食用香料香兰素和乙基香兰素的合成新进展

介绍香兰素和乙基香兰素的合成方法，并综述了近十年来香兰素和乙基香兰素合成技术的新进展，同时对草酸电解法，对羟基苯甲醛对以及生物转化法等新技术作了若干展望。     

奶粉中香兰素、甲基香兰素和乙基香兰素的测定

建立了同时测定奶粉香兰素、甲基香兰素和乙基香兰素的超高效液相色谱法。样品用水溶解后使用Pro Elut PXA固相萃取柱进行样品前处理净化,C18柱分离,超高效液相色谱仪进行色谱分析。结果表明,香兰素、甲基香兰素和乙基香兰素在0.5~20 mg/L范围内线性关系良好;方法的检出限(S/N=3)分别为0.20,0.25,0.25 mg/L;样品的加标回收率为80.3%~102.7%,相对标准偏差为1.85%~4.11%。该方法结果准确可靠,可实现香兰素、甲基香兰素和乙基香兰素的快速同步分析。     

GC和GC-MS法测定饮料中香兰素和乙基香兰素含量

本文建立了一种气相色谱(GC)和气相色谱-质谱(GC-MS)法测定饮料中香兰素和乙基香兰素含量的方法。无色样品经乙醚萃取、离心、取上清液浓缩定容经0.22μm有机相滤膜净化进样,有颜色样品经乙醚萃取、离心、取乙醚上清液浓缩至近干,丙酮溶解混匀,过石墨化碳黑柱净化,浓缩定容,分别进GC-FID和GC-MS测定及确证,外标法定量。GC法测定香兰素和乙基香兰素的添加回收率范围为80%~105%,相对标准偏差(RSD)小于6.0%。GC-MS法测定香兰素和乙基香兰素的添加回收率范围为81%~110%,相对标准偏差(RSD)小于6.0%。该方法中GC仪器操作简单、成本较低,可广泛应用于饮料中香兰素和乙基香兰素日常检测,GC-MS法采用选择离子扫描(SIM)排除GC法测定的假阳性结果,使测定结果更准确可靠,两种方法互补使用,适合饮料中香兰素和乙基香兰素的日常分析检测和质量控制。     

乙基香兰素合成工艺改进

采用氯化溴法合成3-溴-4-羟基苯甲醛,再通过乙氧基化合成乙基香兰素.对反应温度、反应时间、原料配比、溴化剂的滴加速度、溶剂等影响中间体产率的因素进行了研究.在溴化阶段用氯化溴代替溴素,用氯仿作溶剂,乙酸乙酯作助溶剂,使-溴化物的产率提高了9.4%;在乙氧基化步骤中用CuO作催化剂,用乙醇和DMF作反应溶剂,对原料配比和催化剂用量做了研究,使得最终产物乙基香兰素的产率达到82.5%.     

奶粉中香兰素、甲基香兰素和乙基香兰素的测定

建立了同时测定奶粉香兰素、甲基香兰素和乙基香兰素的超高效液相色谱法。样品用水溶解后使用Pro Elut PXA固相萃取柱进行样品前处理净化,C18柱分离,超高效液相色谱仪进行色谱分析。结果表明,香兰素、甲基香兰素和乙基香兰素在0.5 mg/L~20 mg/L范围内线性关系良好;方法的检出限(S/N=3)分别为0.20、0.25、0.25 mg/L;添加水平在2.5 mg/L~10.0 mg/L时加标回收率为80.3%~102.7%,相对标准偏差为1.85%~4.11%(n=6)。该方法结果准确可靠,可实现奶粉中香兰素、甲基香兰素和乙基香兰素的快速同步分析。     

乙基香兰素合成工艺改进

采用氯化溴法合成3-溴-4-羟基苯甲醛,再通过乙氧基化合成乙基香兰素。对反应温度、反应时间、原料配比、溴化剂的滴加速度、溶剂等影响中间体产率的因素进行了研究。在溴化阶段用氯化溴代替溴素,用氯仿作溶剂,乙酸乙酯作助溶剂,使一溴化物的产率提高了9.4%;在乙氧基化步骤中用CuO作催化剂,用乙醇和DMF作反应溶剂,对原料配比和催化剂用量做了研究,使得最终产物乙基香兰素的产率达到82.5%。     

高效液相色谱法测定软饮料中香兰素和乙基香兰素

目的建立软饮料中香兰素和乙基香兰素的高效液相色谱法检测方法。方法样品中的香兰素和乙基香兰素在酸性条件下经乙腈提取,利用盐析作用分层净化,提取液浓缩复溶解后,供液相色谱检测。检测波长308 nm,外标法定量。结果香兰素和乙基香兰素在0.5~50.0?g/m L浓度范围内线性关系良好,相关系数均大于0.9999。添加水平为5、30、63 mg/kg时,香兰素和乙基香兰素的平均回收率分别为98.4%和100.4%,96.7%和100.2%,97.8%和100.3%,相对标准偏差在3.53%~4.70%,检出限均为0.5 mg/kg。结论方法操作简便、快速,经济实用,适用性强,结果准确可靠,可用于样品批量快速检测。     

婴幼儿配方粉中香兰素和乙基香兰素的检测方法比较

目的 建立婴幼儿配方粉中香兰素、乙基香兰素的液相色谱法和同位素稀释液相色谱质谱联用两种测定方法。方法 液相色谱法: 样品经乙酸锌沉淀蛋白、Oasis MAX SPE柱净化, HSS T3色谱柱分离后, 在279 nm波长处进行检测, 外标法定量。同位素稀释液质联用法: 样品采用乙腈沉淀蛋白稀释净化后, 采用Waters BEH C18柱分离, 在质谱检测器多反应监测(UPLC-MS/MS)模式下, 用同位素稀释液质联用法进行检测。结果 液相色谱法: 香兰素、乙基香兰素的定量下限(LOQ)均为0.1 mg/kg。香兰素的方法回收率为88%~90.8 %, 相对标准偏差(RSD)小于5.2 %; 乙基香兰素的方法回收率为84%~93.3 %, RSD小于6.2 %。同位素稀释液质联用法香兰素、乙基香兰素的LOQ分别为香兰素1、0.5 mg/kg。香兰素、乙基香兰素的方法回收率分别为82.1%~91.2 %、90.2%~97.6 %, RSD分别小于6.1 %、5.8 %。结论 本文建立的两种方法对同一样品的检测结果一致, 为婴幼儿配方粉中香兰素、乙基香兰素的定量检测提供了较为理想的方法。     

顶空固相微萃取-气质联用法测定奶茶中的香兰素和乙基香兰素

采用顶空固相微萃取(HS-SPME)和气相色谱质谱联用技术(GC/MS),建立了测定奶茶中香兰素和乙基香兰素的分析方法。选取了75μm carboxen/聚二甲基硅氧烷(CAR/PDMS)萃取纤维,考察了萃取温度、萃取时间和盐浓度等因素对萃取效率的影响。采用3,4-亚甲二氧苯乙酮作为内标,对香兰素和乙基香兰素进行定量。结果表明,在检测范围0.5~25.0μg内,该方法对香兰素(R2=0.9974)和乙基香兰素(R2=0.9987)具有良好的线性关系,固体样品中香兰素和乙基香兰素的检出限分别为0.5 mg/kg和0.3 mg/kg,液体样品中检出限分别为0.05 mg/kg和0.03 mg/kg,香兰素的平均回收率为88.99%~105.15%,相对标准偏差(RSDs)为2.40%~9.26%,乙基香兰素的平均回收率为91.57%~105.13%,相对标准偏差为2.35%~8.49%。该方法操作简便、准确可靠,适合于奶茶中香兰素和乙基香兰素的分析要求。     

总局关于发布食品中香兰素、甲基香兰素和乙基香兰素的测定等2项食品补充检验方法的公告

正2017年第64号按照《食品补充检验方法工作规定》有关规定,《食品中香兰素、甲基香兰素和乙基香兰素的测定》和《食品中氯酸盐和高氯酸盐的测定》2项食品补充检验方法已经国家食品药品监督管理总局批准,现予发布。特此公告。附件:1.食品中香兰素、甲基香兰素和乙基香兰素的测定(BJS 201705)2.食品中氯酸盐和高氯酸盐的测定(BJS 201706)     

饮料酒中香草醛的研究进展

香草醛是饮料酒中一种非常重要的香气化合物,因其具有令人愉悦的甜香及香荚兰豆香草香气,同时具有一定的生理功能而被广泛关注。香草醛具有很强的极性且在酒中含量甚微,常规的检测方法难以有效检出饮料酒中香草醛的含量,探究酒中香草醛的分析方法一直是研究的课题。饮料酒的原辅料细胞壁中含有丰富的木质素、阿魏酸等,是形成香草醛的重要前驱物质,它可以通过真菌、细菌等微生物经非氧化脱羧反应等代谢途径在酿造过程中转换成香草醛。本文从饮料酒中香草醛的分析方法、香气贡献、含量差异及形成机理等方面进行综述,以期为我国饮料酒中香草醛的研究提供理论参考。     

香兰素和维生素C对卤煮牛肉中杂环胺含量的影响

目的探索牛肉卤煮加工过程中添加香兰素和维生素C对杂环胺形成含量的影响。方法采用固相萃取前处理技术,结合不同处理情况下高效液相紫外和荧光检测法测定肉样中杂环胺的含量。结果香兰素和维生素C都能够减少卤煮牛肉中杂环胺的形成。当维生素C的添加浓度量达0.15%时,杂环胺总量减少90%以上。当维生素C浓度增大到0.5 mg/m L时,维生素C对1,1-二苯基-2-三硝基苯肼(1,1-diphenyl-2-picrylhydrazyl,DPPH)自由基清除率高达90%;当维生素C添加浓度为0.4 mg/m L时,其对超氧阴离子的清除率高达84%左右。结论维生素C和香兰素均可减少卤煮牛肉中杂环胺的生成,维生素C对DPPH自由基清除率和超氧阴离子自由基清除率均比香兰素高,且对卤煮牛肉中杂环胺的抑制效果比香兰素好。     

Effect of Tissue Disruption by Different Methods Followed by Incubation with Hydrolyzing Enzymes on the Production of Vanillin from Tongan Vanilla Beans

Vanilla is one of the most popular and valuable flavorings worldwide. Natural vanilla is extracted from the cured vanilla pods of Vanilla planifolia. The main aromatic compound in vanilla is vanillin, a phenolic aldehyde, which is produced by enzymatic hydrolysis of glucovanillin during the curing process. Although the amount of glucovanillin in the uncured green bean is present at the level of 10–15%, only an average of about 2% vanillin yield results from the traditional curing process. Therefore, the aim of the experiment was to increase the vanillin yield by obtaining the maximum conversion of glucovanillin. This was obtained by the addition of exogenous cellulase, pectinase, and beta glucosidase enzymes and cellular-damaging techniques on green Tongan vanilla beans to enhance the interaction between glucovanallin substrate and enzymes and successfully achieved vanillin production ranging from 4.25 to 7.00% on a dry weight basis. These techniques may be further refined and translated into industrial curing practices for improvement of natural vanillin yield from vanilla beans.     

Design of a fungal bioprocess for vanillin production from vanillic acid at scalable level by Pycnoporus cinnabarinus

The biotechnological process of vanillin production from vanillic acid by Pycnoporus cinnabarinus was scaled-up at the laboratory level. Vanillin production was studied in two types of bioreactors, a mechanically agitated and an air-lift bioreactor. In the mechanically agitated bioreactor where vanillin was produced in greater quantities, oxygen availability was studied during the growth and production phases. A maximal aeration rate (90l/h equivalent to 0.83 volume of air/volume of medium/min or vvm) during the growth phase and a minimal aeration rate (30 l/h equivalent to 0.28 vvm) during the production phase were necessary to increase vanillin production to 1260 mg/l. Vanillic acid bioconversion to vanillin occurred under the conditions of reduced dissolved oxygen concentration, gentle agitation, high carbon dioxide production and low specific growth rate. However, under these conditions, vanillin production was accompanied by a significant amount of methoxyhydroquinone. Vanillin over a concentration of 1000 mg/l was shown to be highly toxic to the growth of P. cinnabarinus on agar medium. The application of selective XAD-2 resin led to a reduction of vanillin concentration in the medium, thus limiting its toxicity towards the fungal biomass as well as the formation of unwanted by-products such as methoxyhydroquinone and allowed the concentration of vanillin produced to reach 1575 mg/l.     

A kinetic study of the release of vanillin encapsulated in Carnauba wax microcapsules

Thermal release of vanillin encapsulated in Carnauba wax microcapsules was studied by isothermal thermogravimetric analysis at 443, 453, 473, and 483 K. The thermal analysis data were analyzed kinetically and it was found that they can be satisfactorily described mathematically by the Avrami-Erofe’ev kinetic model A3. However, application of the isoconversional Friedman’s method showed that the activation energy of the vanillin release changes significantly with the degree of conversion, implying that the release is not a single-step reaction but a complex kinetic process. Nonetheless, the activation energies throughout the process remain relatively low (below 40 kJ mol⁻¹), meaning that the Carnauba wax as a carrier can easily release vanillin in food processing.     

气相色谱-质谱法测定奶粉中香兰素的不确定度评估

目的采用气相色谱-质谱法对奶粉中香兰素含量的不确定度评估。方法建立不确定度评估的数学模型,通过对不确定度的各主要分量进行分析计算,得出合成不确定度以及扩展不确定度。结果当香兰素的测定结果为57.1 mg/kg时,其扩展不确定度为4.4 mg/kg,k=2。结论采用气相色谱-质谱法测定奶粉中香兰素含量,其不确定度的主要来源为样品的回收率和最小二乘法拟合的标准曲线,该评估模型为检测奶粉中香兰素的不确定度评估提供了参考依据。     

Encapsulation of vanillin/cyclodextrin inclusion complex in electrospun polyvinyl alcohol (PVA) nanowebs: Prolonged shelf-life and high temperature stability of vanillin

We produced functional nanowebs, containing vanillin, having prolonged shelf-life and high temperature stability facilitated by cyclodextrin (CD) inclusion complexation. Polyvinyl alcohol (PVA) nanowebs incorporating vanillin/cyclodextrin inclusion complex (vanillin/CD-IC) were produced via electrospinning technique. The vanillin/CD-IC was prepared with three types of CDs; α-CD, β-CD and γ-CD to find out the most favourable CD type for the stabilization of vanillin. PVA/vanillin/CD-IC nanofibres, having fibre diameters around ∼200 nm, were successfully electrospun from aqueous mixture of PVA and vanillin/CD-IC. Our results indicated that vanillin with enhanced durability and high temperature stability was achieved for PVA/vanillin/CD-IC nanowebs due to complexation of vanillin with CD, whereas the PVA nanofibres without CD-IC could not effectively preserve the vanillin. Additionally, we observed that PVA/vanillin/γ-CD-IC nanoweb was more effective for the stabilization and slow release of vanillin suggesting that the strength of interaction between vanillin and the γ-CD cavity is stronger when compared to α-CD and β-CD.     

生物法生产香兰素研究进展

香兰素广泛用于食品工业和其它行业中,世界上年消费量达6000吨。目前市场上销售的香兰素主要为人工合成,但天然香兰素更受人们欢迎,价格也高得多。本文综述了国外采用生物方法利用不同前体物质生产香兰素的研究进展。     

Sensory Evaluation of Binding of Vanillin by Fababean Proteins

Sensory studies were conducted to estimate the perceived vanillin flavor of protein-vanillin systems that contained free vanillin and vanillin bound to fababean protein micellar mass (PMM). Nine panelists used the magnitude estimation technique to evaluate vanillin flavor by tasting. A power function was established from a series of different concentrations of vanillin solutions versus their respective sensory estimates of vanillin flavor and used to convert sensory estimates to perceived vanillin concentrations of the vanillin-PMM slurries. The perceived vanillin in vanillin-PMM systems was directly related to the free vanillin in the corresponding system as determined by HPLC, indicating that only the free vanillin contributed to the flavor. Thus, instruments can be used to predict human perception of a particular flavorant in a food system of flavor-protein interactions.     

苦荞奶茶的配方优化

以经气流膨化后的苦荞米花为原料,采用超微粉碎、搅拌、包装等工艺流程,通过设置不同比例的膨化苦荞粉、白砂糖、植脂末、香兰素精、脱脂无糖奶粉、羧甲基纤维素钠,对苦荞奶茶的配方进行研究.试验结果表明:苦荞奶茶的最佳配方为膨化苦荞粉25％、白砂糖35％、植脂末19％、香兰素精6％、脱脂无糖奶粉14％、羧甲基纤维素钠1％.