博士保罗·洛曼(Paul Lohmann Gmbh)

假矿物质盐 - 很棒的发现还是很棒的欺诈?

大众媒体受到“虚假新闻”的威胁,但是食品行业也出现了另一个话题:“假矿物”。This is a form of food fraud and more specially: “ingredient fraud”, which is essentially the fraudulent replacement of an original (more expensive) raw material with a less expensive one, without the purchaser’s knowledge, for economic profits or competitiveness in the market. Adulteration and fraudulence of ingredients are global concerns for stakeholders, industries, risk assessors and consumers. The issue of food fraudulence is a current world-wide concern. There has been a massive increase in the number of cases that range from horsemeat in lasagne to melamine in infant formula. Less well known, is the fact that individual ingredients in foods or dietary supplements, that claim to be in the product for beneficial health reasons, can also be “faked”. In the world of food fraud, Mineral Salt adulteration is one act of defrauding buyers, product developers and in the end consumers for economic gain. Mainly organic Mineral Salts such as Citrates, Lactates, Gluconates, Bisglycinates and many more are adulterated and in focus to be replaced by using all kinds of substances – mainly cheap and inactive. Instead of using fully reacted pure Mineral Salts, food or food supplement producers end up in processing unreacted compounds of inorganic substances such as Oxides, Carbonates or others. This can lead to uncontrolled impurity profiles, formulation stability problems or misbranded and finally adulterated products without the positive effect of fully reacted Mineral Salts like a good bioavailability and less side effects. Fully reacted Mineral Salts have genuine health benefits. The practice of substituting fully reacted organic Mineral Salts with unreacted blends has the potential to prevent individuals consuming these products for health reasons and from receiving the benefits they are in fact seeking. Fraudulent products that have been adulterated from their pure form will not show the same functionality in the body and would not show the same positive attributes as evidenced in scientific studies. Meanwhile, unknown reactions in the body may take place. The body is used as reaction vessel as the reaction of e.g. Magnesium Carbonate in combination with citric acid leads to the formation of Magnesium Citrate in the stomach. The absorption of valuable components might be strongly reduced. Any product subject to adulteration does not meet health requirements beneficial to customers and certainly will not withstand the standards of the manufacturer distributing final products. Moreover, uncontrolled impurity profiles due to raw materials that are contaminated with e.g. heavy metals might occur. In the case of chemically synthetically manufactured products that are fully reacted, purification processes are used to remove any undesirable substances.

完全反应的矿物质盐

√高纯度

√真正的健康益处

√高生物利用度

√更少的副作用假矿物质盐

√不受控制的杂质概况

√低吸收

√配方稳定性问题

√品牌和掺假的最终产品不正确

监管状况

矿物质盐用于食品补充剂是食品法中最复杂的主题之一。在欧洲,在美国以及亚洲遵守食品法规定的规定,都由主管监督当局监督。尽管最终产品必须在地方当局注册,但仅随机检查它们。制造商负责其产品的安全和正确声明;但是,缺乏许多广泛使用的矿物质盐的发表专着使买家,产品开发商和质量部门想知道他们购买的产品是否确实很安全。这些不可靠的做法继续对化学制造过程产生不确定性,并且太多怀疑所需的产品是否实际上是完全反应的有机矿物质盐。

制造过程

高纯度完全反应的有机矿物盐对人体具有高度生物利用。它们通常是由化学反应制造的,其中酸和碱性矿物质源在水溶液中反应。完全反应的结果是形成了高度纯且完全反应的盐化合物。该过程是一种所谓的中和反应,在该反应中,强酸和坚固的碱基相互抵消,并获得具有7个pH值的中性溶液。这就是为什么大多数完全反应的矿物质盐具有相当中性的pH值的原因。另一方面,这与表现出酸性或碱性pH值的干燥混合物形成对比。(请参阅表1)

标签。1:完全反应有机盐及其pH值的矿物质含量的例子

只能通过使用复杂的制造过程来确保生产过程中纯化的可能性以及最终有机盐的明确定义结构。在这种情况下,净化过程包括消除诸如重金属,采矿,异物等的残留物等杂质。对于每个元素,个体杂质都是特征的:镁通常伴有镍,而锌则与铅和镉发生。此外,BOB线上娱乐铁盐通常伴有各种重金属,纯化步骤至关重要。

©Paul Lohmann博士

矿物质盐的例子和缺陷“假货”

例如,完全反应的三膜酸酯显示了几乎中性的pH值。一种证明未反应矿物基碱的简单方法是添加酸。与碳酸盐或氧化物混合的产品将产生冒泡反应。许多氧化物本质上含有碳酸盐残基。例如,这些碱性成分可以与任何酸性成分反应并产生CO2。未反应的混合物会引起其他无法控制和不可预见的反应。由于最终产品配方中的反应缓慢但持续的反应,未反应盐的混合物可能不稳定。这种反应还可以导致粉末配方蛋白粉或爆发/突发的水泡包装,并带有瓦片的片剂。这些碱性物质也可以与制剂中的其他物质反应,例如维生素C或引起不可预测的放热反应。 Decomposed mixtures could even comprise hazardous, corrosive substances. In liquid applications, like beverages, an adulterated/blended product might not show the solubility of a fully reacted Mineral Salt. It might dissolve in an inappropriate time or even become sedimentary, thereby damaging the integrity of the final product being sold and consumed. Formulations that contain blends of mineral ingredients may have inappropriate or misleading ingredient labelling. In the case of Trimagnesium Dicitrate, one should become conscientious when purchasing a product with a content of 20% Magnesium. Due to the stoichiometry of a fully reacted Magnesium Citrate it can only offer a maximum of 16% Magnesium in the anhydrous form. Even with the best drying capabilities, a higher Magnesium content cannot be achieved. Therefore, products claiming a higher mineral content are blends and should be labelled in the ingredients lists accordingly e.g. Magnesium Citrate and Magnesium Oxide/Magnesium Carbonate. Another example is a “chelated taste free Iron Salt”, which sounds like the perfect solution for any application where taste and bioavailability are required. Unfortunately, this is not possible. Chelated Mineral Salts are fully reacted complex molecules. In the case of Bisglycinates they are Salts of the endogenous amino acid glycine. They bind the glycine directly through a highly sophisticated chemical manufacturing process in the presence of citric acid until they are fully reacted: meaning that a bonding has been formed in the complex between the mineral ion and its ligands. The chelate structure has a positive effect on the solubility, which improves the bioavailability of this organic compound.[1,2] Moreover, the amino acid chelate is only digested in the intestine, which optimizes the absorption.[3] Most chelated Minerals have a strong (often negative) taste impression. In case of chelated Iron they even leave a metallic taste in the mouth. It is apparent that products claiming to be tasteless like a “taste free Iron Bisglycinate” are blends of unreactive salts. When taking a closer look to those products one can recognize that, a reddish material, which shows high magnetic properties, cannot be a fully reacted Ferrous Bisglycinate with a typically greenish-brown colour and without any magnetic characteristics. This would rather be a blend of Iron(III) Oxide and Iron powder and the amino acid glycine. Analysis is tricky in this case because it is possible to find Fe(II) when doing a wet-chemical analysis even though the ingredients of the blend are entirely unreactive. Another example could be Magnesium Taurinate that has been used rather rarely so far. It is permitted for the use in food supplements in Europe.[4] It features a bioavailable source of Magnesium combined with the natural body constituent taurate, which most customers know as core ingredient in “energy drinks” (taurine, a naturally occurring beta-amino acid). However, there are products on the market which are only dry blends of Magnesium Oxide and taurine. Apart from the fact that the alleged fully reacted material is not soluble a more detailed examination, for example with a complementing combination of two methods like an elemental and structural analysis (by using XRD and EDX on the electron microscope), can be used to identify the material. In the qualitative analysis of the surface of solid or powdery materials, the Energy Dispersive spectroscopy by X-rays (EDX) is used to identify the elements. In SEM (Scanning Electron Microscope) pictures a heterogeneous structure provides the first hint on an unreacted compound. The SEM picture (see fig.2) of the fake Mineral shows smooth, large taurine crystals and then the small, composite Magnesium Oxide particles. The fake taurinate does not have a uniform crystal structure, which also affects its physical properties such as solubility. The taurine can go into solution, while the Magnesium Oxide remains undissolved. A fully reacted Magnesium Taurinate in turn would show a homogeneous structure due to the wet-chemical production process that is necessary. Furthermore, the X-Ray Diffraction (XRD) gives information on the identity of a crystalline substance. Compared with the X-ray diffractograms of single ingredients one will see if the material is a compound of pure taurine and e.g. Magnesium oxide or a fully reacted Magnesium Taurinate. There are several other ways to differentiate between a fully reacted Mineral Salt and a blend of reactants or fraudulent Mineral Salts. Precise analytical detection methods like chemo metric data analysis as well as simple sensory evaluations, electron microscopy for crystal structure analysis, thermogravimetric analysis or even x-ray diffraction can help to detect fraudulent Mineral Salts.

图2

进一步的检测方法

一种简单且非常有明显的识别方法,表征和结构阐明是红外光谱。为了区分完全反应的矿物质盐和反应物红外射线(波长约800nm-1mm)的混合物,插入要测试的材料中,并使单个分子振动。某些波长被材料吸收;反过来,这是作为吸收带的成像。红外光谱就像分子的“指纹”一样,是研究分子的特征。该方法可以确保完全反应的矿物质盐具有正确的分子结构。NMR(核磁共振)光谱拷贝是分析和鉴定物质以及主要是有机化合物的结构表征的一种非常强大的方法。它基于在外部强磁场的影响下磁性原子核的不同行为。例如,使用NMR光谱法来确保所示化合物实际上是感兴趣的实质。NMR光谱映射分子的“指纹”。 The NMR profile of Lysine HCI in comparison to Magnesium Bislysinate HCI show a shift of approx. 6 ppm the first C atom from 175 ppm for the free amino acid Lysine HCI to 181 ppm for the fully reacted Magesium Bislysinate. The same observation can be made for the comparison of Glycine vs. Magnesium Bisglycinate. The shift is from 179 ppm for the free amino acid Glycine to 173 ppm for the fully reacted Magnesium Bisglycinate. In both cases the second C atom remains unaffected.

标签。与双甘油镁HCl相比,赖氨酸HCl的2 NMR曲线

标签。与双甘氨酸镁相比,甘氨酸的3 NMR曲线

可比较的产品

对标签和包装的细致检查是揭露欺诈的另一种方法。如果似乎没有什么尚不清楚或误导性,食品企业主应该提出问题,如果没有保证,他们不应购买食材。允许在食品或饮食补充剂中使用的合法矿物质盐将经过广泛研究的地方当局批准,包括生物利用度和毒理学特征证明。在欧洲,例如EFSA(欧洲食品安全局)进行了安全评估,以评估消费者的原材料的安全性。矿物质盐通常由相关的质量描述(例如药典或电子数字)明确定义。这些参数应在制造商的产品规范中找到(通常列出了诸如“身份”,“测定”,“ pH”之类的参数):规格中列出的参数应针对每个生产批次进行相应分析。正常范围内的任何东西都应该是可疑的。仍然在某些情况下,如果参数“身份”或“测定”适合所需的材料,专家发现很难检查它是否是假的 - 最好的方法可以证明它是否确实是完全反应的有机矿物质盐将取决于所使用的分析方法(如上所述)。 Very helpful can be the comparison of a product with a reliable product that is already sold on the market.

价格

购买食材时,食物链上的所有买家也应尽职尽责,如果提供远低于正常成本价格的产品,则可能是可疑的。即使他们非常确定当前供应商的选择,也应该毫不犹豫地批判性地质疑出售给他们的产品的合法性。买方应避免以固定价格购买劣质或混合商品,以便尽可能便宜地购买产品。

打击矿物质盐掺假

尽管有公共数据库编译有关食品欺诈的报告,但没有矿物质盐等成分的工具。购买原材料时,食品补充剂的生产者应使用良好的判断力。不幸的是,没有可用的教育资源,也没有针对这些产品的质量保证和安全的指导。食物欺诈的发现并不容易,尤其是在矿物质盐掺假的情况下。那么,哪些工具可以阻止欺诈者或早日发现欺诈性盐?

与建立食品标准的专业生产商的合作关系

为了保持产品的完整性,应该依靠与原材料制造商的合作伙伴关系而不是纯交易活动。具有广泛专业知识的生产者,可以处理可信赖资源的原材料以及对生产公开和透明的策略的策略,将使自己与行业中的欺诈者区分开来。自2017年发布的GFSI(全球食品安全计划)的所谓基准测试要求以来,对于所有GFSI批准的食品安全标准都必须包括在2017年发布的针对食品欺诈的明确要求。[5,6]这适用于这适用IFS标准以及BRC或FSSC 22000,这是食品制造商用于防止食品欺诈的系统。监督,信息和沟通对于消除食品欺诈的生产和有益系统至关重要。中心要素是危害分析和风险评估实施。

很棒的发现还是很棒的欺诈?

尽管现有的产品欺诈计划一直集中在食品,食品补充剂和药物上,但很少关注成分欺诈的新,复杂和跨学科的线索。掺假的矿物质盐的流行率是支持积极预防方法的必要性证据,并更加专注于监管和监督。目前尚不存在有关已知有问题的矿物质盐和检测方法的全面汇编。因此,对于消费者,制造商,零售商和当局而言,掺假问题将继续存在。由于全球化和商品流以及伪造的创造性形式和新的分析证明方法的分裂,矿物质盐的掺假仍然是行业挑战,即使行业和消费者越来越多地要求在采购和标签方面更加透明度。不幸的是,只要食品和食品补品行业继续主要在价格上竞争,某些公司将继续破坏其产品以削弱其竞争对手。掺假似乎是削减利润成本的一种方法,因为它提供了令人惊讶的便宜产品和替代品。掺假给供应商和消费者带来许多严重和长期的风险和后果。如果不受监管,它有可能超越合法资源,并最终在全球范围内造成健康和安全问题。PaulLohmann®博士是全球领先的制造商和高价值矿物质盐的提供商,用于食品,营养补充和制药行业。 Since 1886, a high level of flexibility and an innovative spirit enables Dr. Paul Lohmann® to respond to changing needs. Customers can profit from the broadest available portfolio of high value Minerals, with more than 400 products in a range of qualities, designed to provide optimum performance across a wide range of applications. In the GMP and FSSC 22000 certified facilities, Mineral Salts are produced at quality levels stipulated by pharmacopoeias, regulatory food guidelines or tailored according to customers’ specifications. Dr. Paul Lohmann® also carries out product and application development in close cooperation with customers. This includes the adaptation of chemical and physical parameters such as bulk density, wettability, particle size, purity or pH-value.

参考:

1 Ferrari,P.,Nicolini,A.,Manca,M.L.,Rossi,G.,Anselmi,L.,Conte,M.癌症患者中轻度非化学疗法诱导的铁缺乏症的治疗:口服双甘Glycinate螯合物和硫酸亚铁之间的比较。生物医学和药物治疗,66(6),414-418。

2 Name,J.J.,Vasconcelos,A。R.,Maluf,V。R.和Cristina,M。(2018)。双甘氨酸铁螯合物和聚合蛋白铁可用于治疗铁缺乏贫血:试验随机试验。当前的儿科评论,14(4),261-268。

3 Bagna,R.,Spada,E.,Mazzone,R.,Saracco,P.,Boetti,T.,Cester,E。A.,…&Coscia,A。(2018年)。与早产儿中双甘氨酸螯合物相比,硫酸铁补充的功效。当前的儿科评论,14(2),123-129。

4欧洲议会的2002/46/EC指令和2002年6月10日的理事会有关成员国法律与食品补充有关的法律的近似

5https://mygfsi.com/press_releases/gfsi-releases-new-edition-new-edition-of-benching-requirements/

6https://mygfsi.com/press_releases/version-7-1-of-gfsis-benchmarking-requirements-furthering-harmonisation/

保罗·洛曼(Paul Lohmann)Gmbh&Co。KGAA

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31860 Emmerthal/Germany

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