简述美拉德(Maillard)反应

简述了美拉德反应的机理及影响因素,总结了MRPs的抗氧化性、与突变的关系及其在食品上的作用,最后说明了美拉德反应进度的判断依据。     

Effect of amino acids in the Maillard reaction products generated from the reaction flavors of Tenebrio molitor (mealworm) protein and d-xylose

Food Science and Biotechnology - In this study, Tenebrio molitor (mealworm) protein and reducing sugar were thermally reacted without (MP-RF) or with amino acids (MPA-RFs, A is then replaced with...     

美拉德反应研究进展

美拉德反应(Maillard Reaction)是指氨基化合物和羰基化合物之间的一类化学反应,此类反应常存在于食品加工、烟草研制、中药炮制、疾病生理以及饲料制备和酒业酿造等过程中。近年来,Maillard反应的研究主要集中在中药现代化和疾病生理等方面,尤其关注抗氧化产物以及甲基糠醛和丙烯酰胺等与人类健康密切相关方面的研究。拟对Maillard反应研究进展做一简要综述,并在此基础上对Maillard反应在各领域中的前景作一展望,为Maillard反应各类研究及应用提供一定的参考。     

The mechanism of peptide bonds cleavage and volatile compounds generated from pentapeptide to heptapeptide via Maillard reaction

This study is focused on the mechanism of peptide bond cleavage and volatile Maillard reaction products (MRPs) following reaction of 10 artificial oligopeptides with cysteine, xylose and thiamine. LC-TOF/MS was used to detect the chemistry of peptide bond cleavage in liquid media. GC–O–MS and a carbohydrate module labelling (CAMOLA) method were used to analyse and identify the formation pathways of volatile and semi-volatile MRPs. In this study, the theoretical foundation of seven principles of influencing factors acting on peptide chain cleavage has initially been summarised. At the start of this study assumptions were also made relating to heat resistance of peptide chain positions. A universal formation pathway map and a model of possible mechanisms of common product formation were proposed. This model was authenticated by this scientific study.     

抗氧化剂对美拉德反应的影响

采用葡萄糖分别与天冬酰胺和甘氨酸在160℃下反应建立美拉德反应的模拟体系,通过HPLC分析和褐变程度的测定,探讨了4种抗氧化剂BHA、BHT、TBHQ、Vc对美拉德反应的影响。结果表明,添加抗氧化剂对其HPLC色谱峰的出峰数、峰面积都有较大影响。相同条件下,添加抗氧化剂对甘氨酸-葡萄糖体系影响较大。     

脂类对反应型香精风味形成影响的研究

根据3种不同原料所含主要脂肪酸及不饱和度的不同,通过反应所生成主要风味物质差异来进一步探讨反应型香精风味形成机理。     

热反应肉味香精质量与价格关系的评价方法

提出一种评价热反应肉味香精(Maillardreactionmeatflavoring)质量与价格关系的方法,利用该方法能比较准确的用数字化的方式表达热反应肉味香精质量与价格之间的关系。     

Studies on melanoidin-type colorants generated from the Maillard reaction of protein-bound lysine and furan-2-carboxaldehyde – chemical characterisation of a red coloured domaine

 The identification of a coloured substructure of melanoidin-type colorants is reported in the present paper. Brown-orange melanoidins with mass >10000 daltons were isolated from a thermally treated aqueous solution of casein and furan-2-carboxaldehyde using ultracentrifugation. After complete enzymatic digestion of the protein skeleton, two intense red coloured compounds were detected in the melanoidin hydrolysate by HPLC. These compounds were identified as the previously unknown chromophoric amino acid (S)-2-amino-6-{4-[(E)-1-formyl-2-(2-furyl)ethenyl]-5-(2-furyl)-2-[(E)-(2-furyl) methylidene]-2,3-dihydro-3-oxo-1H-pyrrol-1-yl}hexanoic acid and its 2-[(Z)-(2-furyl)methylidene] isomer, by using several NMR techniques, by MS, UV, and IR spectroscopy. The identification of these novel compounds verifies the idea that melanoidin-type colorants can be generated by a cross-linking reaction between a low molecular weight chromophore and a non-coloured high molecular weight biopolymer. Received: 19 August 1997 / Revised version: 24 October 1997     

Studies on melanoidin-type colorants generated from the Maillard reaction of protein-bound lysine and furan-2-carboxaldehyde – chemical characterisation of a red coloured domaine

 The identification of a coloured substructure of melanoidin-type colorants is reported in the present paper. Brown-orange melanoidins with mass >10000 daltons were isolated from a thermally treated aqueous solution of casein and furan-2-carboxaldehyde using ultracentrifugation. After complete enzymatic digestion of the protein skeleton, two intense red coloured compounds were detected in the melanoidin hydrolysate by HPLC. These compounds were identified as the previously unknown chromophoric amino acid (S)-2-amino-6-{4-[(E)-1-formyl-2-(2-furyl)ethenyl]-5-(2-furyl)-2-[(E)-(2-furyl) methylidene]-2,3-dihydro-3-oxo-1H-pyrrol-1-yl}hexanoic acid and its 2-[(Z)-(2-furyl)methylidene] isomer, by using several NMR techniques, by MS, UV, and IR spectroscopy. The identification of these novel compounds verifies the idea that melanoidin-type colorants can be generated by a cross-linking reaction between a low molecular weight chromophore and a non-coloured high molecular weight biopolymer. Received: 19 August 1997 / Revised version: 24 October 1997     

美拉德反应与食品风味

主要介绍了美拉德反应及简单叙述了影响美拉德反应的一些因素,以及美拉德反应产物对一些食品风味所作的一些贡献做了简单的介绍。     

News on the Maillard reaction of oligomeric carbohydrates: a survey

The reaction behaviour of monosaccharides in the Maillard reaction is well investigated. Amadori compounds, for instance, form deoxyhexosuloses which are responsible for the formation of volatile flavour substances and melanoidins. These intermediates can be quantified by a trapping reaction with o‐phenylendiamine as stable quinoxalines. However the reaction behaviour of oligo and polymeric carbohydrates in non‐enzymatic browning reactions are hardly known. Therefore maltooligosaccharides and in some cases starch were used together with glycine as model substances to investigate the Maillard reaction mechanism of oligo and polysaccharides. In quasi waterfree reaction systems oligosaccharides form α‐dicarbonyl compounds via a “peeling off” mechanism. The Maillardreaction with the amino compound starts at the reducing end of an α‐glucane residue and results in the formation of 1,4‐dideoxyhexosulose. This is the main α‐dicarbonyl compound found by trapping reaction with o‐phenylendiamine during thermally induced degradation of maltooligosaccharides. The thermal reaction of maltooligosaccharides is accompanied by transglycosylations leading to formation of branched carbohydrate structures and by dehydrations forming anhydrosugars. The reaction mechanism which is responsible for degradation of oligomeric carbohydrates in aqueous model systems differs significantly from pathways mentioned above for water free reaction conditions. As the main α‐dicarbonyl compound 3‐deoxypentosulose is formed which can be proved also by trapping reactions. Under aqueous reaction conditions the formation of other α‐dicarbonyls plays only a marginal role in the Maillard reaction of oligomeric carbohydrates. In an aqueous system transglycosylation and dehydration of maltooligosaccharides are not important.     

反应温度和反应时间对抗坏血酸-半胱氨酸模式反应形成香味化合物的影响

以固相微萃取-气相色谱-质谱联用(SPME-GC-MS)技术对抗坏血酸与半胱氨酸(ASA-Cys)的模式反应产物进行鉴定,研究了酸性条件(pH5.00)下反应温度和反应时间对ASA-Cys模式反应形成香味化合物的影响。模式反应的早期阶段主要是ASA和Cys的热降解,此段对反应温度的依赖性很大。140℃的反应温度能使ASA和Cys快速热降解,从而加快Maillard反应的进行,形成风味较佳的肉香味。在此温度下,反应150min,模式反应形成的各类香味化合物的量达到最大,继续延长反应时间,各类香味化合物的量逐渐减少。结果表明140℃的反应温度以及该温度下150min的反应时间对模式反应形成香味化合物是合适的。     

乳清蛋白肽美拉德反应产物的制备及其抗氧化特性的评价

以乳杆菌A-2发酵乳清蛋白与乳糖发生美拉德反应,制备得乳清蛋白肽美拉德反应产物,对其进行分离纯化并研究抗氧化活性。将乳杆菌A-2接种于复原乳清粉培养基经热加工得发酵产物,经Sephadex G 15层析柱分离,采用SDS-PAGE图谱证实乳杆菌A-2发酵乳清粉在干热处理条件下确实发生了美拉德反应;以抗坏血酸(维生素C)和丁基羟基茴香醚(BHA)为阳性对照,用ABTS法和ORAC法来测定和评价乳杆菌9029乳清蛋白发酵产物的抗氧化作用。在反应体系中,H-DPWF-1、BHA和维生素C的ABTS清除率分别是77.38%、86.47%和73.95%,H-DPWF-1清除ABTS自由基的能力的介于维生素C和BHA之间;样品H-DPWF-1的相对ORAC值为3.43mmol TE/g,维生素C的相对ORAC值为9.67mol TE/g,即H-DPWF-1清除AAPH的能力为维生素C的1/3。结果显示H-DPWF-1具有较强的抗氧化活性,具有广阔应用前景和潜力。     

Maillard反应对卵白蛋白稳定性的影响

为了确定Maillard反应对卵白蛋白稳定性的影响,本文研究了Maillard反应卵白蛋白处于酶解、酸性环境、加热、变性剂、反复冻融等不利条件下的理化特点。结果表明Maillard反应抑制了蛋白酶对卵白蛋白的酶解效果。Maillard反应卵白蛋白在p H2~7的范围内,空间结构伸展程度较小。Maillard反应将卵白蛋白的变性温度从71.3℃提高到76.9℃,明显改善了卵白蛋白的热稳定性。6mol·L-1的尿素能够使热处理卵白蛋白和天然态卵白蛋白完全变性,而只能使Maillard反应卵白蛋白部分变性。Maillard反应能够提高卵白蛋白的溶解度,其溶解度经过反复冻融后仍处于较高水平。Maillard反应可以有效提高卵白蛋白稳定性,从而保证卵白蛋白功能性的发挥。     

食品中的美拉德反应及其影响

探讨了食品中发生的美拉德反应途径、底物、温度、水分活度、pH和金属离子等影响因素,同时讨论了抗茵性、抗氧化性和乳化性等食品功能性以及蛋白质的糖基化、溶解性和风味特性的修饰改进,并介绍了其时生物活性体的影响性以及丙烯酰胺等有害物质的生成与消除,丰富了食品化学理论并对食品加工生产应用有很好的指导意义.     

Maillard reaction products profile and intake from Spanish typical dishes

The Mediterranean diet is proposed as one of the healthiest dietary models, but its contribution to Maillard reaction products (MRP) intake is unknown. Several Spanish dishes typical of the Mediterranean diet (paella, Spanish omelette, salmorejo or churros) were selected to evaluate MR extension and the presence of MRP. CIELab colour, browning at different wavelengths, furosine, hydroxymethylfurfural, furfural and acrylamide were determined, and content/serving was calculated. Development of MR was affected by ingredients: when protein levels were high and carbohydrates low, early MRP were formed, regardless of the culinary process. There was found a correlation between acrylamide and hydroxymethylfurfural. The possible underestimation of deterministic calculations of acrylamide dietary exposure is discussed. This study presents a first approximation to enable the MRP intake from the Mediterranean diet to be calculated, taking into account the moisture content and the serving size of dishes.     

反应温度和时间对抗坏血酸/精氨酸Maillard反应体系中挥发性化合物形成的影响

采用顶空固相微萃取-气相色谱-质谱联用技术对抗坏血酸/精氨酸反应体系在不同反应温度和时间下的产物进行鉴定,共鉴定出包括吡嗪、醛、呋喃、醇和吲哚在内的24种化合物,其中14种吡嗪化合物为主要香味化合物。考察了反应温度和时间对产物特别是对吡嗪化合物的影响。结果表明,随着反应温度的升高和反应时间的延长,吡嗪类化合物的总量均增加;其中,随反应温度的升高,相对其他吡嗪化合物2-乙基-6-甲基吡嗪、3-乙基-2,5-二甲基吡嗪的量明显增加;随反应时间的延长,2-乙基-6-甲基吡嗪的量明显增加。     

News on the Maillard reaction of oligomeric carbohydrates: a survey.

The reaction behaviour of monosaccharides in the Maillard reaction is well investigated. Amadori compounds, for instance, form deoxyhexosuloses which are responsible for the formation of volatile flavour substances and melanoidins. These intermediates can be quantified by a trapping reaction with o-phenylendiamine as stable quinoxalines. However the reaction behaviour of oligo and polymeric carbohydrates in non-enzymatic browning reactions are hardly known. Therefore maltooligosaccharides and in some cases starch were used together with glycine as model substances to investigate the Maillard reaction mechanism of oligo and polysaccharides. In quasi waterfree reaction systems oligosaccharides form alpha-dicarbonyl compounds via a "peeling off" mechanism. The Maillard reaction with the amino compound starts at the reducing end of an alpha-glucane residue and results in the formation of 1,4-dideoxyhexosulose. This is the main alpha-dicarbonyl compound found by trapping reaction with o-phenylendiamine during thermally induced degradation of maltooligosaccharides. The thermal reaction of maltooligosaccharides is accompanied by transglycosylations leading to formation of branched carbohydrate structures and by dehydrations forming anhydrosugars. The reaction mechanism which is responsible for degradation of oligomeric carbohydrates in aqueous model systems differs significantly from pathways mentioned above for water free reaction conditions. As the main alpha-dicarbonyl compound 3-deoxypentosulose is formed which can be proved also by trapping reactions. Under aqueous reaction conditions the formation of other alpha-dicarbonyls plays only a marginal role in the Maillard reaction of oligomeric carbohydrates. In an aqueous system transglycosylation and dehydration of maltooligosaccharides are not important.     

影响蒜氨酸美拉德反应速度的因素

为了解蒜氨酸美拉德(Maillard)反应对大蒜加工品质量和风味的影响,使合成蒜氨酸、果糖、葡萄糖在80～120℃,pH5～10条件下反应1～1.5h,通过感观评价和测定反应物的吸光度,评价Maillard反应效果。结果表明:在80～120℃、pH5～10、含水量10%条件下反应2.5h时,Maillard反应达到最大值,反应产物具有明显的大蒜辛辣味,反应物颜色为红棕色(与果糖反应)或桔红色(与葡萄糖反应)。这些结果对于控制大蒜加工品的质量与风味有参考价值。     

Characteristics and antioxidant activity of Maillard reaction products from fructose-glycine oligomer

The pH of Maillard reaction products (MRPs) derived from the Gly model system (Gly) decreased markedly as heating time increased. However the Digly model system (Digly) exhibited the highest increase in absorbance at 294 and 420 nm. Moreover, the loss of fructose and degree of sugar enolization in MRPs derived from the Trigly model system (Trigly) was the highest, whereas the glycine oligomer content in the Digly noticeably decreased as heating time increased. Furthermore, the gel permeation chromatograms (GPC) patterns of all MRP samples exhibited rising intensities as a function of the heating time, whereas the major peaks of each MRP sample were eluted at different retention times as glycine oligomer. Antioxidant activity of each MRP sample was investigated by Fe²⁺ and Cu²⁺ chelating activity, Trolox, ABTS, 1,1-diphenyl-2-picryl-hydrazil (DPPH) radical scavenging activity, and ferric reducing ability of plasma (FRAP) assay. MRPs derived from the glycine oligomer were found to be effective antioxidants in different antioxidant activity assays.