Detection of 4-aminocarminic acid in beverages and cake glaze from the German market: a food additive not approved in the EU

In the European Union, carminic acid and its ammonium, calcium, potassium or sodium salts and its aluminium lakes are approved as food additive E120. In beverages obtained from the German market 4-aminocarminic acid (“acid-stable carmine”) was detected by HPLC–PDA and LC–MS/MS. Isolation of the colorant from a liquid dye preparation used for the production of a beverage sample and subsequent NMR analysis confirmed the presence of 4-aminocarminic acid. Synthesis of ¹⁵N-4-aminocarminic acid clearly demonstrated that “acid-stable carmine” is not the ammonium salt of carminic acid, which is approved as food additive in the European Union. In fact, nitrogen in “acid-stable carmine” is covalently bound. The molecular structure of carminic acid is chemically modified and 4-aminocarminic acid does not comply with the specifications laid down for E120 in Commission Regulation (EU) No 231/2012. 4-Aminocarminic acid was also detected in the red-colored glaze of a raspberry cake and in the liquid dye preparation used for coloring this glaze.     

Structure of acid-stable carmine

Acid-stable carmine has recently been distributed in the U.S. market because of its good acid stability, but it is not permitted in Japan. We analyzed and determined the structure of the major pigment in acid-stable carmine, in order to establish an analytical method for it. Carminic acid was transformed into a different type of pigment, named acid-stable carmine, through amination when heated in ammonia solution. The features of the structure were clarified using a model compound, purpurin, in which the orientation of hydroxyl groups on the A ring of the anthraquinone skeleton is the same as that of carminic acid. By spectroscopic means and the synthesis of acid-stable carmine and purpurin derivatives, the structure of the major pigment in acid-stable carmine was established as 4-aminocarminic acid, a novel compound.     

红花红色素研究进展

从红花提取红色素是一种安全天然食用色素,可作为食品添加剂和化妆品染色剂等,在功能性食品和医药领域有非常广阔发展前景。该文综述红花红色素化学组成、分子结构、功效特性、提取及检测方法,探讨生产过程中酶法转化作用,为红花红色素研究开发提供依据。     

Al3+荧光增敏快速检测酸奶和乳酸菌饮料中的胭脂虫红酸（英文）

研究溶剂、浓度、pH值以及金属离子对胭脂虫红酸荧光性能的影响,表明胭脂虫红酸在pH 4且其物质的量浓度为2.0×10^-4 mol/L的水溶液中荧光最强;而胭脂虫红酸对金属离子选择性识别的结果显示,Al^3+能使胭脂虫红酸的荧光强度显著增强从而提高检测的灵敏度。以Al^3+(2.0×10^-3 mol/L)为标准溶液检测样品中胭脂虫红酸含量时,胭脂虫红酸的物质的量浓度在1.0×10^-5~8.0×10^-5 mol/L范围内与其荧光强度呈良好的线性关系,检测限为5.0×10^-6 mol/L。实际应用结果表明,用荧光法检测不同酸奶和乳酸菌饮料中添加的胭脂虫红酸的含量,样品回收率在96.6%~110.5%之间,相对标准偏差小于5.9%。本研究为快速、有效、定量地检测食品中的胭脂虫红酸提供了一种有效的方法。     

Stability of Anthocyanins from Sweet Potatoes in a Model Beverage

Model beverages containing a citrate-phosphate buffer at pH 2.8, 13% sucrose, and a colorant were stored at room temperature for 1 yr in the dark. The colorants consisted of pigment extracts from red sweet potatoes, the same extract with the acyl groups removed, cyanidin-3-glucoside from blackberries, and a commercial sample of enocyanin from grapes. The sweet potato pigments were the most stable, closely followed by those from blackberries. The deacylated samples and those containing enocyanin were much less stable, as judged by color measurements and pigment analyses.     

Structure determination of minor red pigment in carthamus red colorant isolated by preparative LC/MS.

Carthamin is a well-known major pigment in carthamus red colourant. When analysed by HPLC on an ODS column, the colorant separated into two distinct reddish pigments, with both components having almost identical photodiode array spectra. LC/MS analysis suggested one of the compounds was carthamin, whilst the other was an unknown minor pigment. The minor pigment was purified and isolated from the colorant by preparative LC/MS collecting the faction based on monitoring the deprotonated molecule [M-H](-) m/z 953 in electrospray negative-ion mode. The structure was elucidated as a hydroxyethyl ether of carthamin, a novel compound, by means of NMR and HR-FAB-MS analyses.     

Retrospective analysis for the identification of 4-aminocarminic acid photo-degradation products in beverages

This article deals with the identification of the photo-degradation products of 4-aminocarminic acid potentially present in commercial beverages. Sixteen beverages of different composition but all containing the E120 dye were previously analysed by ultra-high-performance liquid chromatography (UHPLC) coupled with quadrupole-time of flight mass spectrometry to identify the common degradation products of the E120 dye. Since it is plausible to find unauthorised 4-aminocarminic acid in beverages which report generic E120 dye on the label, retrospective analysis was employed here not only to search for the possible presence of 4-aminocarminic acid but also to investigate the potential formation of photo-degradation products derived from this compound. For this purpose, a statistical approach based on Student’s t-test was used to compare the degraded beverages containing 4-aminocarminic acid with all the others. Five degradation products were identified and their structures were elucidated on the basis of the high-accuracy and high-resolution of mass and mass/mass spectra. The toxicity of the degradation products was evaluated through the Ames Salmonella/microsome mutagenicity assay. No evidence of mutagenicity was obtained for the beverages subjected or not to irradiation, whereas a toxic effect of the 4-aminocarminic acid standard solution already at 100.0 µg l^?1 was found. This leads, once again, to the conclusion that the toxicity study must be carried out on the beverages in order to take into account of all the possible masking/protection interactions among the ingredients.     

Influence of copigment derived from Tasmannia pepper leaf on Davidson's plum anthocyanins

Davidson's plum (Davidsonia pruriens, F. Muell.), a native to Australian rainforests, large, crimson-red fruit, which superficially resembles plum, has been commercially cultivated in Australia since 1990s. The current production volume exceeds market demands therefore this study was designed to evaluate the suitability of Davidson's plum extract as a source of anthocyanin-based food colorant. The stability of the Davidson's plum extract towards heat treatment at 95 °C was higher than that of commercial mulberry colorant, but inferior to colorants derived from red cabbage and purple sweetpotato. An addition of a variety of phenolic acids significantly increased color intensity indicating the formation of copigmentation complexes. Commercial chlorogenic acid as well as extract from a native Australian herb rich in chlorogenic acid, Tasmannia pepper leaf (Tasmannia lanceolata, R. Br.), were both tested in model soft drink solutions subjected to light irradiation and heat treatment. In both cases, the addition of the copigment resulted in a lasting increase in color intensity. In conclusion, Davidson's plum extract can successfully be utilized as a source of natural food color. Extract from Tasmania pepper leaf can be used as a co-pigment for Davidson's plum anthocyanins. PRACTICAL APPLICATION: The color properties of an anthocyanin colorant derived from the native Australian fruit Davidson's plum are comparable to those of mulberry, which is currently applied as a food colorant in Australian food products. Utilization of Davidson's plum fruit as a source of natural color will allow the industry to increase the range of natural pigments and will create new opportunities for the emerging native food industry.     

Detection of the color adulteration of green table olives with copper chlorophyllin complexes (E-141ii colorant)

The present work proposes a procedure for the detection of the color adulteration of green table olives with E-141ii colorant. Addition of this colorant to table olives to obtain a green permanent color in the product is a fraudulent practice, because the FDA allows its use only in citrus-based dry beverage mixes and European Union regulations do not permit the addition of colorants to table olives. The method consists of a pigment extraction in liquid phase and subsequent analysis by HPLC-DAD. The fraudulent addition of E-141ii is determined from the detection in fruit and/or packing solution, of peaks identified as copper chlorophyllin complexes, which are compounds completely foreign to the natural pigment profile of green table olives. The proposed methodology allows controlling the color quality of green table olives.     

红枣红色素的研究进展

随着食品工业的迅猛发展,食品添加剂在人们生活中发挥的作用日益显著。近年来,食品安全屡遭质疑,人们对食用色素也提出了更高的要求,相较于大多数具有致癌风险的合成色素,取自天然、无污染的植物色素更受到人们的青睐。枣红色素是一种提取自红枣果皮的天然色素资源,但开发和利用这一天然色素资源还存在许多问题。本文就色素组成、性质、药理活性、提取和精制方法及深加工技术进行了介绍,综述了近年来红枣红色素在提取、加工和应用方面的研究概况。分析表明,红枣红色素原料来源丰富,提取方便,是一种值得深度开发的性能优异的天然色素资源,但在色素结构鉴定、高效低能耗提取方法开发和产品干燥制粉等方面目前开展的工作较少,文末就此对枣红色素的研究进行了展望。     

一种微生物发酵产蓝色素的稳定性及毒性研究

天然蓝色素十分罕见，直接采用微生物发酵并能用于食用的天然蓝色素至今未见报道。我们利用一株链霉菌（Ｓｔｒｏｐｔｏｍｙｃｅｓ）ＬＳ－１进行发酵，对其产生的蓝色素的稳定性、毒性进行了研究。实验结果表明本色素是蓝色粉末，几乎无臭无味，易溶于水和含水乙醇，在碱性时呈鲜明蓝色，在酸性时呈红色，耐热（８０～１００℃６０ｍｉｎ）不褪色，在ｐＨ＞７时光（包括紫外光）稳定性强，金属离子Ｎａ＋、Ｍｇ２＋对本色素无影响。本色素对革兰氏阴性细菌、酵母菌及丝状真菌无抑制作用，对革兰氏阳性细菌有微弱的拮抗作用。粗品毒性试验ＬＤ５０＞１５０００ｍｇ／ｋｇ，致突变试验阴性，色素粗品属无毒。发酵液色价吸光度（１０倍稀释水溶液）０．４（λｍａｘ＝５８１ｎｍ），发酵周期８０±２ｈ。研究结果认为本色素是一种很有开发前景的微生物天然蓝色素。     

Protoporphyrin-IX as a Substitute for Nitrite in Cured-Meat Color Production

The iron-free heme derivative protoporphyrin-IX, was added to a cooked emulsified beef product to mimic the typical cured-color obtained with nitrite. Although the pigment was stable and could be recovered from the emulsion it imparted a purple hue as noted by visual observation and Hunterlab color values (L,a,b). The possible implications of this pigment as a meat colorant are discussed.     

猪血亚硝基血红蛋白在肉品中的应用研究

为了进一步确定HbNO在肉品中的可应用性，将适量亚硝摹血红蛋白作为着色剂制成火褪肠，感官状态完全接近哑硝酸钠发色效果，优于红曲色素的着色效果。由于具有很强的耐热性，亚硝基血红蛋白作为肉制品着色剂添加到高温火腿肠中是可行的。     

桑椹红色素稳定性的研究

桑椹红色素是一种安全、无毒的天然食用色素。试验从桑椹果渣中提取桑椹红色素,从p H值、温度、光照、Vc、H_2O_2以及亚硫酸钠等方面对其稳定性作了研究。结果表明,桑椹红色素的呈色与p H值有关,在酸性条件下有较好的颜色表现力;其色值受加热温度和加热时间影响较大;在低温避光条件下光稳定性较好,添加少量的Vc可以起到一定的护色作用;其耐氧化性和耐还原性较差,在生产过程中需要注意防氧化和防还原。     

Determination of color, pigment, and phenolic stability in yogurt systems colored with nonacylated anthocyanins from Berberis boliviana L. as compared to other natural/synthetic colorants

ABSTRACT:  Anthocyanins are of interest to the food industry because of their antioxidant power, attractive color, and stability in high acid foods. Powder from the Peruvian berry Berberis boliviana Lechler, rich in nonacylated anthocyanins (7% to 8% dry weight), was incorporated into yogurt samples containing 3 different fat levels. Color (CIE L , a , b , chroma, and hue angle), pigment (monomeric anthocyanin and polymeric color), and total phenolics were monitored over 8 wk of storage and compared to yogurt treatments containing purple carrot acylated anthocyanins, red beet betalaines, or FD&C Red nr 40. Anthocyanin profiles were analyzed by HPLC coupled to photodiode array and mass detectors. Color of yogurt containing B. boliviana anthocyanins at 20 mg cyanidin-3-glucoside (cy-3-glu) equivalents/100 g yogurt ( L *= 65, chroma = 14, and hue angle = 335°) was similar to commercial blueberry yogurt ( L *= 65, chroma = 10.5, and hue angle = 341°). High color, pigment, and phenolic stability were observed in yogurts colored with B. boliviana , independent of the fat matrix. Acylated anthocyanins from purple carrot extracts exhibited increased stability with higher fat content. Anthocyanin degradation followed 1st-order kinetics. Pigment half-lives were 125 and 104 d for nonacylated anthocyanins at 10 and 20 mg cy-3-glu equivalents/100 g yogurt and 550.2, 232.6, and 128.9 d for acylated anthocyanins at 20 mg of cy-3-glu equivalents/100 g of 4%, 2%, and 0% fat yogurt. Addition of B. boliviana whole berry powder to yogurt matrices produced an attractive, stable anthocyanin-rich product, eliminating the need for industrial colorant extraction.     

Amaranthus Betacyanin Pigments Applied in Model Food Systems

Amaranthus betacyanin pigments and commercial colorants were evaluated to determine color characteristics and stability at different temperatures in jelly, ice cream, and a model beverage. The betacyanin exhibited brighter color characteristics than red radish anthocyanin, with similar color stability during 20-wk storage (≤ 14 °C) or during the initial 4-wk storage (≤ 25 °C), but was less stable than red radish anthocyanin at 37 °C. The betacyanin was not as stable as synthetic Food, Drug, and Cosmetics Red No. 3 under most storage conditions. Ascorbic acid had a protective effect on Amaranthus pigments. Excessive sucrose (≥ 16%) decreased stability of the pigments. The betacyanin tested may be a feasible natural colorant for jelly, higher pH beverages, and ice cream under selected conditions.     

欧李红色素的性质和应用

本文研究了欧李红色素的性质及其在食品中的应用,结果表明:欧李红色素具有较强的抗氧化性能,对光、热、常见食品添加剂及常见金属离子(除Fe3+、Sn2+外)均比较稳定,而苯甲酸钠、氧化剂及还原剂对其有较大的破坏作用;用于酸性饮料及白酒中的热稳定性较好,光稳定性较差,在液体饮料中添加0.05%～0.1%,着色效果较好。     

HPLC/PDA determination of carminic acid and 4-aminocarminic acid using relative molar sensitivities with respect to caffeine

To accurately determine carminic acid (CA) and its derivative 4-aminocarminic acid (4-ACA), a novel, high-performance liquid chromatography with photodiode array detector (HPLC/PDA) method using relative molar sensitivity (RMS) was developed. The method requires no analytical standards of CA and 4-ACA; instead it uses the RMS values with respect to caffeine (CAF), which is used as an internal standard. An off-line combination of ¹H-quantitative nuclear magnetic resonance spectroscopy (¹H-qNMR) and HPLC/PDA was able to precisely determine the RMSs of CA^274nm/CAF^274nm and 4-ACA^274nm/CAF^274nm. To confirm the performance of the HPLC/PDA method using RMSs, the CA and 4-ACA contents in test samples were tested using four different HPLC-PDA instruments and one HPLC-UV. The relative standard deviations of the results obtained from five chromatographs and two columns were less than 2.7% for CA^274nm/CAF^274nm and 1.1% for 4-ACA^274nm/CAF^274nm. The ¹H-qNMR method was directly employed to analyse the CA and 4-ACA contents in test samples. The differences between the quantitative values obtained from both methods were less than 5% for CA and 3% for 4-ACA. These results demonstrate that the HPLC/PDA method using RMSs to CAF is a simple and reliable quantification method that does not require CA and 4-ACA certified reference materials.     

紫色红曲霉固态发酵三七渣生产红色素的动力学研究

该实验在紫色红曲霉固态发酵三七渣生产红色素过程中考察了生物量、淀粉含量、总糖含量、还原糖含量、红色素色价和pH等参数随时间的变化情况,并建立了菌体生长、基质降解和产物生成的动力学模型。结果表明,菌体生长、基质降解和产物生成动力学分别适合采用对数模型、四参数对数模型、Boltzmann模型进行描述。最大菌体生物量Xm为0.241 6 g/g发酵培养物（干基）,比生长速率常数μ为0.457 4 d-1。最大红色素色价B2为14.63 U/g发酵培养物（干基）,红色素色价达到最大值一半时需要的发酵时间t0=4.21 d。发酵末期发酵培养物（干基）中总糖含量D2为28.84%,总糖降解的半衰期t50%为3.536 d。     

米团花色素在果汁、果冻中的应用

考察米团花色素在果汁和果冻中的应用效果,探讨该色素的应用范围。将米团花色素添加到果汁和果冻中,以柠檬黄为对照,研究其对食品感官的影响及其在储藏过程中的稳定性。结果表明:果汁和果冻添加米团花色素后色泽良好,储藏7周后,果汁和果冻中米团花色素含量分别降低4.1%和0.6%;米团花色素可用作果汁和果冻着色剂。