DE102015103692A1 - Method for detecting honey adulteration - Google Patents

Method for detecting honey adulteration Download PDF

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DE102015103692A1
DE102015103692A1 DE102015103692.4A DE102015103692A DE102015103692A1 DE 102015103692 A1 DE102015103692 A1 DE 102015103692A1 DE 102015103692 A DE102015103692 A DE 102015103692A DE 102015103692 A1 DE102015103692 A1 DE 102015103692A1
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honey
psicosis
syrups
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fructose
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Bernd Kämpf
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Breitsamer & Ulrich & Co KG GmbH
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/02Food
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N2030/042Standards
    • G01N2030/047Standards external
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/8813Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample biological materials
    • G01N2030/8836Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample biological materials involving saccharides
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/8872Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample impurities
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/62Detectors specially adapted therefor
    • G01N30/74Optical detectors

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Abstract

Die Erfindung betrifft ein Verfahren zum Nachweis von Honigverfälschungen durch Fructose enthaltende Sirupe, wobei Psicose als Markersubstanz verwendet wird und eine Probe eines zu überprüfenden Honigs auf das Vorhandensein von Psicose untersucht wird.The invention relates to a method for detecting honey adulteration by fructose-containing syrups, wherein psicose is used as a marker substance and a sample of a honey to be tested for the presence of psicosis is examined.

Description

Die Erfindung betrifft ein Verfahren zum Nachweis von Honigverfälschungen.The invention relates to a method for detecting honey adulterants.

Honig als naturbelassenes Lebensmittel ist mittlerweile ein Produkt mit steigender Nachfrage, aber sinkendem Angebot und unterliegt somit weltweit einem starken Preisanstieg. Dies hat zur Folge, dass vermehrt Verfälschungen auf dem Markt auftauchen, wobei Honige derzeit vor allem mit verschiedensten billigen Sirupen gestreckt werden, um einerseits die Menge zu erhöhen und um dem steigenden Preisen entgegenzuwirken. Man hat daher bereits Messverfahren entwickelt, mit denen die Zumischung bestimmter Sirupe analytisch nachgewiesen werden können.Honey as a natural food is now a product with increasing demand, but falling supply and is thus subject to a sharp price increase worldwide. As a result, more and more adulterants appear in the market, with honey currently being stretched, especially with a variety of cheap syrups, on the one hand to increase the quantity and to counteract the rising prices. It has therefore already developed measuring methods with which the addition of certain syrups can be detected analytically.

Die meisten gängigen Analyseverfahren zum Nachweis von Honigverfälschungen beruhen auf Unregelmäßigkeiten im Zuckerspektrum. Zuletzt wurden daher Sirupe entwickelt, die bezüglich Ihres Zuckerspektrums dem natürlichen Zuckerspektrum des Honigs sehr nahe liegen, sodass derartige Verfälschungen anhand des Zuckerspektrums kaum mehr nachgewiesen werden können.Most common analysis methods for the detection of honey adulteration are based on irregularities in the sugar spectrum. Therefore, syrups have recently been developed that are very close in terms of their sugar spectrum to the natural sugar spectrum of honey, so that such distortions can hardly be detected on the basis of the sugar spectrum.

Der Erfindung liegt daher die Aufgabe zugrunde das Verfahren zum Nachweis von Honigverfälschungen zu verbessern, sodass insbesondere auch Verfälschungen mit Sirupen erkannt werden, die bezüglich Ihres Zuckerspektrums dem natürlichen Zuckerspektrum des Honigs sehr nahe liegen.The invention is therefore based on the object to improve the method for the detection of honey distortions, so that especially distortions with syrups are recognized, which are very close to the natural sugar spectrum of honey with respect to their sugar spectrum.

Erfindungsgemäß wird diese Aufgabe durch die Merkmale des Anspruches 1 gelöst. Vorteilhafte Ausgestaltungen des Verfahrens sind Gegenstand der weiteren Ansprüche.According to the invention, this object is solved by the features of claim 1. Advantageous embodiments of the method are the subject of the other claims.

Die erfindungsgemäße Lösung beruht auf dem Ansatz, etwaige Verfälschungen durch den Nachweis einer Markersubstanz zu erkennen. Dabei mussten geeignete Markersubstanzen gesucht werden, die entweder einen natürlichen Bestandteil der Edukte der Sirupe darstellen oder im Herstellungsprozess der Sirupgewinnung gebildet werden. Darüber hinaus muss ausgeschlossen werden, dass eine derartige Markersubstanz natürlicher Bestandteil des Honigs sein kann, da nur dann ein Nachweis einer bestimmten Markersubstanz eine Verfälschung aufzeigen kann. The solution according to the invention is based on the approach of recognizing any adulteration by the detection of a marker substance. In this case, suitable marker substances had to be searched for, which either represent a natural constituent of the educts of the syrups or are formed during the production process of the syrup production. In addition, it must be ruled out that such a marker substance can be a natural constituent of honey, since only then can a detection of a particular marker substance show a falsification.

Die Grundlage vieler Sirupe ist Mais, da Mais weltweit großflächig angebaut wird und enorme Erntemengen vorliegen. Im Produktionsprozess von Maissirupen wird die Maisstärke zu Saccharose, Fructose und Glucose umgesetzt, wobei auch die Saccharose zusätzlich noch zu Fructose und Glucose abgebaut werden kann. Diese sogenannten Maissirupe setzen sich nun hauptsächlich aus Fructose und Glucose und einem gewissen Anteil an Saccharose zusammen und haben damit ein ähnliches Zuckerspektrum wie Honig. Dieser günstigen Eigenschaft stehen nun trotzdem zwei Nachteile gegenüber, die einer Nutzung zur Verfälschung von Honig in großem Umfang entgegenstehen:

  • – Saccharose kann analytisch leicht nachgewiesen werden, da Saccharose in Honig natürlicherweise nur in sehr geringen Mengen vorkommt und daher ein Positivbefund von Saccharose eine Verfälschung anzeigt und
  • – ein hoher Anteil an Glucose, so wie er in diesen Sirupen vorliegt, eine schnelle Kristallisation des Produktes bedingt und somit zur Einmischung in Honig wenig geeignet ist.
The basis of many syrups is corn, as maize is cultivated on a large scale worldwide and there are enormous amounts of harvest. In the production process of corn syrups, the corn starch is converted to sucrose, fructose and glucose, whereby the sucrose can also be broken down into fructose and glucose. These so-called corn syrups are now composed mainly of fructose and glucose and a certain amount of sucrose and thus have a similar sugar spectrum as honey. Nevertheless, there are two disadvantages to this favorable property, which are contrary to use for the adulteration of honey on a large scale:
  • - sucrose can be easily detected analytically, since sucrose in honey occurs naturally only in very small quantities and therefore a positive finding of sucrose indicates a falsification and
  • - A high proportion of glucose, such as is present in these syrups, causes a rapid crystallization of the product and thus is not very suitable for mixing in honey.

Damit die Kristallisation des Sirups vermieden werden kann, wird die Glucose, die für die Kristallisation hauptsächlich verantwortlich ist, in einem weiteren Prozessschritt zu Fructose umgewandelt. Fructoselösungen haben die Eigenschaft, auch bei sehr hohen Konzentrationen an Fructose sehr lange flüssig zu bleiben. In order to avoid the crystallization of the syrup, the glucose, which is mainly responsible for the crystallization, is converted to fructose in a further process step. Fructose solutions have the property of remaining liquid for a very long time even at very high concentrations of fructose.

Derartige Fructosesirupe sind jedoch sehr aufwendig und damit teuer herzustellen, um sie direkt weiter zu vermarkten. Es werden daher Mischungen aus Fructosesirupen und Maissirupen hergestellt. Diese Lösungen werden als Hoch-Fructose-Mais-Sirupe (High-Fructose-Corn-Syrup, HFCS) bezeichnet und in verschiedensten Mischungsverhältnissen im Handel für die Lebensmittelindustrie angeboten. Ein derartiger Sirup eignet sich somit sehr gut um Honig zu verfälschen, da er flüssig ist und ein honigähnliches Zuckerspektrum aufweist.However, such fructose syrups are very expensive and therefore expensive to produce in order to market them directly. There are therefore prepared mixtures of fructose syrups and corn syrups. These solutions are referred to as high-fructose corn syrups (HFCS) and are available in a variety of compounding ratios for the food industry. Such a syrup is thus very good for falsifying honey, since it is liquid and has a honey-like sugar spectrum.

Die Verwendung von Psicose als Markersubstanz zum Nachweis von Honigverfälschungen beruht auf der Erkenntnis, dass sich im Produktionsprozess der Fructosesirupe, bei der Umwandlung der Glucose zu Fructose, der Monozucker Psicose bildet. Nachdem Psicose natürlicherweise in Honig nicht vorkommt, stellt Psicose somit eine Markersubstanz für Fructosesirupe und HFCS dar. Ein positiver Nachweis von Psicose in einer Honigprobe zeigt somit eine Verfälschung des Honigs mit einem Fructose enthaltenden Sirup und insbesondere auch mit HFCS an.The use of psicose as a marker substance for the detection of honey adulteration is based on the realization that in the production process the fructose syrup, in the conversion of glucose to fructose, forms the mono-sugar psicose. Since psicose does not naturally occur in honey, psicose is thus a marker substance for fructose syrups and HFCS. Positive detection of psicose in a honey sample thus indicates adulteration of the honey with a fructose-containing syrup and in particular also with HFCS.

Durch die Verwendung von Psicose als Markersubstanz liegt nun ein Verfahren vor, um den hohen Stellenwert von Honig, insbesondere in der europäischen Union, als unverfälschtes Produkt zu schützen.The use of psicose as a marker substance is now a procedure to protect the high value of honey, especially in the European Union, as an unadulterated product.

Der Nachweis von Psicose kann dabei qualitativ und/oder quantitativ erfolgen. Das Vorhandensein von Psicose wird zweckmäßigerweise mittels Flüssigkeitschromatographie untersucht, wobei insbesondere ein Lichtstreudetektor zur Anwendung kommen kann. Alternativ kann das Vorhandensein von Psicose auch mittels Kernspinresonanzspektroskopie untersucht werden.The detection of psicosis can be done qualitatively and / or quantitatively. The presence of psicosis is expediently investigated by means of liquid chromatography, wherein in particular a light scattering detector can be used. Alternatively, the presence of psicosis can also be studied by nuclear magnetic resonance spectroscopy.

Gemäß dem bevorzugten Analyseverfahren wird die Probe des zu überprüfenden Honigs bei der Untersuchung zunächst wässrig gelöst und anschließend zentrifugiert, wobei das Aliquot des Überstandes mittels Flüssigkeitschromatographie untersucht wird. Die chromatographische Trennung erfolgt vorzugsweise mittels eines Gradienten aus Wasser und Acetonitril durch eine Aminophase.According to the preferred method of analysis, the sample of honey to be tested is firstly dissolved in water on examination and then centrifuged, the aliquot of the supernatant being analyzed by liquid chromatography. The chromatographic separation is preferably carried out by means of a gradient of water and acetonitrile through an amino phase.

In der Zeichnung ist ein Chromatogramm einer Untersuchung einer Honigprobe mittels Flüssigkeitschromatographie gezeigt.The drawing shows a chromatogram of a study of a honey sample by liquid chromatography.

Der Peak bei etwa 10 min (Retentionszeit) verkörpert die Konzentration der Psicose. Zum Quantifizieren der Komponente „Psicose“ dienen die Höhe und die Fläche des Peaks. Im dargestellten Beispiel ergab sich ein Anteil von 0,5 Gew.-% Psicose in der untersuchten Honigprobe. Bei den der Erfindung zugrundeliegenden Versuchen hat sich ein Wert von ≥ 0,05 Gew.-% Psicose als positiv Befund herauskristallisiert.The peak at about 10 minutes (retention time) represents the concentration of psicosis. The height and area of the peak are used to quantify the component "Psicose". In the example shown, a proportion of 0.5% by weight of psicose was found in the honey sample investigated. In the experiments on which the invention is based, a value of ≥ 0.05% by weight of psicose has emerged as a positive finding.

Claims (7)

Verfahren zum Nachweis von Honigverfälschungen durch Fructose enthaltende Sirupe, dadurch gekennzeichnet, dass Psicose als Markersubstanz verwendet wird und eine Probe eines zu überprüfenden Honigs auf das Vorhandensein von Psicose untersucht wird.Method for detecting syrups containing fructose-containing syrups, characterized in that psicose is used as a marker substance and a sample of a honey to be tested for the presence of psicosis is examined. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass, ein qualitativer und/oder quantitativer Nachweis von Psicose durchgeführt wird.A method according to claim 1, characterized in that, a qualitative and / or quantitative detection of psicosis is performed. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass, das Vorhandensein von Psicose mittels Flüssigkeitschromatographie untersucht wird.A method according to claim 1, characterized in that the presence of psicosis is investigated by liquid chromatography. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass, das bei der Untersuchung mittels Flüssigkeitschromatographie ein Lichtstreudetektor zur Anwendung kommt.A method according to claim 3, characterized in that, in the examination by means of liquid chromatography, a light scattering detector is used. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass, das Vorhandensein von Psicose mittels Kernspinresonanzspektroskopie untersucht wird.A method according to claim 1, characterized in that, the presence of psicosis is examined by means of nuclear magnetic resonance spectroscopy. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass, das die Probe des zu überprüfenden Honigs bei der Untersuchung zunächst wässrig gelöst und anschließend zentrifugiert wird, wobei das Aliquot des Überstandes mittels Flüssigkeitschromatographie untersucht wird.A method according to claim 3, characterized in that the sample of the honey to be tested first dissolved in the study aqueous and then centrifuged, wherein the aliquot of the supernatant is analyzed by liquid chromatography. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass, das die Probe des zu überprüfenden Honigs mittels eines Gradienten aus Wasser und Acetonitril durch eine Aminophase chromatographisch getrennt wird.A method according to claim 6, characterized in that that the sample to be tested of the honey is chromatographically separated by an amino phase using a gradient of water and acetonitrile.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108181403A (en) * 2018-01-31 2018-06-19 安徽泓顺源生物科技有限公司 A kind of efficient liquid-phase chromatography method of rapidly quantifying honey quality
CN112285228A (en) * 2020-10-19 2021-01-29 秦皇岛海关技术中心 Method for identifying adulterated honey

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DONER, Landis W.; KUSHNIR, Irene; WHITE JR, Jonathan W. Assuring the quality of honey. Is it honey or syrup?. Analytical chemistry, 1979, 51. Jg., Nr. 2, S. 224A-232A. *
Honey: Quality criteria. In: Handbook of indices of food quality and authenticity / Rekha S. Singhal; Pushpa R. Kulkarni; Dinanath V. Rege. Cambridge : Woodhead, 1997 (Woodhead publishing series in food science and technology). Titelseite + S. 358-385. - ISBN 1-85573-299-8 *
HPLC Columns for Carbohydrates. SUPELCO. Product Specification.T494137B. Sigma-Aldrich Co., 1997. URL: https://www.sigmaaldrich.com/content/dam/sigma-aldrich/docs/Supelco/Product_Information_Sheet/4716.pdf [abgerufen am 12.11.2015]. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108181403A (en) * 2018-01-31 2018-06-19 安徽泓顺源生物科技有限公司 A kind of efficient liquid-phase chromatography method of rapidly quantifying honey quality
CN112285228A (en) * 2020-10-19 2021-01-29 秦皇岛海关技术中心 Method for identifying adulterated honey
CN112285228B (en) * 2020-10-19 2022-05-03 秦皇岛海关技术中心 Method for identifying adulterated honey

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