harmless liquids, e.g. B. water called.

The expression "Plüssig-onion product" is understood to mean a liquid product that contains such organic sulfur compounds as are found in many plant species as substances that produce a characteristic smell and taste or aroma.

409849/0801

Onions of the Allium genus of the Liliaceae family, in particular the spice and vegetable onion (Allium cepa) and garlic (Allium sativum), preferably the latter, are present. Such a liquid product can be a juice, an oil or an extract which is obtained from these onions by pressing, distilling or extraction, or a liquid onion product which is obtained from such a juice, oil or extract, e.g. B. is obtained by a concentration or fractionation process or by dilution or concentration reduction. This liquid onion product can also be a product that contains at least one of the characteristic, sulfur-containing flavoring substances mentioned in another way, e.g. B. in synthetic form contains. Examples of this are artificial plant onion aromas and flavors (essences that contain at least one organic sulfur compound of the type found in garlic or the spicy and vegetable onion, as well as at least one alkyl-S-, unsaturated alkyl-S- or -S (O) - Most commercially available artificial onion flavors are solutions of allyl sulfide, allyl disulfide or allyl propyl sulfide or mixtures thereof in a harmless solvent, usually a non-toxic alcohol, e.g. Such artificial, in most cases vegetable onion and cabbage essences can also contain the characteristic constituents of garlic oil representing sulfur compounds allicin (C ₃ H ₅ -S (O) -SC ₃ H ₅ , soluble in ethanol) and / or Alliin (C ₃ H ₅ -S (O) -CH ₂ -CH (NH ₂ ) -COOH,

- D ""

soluble in water, insoluble in ethanol), mixed if necessary with allyl sulfide and / or allyl disulfide and / or allyl propyl sulfide, contain. In addition to solutions in a harmless solvent, emulsions in a harmless liquid, above all water, or a liquid onion product containing organic sulfur compounds can be used of the type mentioned both in solution and in emulsion and optionally also in suspension. The expression "harmless" in connection with the solvent, the emulsion or suspension liquid means that the solvent or the liquid should be suitable for addition to food.

It has been found that by using a liquid onion product according to the above definition together with a liquid cinnamaldehyde according to the above definition a stabilization in the This ensures that the period during which the cinnamon 7 aldehyde remains effective with respect to microorganisms, especially fungi, is extended over the case in which cinnamaldehyde or common cinnamaldehyde-containing products be used for themselves.

This result is surprising because, although it is known, i.a. from H. DoId & A. Knapp "on the antibacterial effect of spices ", magazine for hygiene and infectious diseases, 128 (19 * 8), pages 696 to 706, that the essential oils that in the bulbs of plants of the Liliaceae-Farailfe, in particular

409849/0801

of garlic (Allium sativum), have a good antibacterial effect with respect to a number of types of bacteria, ₃ of which are not known to have any appreciable antifungal effect.

It has not been explained what the lack of stability is regarding the effect of cinnamaldehyde is due, and therefore it cannot be explained in what the actual The reason for the stabilization achieved here can be seen. In this context it should be mentioned that at least one of the commercially available Cinnamon oils, namely Ceylon cinnamon oil, contain very large amounts of eugenol, which as such has a bactericidal effect. It is also stated in the literature that the existing Eugenol stabilizes the cinnamaldehyde against the oxidation to cinnamic acid taking place at the lift. The in connection with the Invention carried out experiments show, however, that the antifungal Effect that can be achieved with such a cinnamon oil, which has a high eugenol content, is in no way noticeable Longer than other types of cinnamon oil with a corresponding eugenol content. The stabilization that comes with the liquid Onion product according to the present invention is achieved, can therefore not be compared with this well-known stabilization by means of eugenol, moreover, the effect is due to Use e.g. B. of garlic oil together with cinnamon oil with a high eugenol content can be achieved, somewhat less than with its use in conjunction with other common cinnamon oils. This may be explained by the condensation of the

A09849 / 0801

Cinnamaldehyde and eugenols. However, this is e.g. Z, just one hypothetical explanation. In this context, however, is to be determined j that, as observed in investigations made in connection with the invention, when eugenol (10 percent by weight) to which cinnamaldehyde is added, the mixture gradually increases as it is stored in an open, colorless glass container getting darker and darker. Such darkening does not occur under appropriate conditions when using garlic juice is added instead of eugenol. The gMche is the case when instead of garlic juice synthetically produced garlic essence (containing a mixture of allyl sulphide and allyl disulphide) is used, which is a corresponding one according to the ultraviolet photospectrographic method possesses a certain strength. In corresponding experiments with cinnamon oil (about $ 85 cinnamaldehyde) Corresponding behavior was observed.

In this context it should also be mentioned that laboratory tests carried out on ripe tomatoes stored at a temperature of + 20 ° C to investigate the antimicrobial effect showed that when these tomatoes were treated with a solution of 0.2 percent by volume of the above-mentioned mixture of cinnamon oil ( or cinnamaldehyde) and eugenol in ethyl alcohol a process of putrefaction of the tomatoes by fungi growing on them took place in the course of about 9 days. When the eugenol was replaced by garlic extract (or synthetic garlic spice) in the manner indicated, the shelf life of the treated tomatoes was extended to about 16 days. It is not possible to have this effect

409849/0801

- Q -

by treating the tomatoes only with cinnamaldehyde or only with garlic extract in the total concentration of the cinnamaldehyde and the garlic sulfur compounds of the mixture corresponding Concentrations to get.

The combined use of cinnamaldehyde and onion products according to the definition given is more effective than the usual Infestation of food by fungi and putrefactive bacteria, d. H. mainly fungi and bacteria of the genera Penicillium, Aspergillus, Mucor, Candida, Lactobacillus, Saccharomyces, Pseudomonas, Streptococcus, Rhizopus, Salmonella, Achromobacter, Escherichia, Bacillus, Proteus and Clostridium.

The liquid cinnamaldehyde and onion products can help treated or to be protected material or object either separately or simultaneously supplied in the form of a mixture will. There is no critical upper concentration limit for the active substance or substances in the for the Protection product used, and with regard to the lower concentrations it should be noted that they are not so low may be that without the use or consumption of an undesirably high amount of ballast material, mainly solvents or emulsion liquid, sufficient protective effect is no longer achieved. It goes without saying, however, that in the cases in which it is a question of adding the treatment substances directly to foodstuffs, the tendency is extremely high

409849/0801

add small amounts of the active substances or substances. ¹ Here , the even distribution of the active substances in or on the food and consequently their intimate contact with it is facilitated by the use of dilute solutions and / or emulsions or suspensions of the active substances. In practice, the cinnamaldehyde is expediently used in a solution, preferably in an ethyl alcohol solution, or in an emulsion in concentrations of from 0.001 to 1 percent by weight, preferably from 0.005 to 0.5 percent by weight. The active substance or substances of the onion product can expediently in a solution, preferably also in an ethyl alcohol solution, and / or in an emulsion in concentrations above C, 5 parts per million, preferably from 1 part per million to 100 parts per million, calculated as Allyl sulfide or allyl disulfide can be used.

As for the amount that should be added directly to the food, it may vary according to the type of food and the conditions to which it is exposed prior to consumption. It is possible to determine the appropriate amount in each individual case through tests, but in practice the rule can apply to mix in as much as possible in each individual case without causing an undesirable aroma or taste effect, whereby the desired protective effect is guaranteed . In most cases where the active substances are mixed with the food, amounts between 0.001 and 0.1 percent by weight are preferred

409849 / 08Q1

between 0.005 and 0.05 percent by weight, based on the cinnamaldehyde and between 0.0001 and 0.01 percent by weight with respect to the onion components, calculated as allyl sulfide or disulfide, sufficient. The mutual ratio of these active substances can vary within very large limits. This relationship can be calculated from the concentration ranges given above. ' A preferred ratio of cinnamaldehyde to onion ingredients in most use cases lies between

20: 1 and 10: 1. In several cases, e.g. B. To preserve fruits such as tomatoes, it is mostly only necessary to make a surface treatment of the food, which od by spraying, brushing, dipping. The like. Can be carried out. In these cases, the consideration of an undesirable aroma or taste effect is usually of secondary importance Significance, so that the active substances can optionally be added in higher concentrations. Such a surface treatment can also be used in cases other than the preservation of fruits or fruit, e.g. B. to Preserving meat patties such as liver patties and other ready-made or semi-finished meat dishes, sliced Bread in packs and the like In many cases it is convenient to include both cinnamaldehyde and the onion product in the food to mix in as well as to carry out a final surface treatment. This can e.g. in connection with the production of ready-made meat dishes such as meat pies or pastes.

409849/0801

To treat the microorganism sources of infection , ie the work tools, the packaging material _} the walls in work and storage rooms, etc., a Plüssig protective agent with a concentration according to the above information can be applied by spraying, brushing or in some other way. In these cases, the aspect of an undesirable aroma or taste effect plays an even less role, but there may be an upper limit for the amounts used from the point of view that an undesirably strong odor, e.g. B. in the work area is to be avoided.

A ready-made mixture of liquid cinnamaldehyde and liquid onion product, which is suitable for protective purposes, can expediently the active substances in the above mutual application relationship included. The liquid cinnamaldehyde and the liquid onion product can be used in one concentrated state with respect to the active substances as a mixture of the pure active substances or as a mixture the same are in a more or less diluted state, either ready for use or to be diluted before use. As indicated, the preferred diluent is ethyl alcohol, but others are also possible Alcohols e.g. B. propylene alcohol or glycerine to use. In practice, the mixture is preferably prepared by Cinnamaldehyde or commercially available cinnamon and onion oil, e.g. B. garlic oil, or onion extract, e.g. B. garlic extract, or synthetic onion spice, e.g. B. Garlic Essence, mixed

409849/0801

- 13 - 2A23076 Loss of respectively. Cinnamon oil Example 2: Cinnamaldehyde Example 3: Cinnamon oil 5 -compositions are will. Such a mixture can be about a long period of time good antifungal and antibacterial effect stored which the following compositions are called: garlic oil Garlic essence, which is essentially , Onion (A. cepa) oil 5 without precautionary measures and without the risk of will. Example 1: Ethyl alcohol ■ borrowed dissolved in ethyl alcohol Ethyl alcohol 1000 To explain such protective means Contains allyl sulfide as a seasoning, ml Ethyl alcohol 2 ml ml 1 ml 1000 "5 ml 3 ml 1000 ml ml ml

409849/0801

-ih-

2A23076

example k :

Cinnamaldehyde 2 ml

Vegetable onion essence, which is essentially allyl propyl sulfide dissolved in ethanol contains as a seasoning, 2 ml ethyl alcohol 1000 ml

Cassia oil containing about 805S cinnamaldehyde was used as cinnamon oil in Examples 1 and 3. As the garlic and onion oil, common oil produced by steam distillation of garlic and onion, respectively, was used. The garlic and vegetable herb essence used in Examples 2 and H had an active substance content of about 0.001 percent by weight.

After a storage time of thirteen months, the compositions given in the * examples showed no change with regard to their antifungal and antibacterial effectiveness. The compositions can match the food to be treated in any way, e.g. B. in the form of a spray or spray mist in a carrier gas, such as carbon dioxide, by immersion, Brushes or the like. Are added. For example, the compositions unfolded when used in practice related to the preparation of liver pate exhibited highly effective antifungal activity on the surfaces of those used in the experiments Liver patties in aluminum bowls brushed with the compositions. After the brushing process, lids were

409849/0801

placed on the bowls or forms and the pies were stored in a refrigerator at h to 6 ^{° C.} After twenty days, these pies were still completely free of mold, even though they were taken out of the refrigerator and the lid removed every day to photograph the contents of the bowls. Corresponding untreated pies showed some mold colonies already after seven days and were completely overgrown with these after fourteen days.

Laboratory tests in which Plüssig cinnamaldehyde and a liquid garlic product, Each applied separately, compared with mixtures thereof, showed the following results

The substances used for the tests are specified in more detail below.

A. Cinnamaldehyde 99-100 weight percent, purchased October 17, 1970, container opened September 22, 1971 in connection with some experiments. On March 25, 197 ¹ "a solution in ethyl alcohol of 0.1 percent by weight of cinnamic aldehyde from this stock was made for the implementation of the things mentioned attempts.

B. Garlic Essence (synthetic); consisting of 0.001 percent by weight of an allyl sulfide derivative consisting essentially of consisted of a solution of allyl disulfide in ethyl alcohol.

C. Garlic extract made by fresh extraction

409849/0801

- Ib -

Garlic, with ethyl alcohol in the ratio of 10g garlic to 1000 ml ethyl alcohol.

D. Mix of equal parts of A (the 0.1 weight percent solution) and B.

E. Mixture of equal parts of A (the 0.! - weight percent

Solution) and C.

F. Mix equal parts of a 0.1 weight percent solution of cinnamaldehyde A in ethyl alcohol and B; Storage of this mixture in a container from September 22, 1971.

The test procedure is described below.

The experiments were carried out according to the "disk method" with round paper filter disks of 12 mm diameter and by determining the horizontal degree of diffusion of the spices examined on malt extract peptone agar agar which was poured into 9.5 cm Petri dishes. Before the experiments, each dish was brushed with 0.1 ml of a microbial suspension, which was then allowed to dry for about 5 minutes. These microbes suspension was obtained by applying a drop of distilled water was poured onto the apex of a carrot, the purchased one from a retailer, ¹ IOO g carrots containing plastic beut el was taken. From this drop, which always has a great variety

409849/0801

Containing microorganisms of the type mentioned above, three platinum loops of the suspension to 10 ml of a physiological Saline was transferred and the resulting suspension was used to inoculate the dishes. On each of the oculated Three pieces of paper filter round disks of the type indicated above were placed with the same mutual spacing of three bowls two of which were impregnated with one of the products A to F and the third was only impregnated with ethyl alcohol as a reference substance. Impregnation was achieved by immersing the circular disks in the various liquids until they were saturated were and 60 see. Allow to dry before placing them on the Maize Extract Peptone-Agar-Agar-Substrate were laid. The substrate dishes were then incubated for 48 hours at + 28 ° C. In each experiment four dishes were used to determine the degree of diffusion used.

Reading the degree of diffusion of the various for which Tests used products A-F was carried out by radial measurement of the ring surrounding the circular disks, the was free of colonies upon visual inspection. In each experiment, the average of the eight round disks was calculated. The results can be specified as follows:

409849/0801

- 18 - product 2423076 description Cinnamaldehyde Degree of diffusion
in mrn A. Garlic essence ^ l . B. Garlic extract " ¹ ^" ¹ 1 C. Cinnamaldehyde +
Garlic essence D. Cinnamaldehyde +
Garlic extract - = 12 E. ~ = 2

P. cinnamaldehyde +

Garlic essence

Regarding the results, it should be noted that the results for both D and Ξ are higher than the results for A, B, and C could be expected. The result of P shows that the effect of cinnamaldehyde is better maintained, if it is fresh at the time of adding the garlic product than if such adding at a later time Time "occurs when the cinnamaldehyde is stored for a long period of time after it has been exposed to the atmosphere has been.

4 09849/0801

Claims (10)

Patent claims: 1. . Method for protecting food against attack by microorganisms, characterized in that the food and / or sources of infection for an infestation of the food by microorganisms with a liquid zirataldehyde and a liquid onion product in a protective effect sufficient amount to be treated. 2. The method according to claim 1, characterized in that a product is used as the liquid onion product, the sulfur-containing essential oil of, plant bulbs of the Allium genus in particular the spiced and vegetable onion (Allium cepa) or garlic (Allium sativum), preferably the latter. 3. The method according to claim 1, characterized in that an artificial onion spice is used as the liquid onion product is used, which contains at least one organic sulfur compound of the kind found in the spice and vegetable onion or in the Garlic occurs and which has at least one alkyl-S- or unsaturated Alkyl-S- or -S (O) group, preferably an allyl-S- or AlIyI-S (O) group. 4. The method according to claim 3, characterized in that an artificial onion spice is used, which is known as Main seasoning component allyl sulfide, allyl propyl sulfide, allyl disulfide or allicin or alliin or a mixture of two or more 409849/0801 these substances in solution in a harmless solvent, such as ethyl alcohol or propylene glycol, and / or in an emulsion and / or suspension in a harmless liquid contains. 5. The method according to any one of claims 1 to 4, characterized in that that as liquid cinnamaldehyde this as such or a cinnamon oil, such as cassia oil, or a solution or emulsion of Cinnamaldehyde or cinnamon oil is used in a harmless solvent, preferably ethyl alcohol, or a harmless emulsion liquid. 6. Means for performing the method according to one of the claims 1 to 5 »characterized in that it is preferably a liquid cinnamaldehyde mixed with a liquid onion product in solution in a harmless solvent such as ethyl alcohol, or in an emulsion or suspension in a harmless one Contains emulsion or suspension liquid. 7. Means according to claim 6, characterized in that the onion product consists of a sulfur-containing essential oil, that from plant bulbs of the Allium genus, especially the spice and vegetable onions (Allium cepa) or garlic (Allium sativum), preferably the latter, is extracted. 8. Composition according to claim 6, characterized in that the onion product has at least one organic sulfur compound 409849/0801 of the kind that occurs in the spiced and vegetable onions or in garlic and which contains at least one alkyl-S- or unsaturated Alkyl-S- or -S (O) group, - preferably at least one Allyl-S or AlIyI-S (O) group contains. 9. Composition according to claim 6, characterized in that the ZwieToelerzeugnis essentially allyl sulfide, allyl propyl sulfide, Contains allyl disulfide or allizine or alliin or a mixture of two or more of these substances. 10. Agent according to one of claims 6 to 9, characterized in that that the cinnamedehyde as such or in the form of cinnamon oil, such as cassia oil, is present. 409849/0801 originally inspected