Amadori化合物合成方法综述

综述了国内外3类主要的合成Amadori化合物的方法:保护和非保护葡萄糖合成法,以及保护果糖合成法,并将这些方法进行了对比,认为热稳定性较差的、与葡萄糖直接反应活性低而又需要较高分离产率的氨基酸可采用保护果糖的方法来制备Amadori化合物。     

Formyline, a new glycation compound from the reaction of lysine and 3-deoxypentosone

A previously uncharacterized glycation compound was isolated from a reaction mixture of N-α-Boc-lysine and 3-deoxypentosone by semi-preparative ion-exchange chromatography and was identified by nuclear magnetic resonance (NMR) spectroscopy as 6-(2-formyl-1-pyrrolyl)-l-norleucine (formyline). 3-Deoxypentosone and pentoses like ribose, arabinose, or xylose were identified as the predominant precursors of the new glycation compound, but formyline can also be formed from lysine and degradation products of disaccharides and glucuronic acid. The Amadori products lactuloselysine and ribuloselysine, which were synthesized by improved methods and characterized by NMR spectroscopy, were shown not to form formyline when heated in dry state without lysine added, indicating that reactions between the lysine side chain and dicarbonyl compounds are the main pathways for formyline formation rather than transformation of lysine containing Amadori products. Finally, it was shown by HPLC analysis after enzymatic digestion that peptide-bound formyline can be formed during incubation of casein and 3-deoxypentosone under conditions comparable to food processing.     

The role of free radicals and antioxidants: How do we know that they are working?

This review briefly discusses how free radicals are formed and the possible participation of free radicals in disease. The review describes the basic radical reactions and the types of products that are formed from the free‐radical reactions of cellular constituents. In many cases, in vivo free‐radical oxidation can be detected by measuring products that were derived from radical reactions. Since aerobic organisms generate oxygen‐containing free radicals during oxygen metabolism, they carry chemicals and enzymes that reduce the threat posed by these radicals. The more common sources of in vivo free radicals are described in the article as well as the methods used by cells to protect themselves from free‐radical damage. Generation of free radicals in vivo also may be the result of exposure to certain chemical agents present in the environment Many of these agents cause pathologic changes to the exposed tissues and organs by initiating free‐radical reactions.     

Effect of heating on Maillard reactions in milk

Heated milk is subject to the Maillard reaction; lactose and lysine residues in milk proteins (mainly casein) are the reactants. An overview is given of the early, advanced and final stages of the Maillard reaction as it occurs in milk. The early Maillard reaction is confined to the formation of the protein-bound Amadori product lactulosyllysine. Breakdown of the Amadori product leads to formation of all kinds of advanced Maillard reaction products such as lysylpyrraline, pentosidine, hydroxymethylfurfural, (iso)maltol, furfurals and formic acid. The content of these compounds in heated milk is, however, very low (with the exception of formic acid), and does not correspond to the breakdown of Amadori product in quantitative terms. The final stage, in which melanoidins (brown pigments) are formed and protein polymerization occurs, is largely unknown from a chemical point of view, let alone quantitatively. The conclusion can only be that not all important compounds are yet identified. Some experimental data for heated milk are given to illustrate the various stages of the Maillard reaction in heated milk. A kinetic analysis of the Maillard reaction is difficult because it is such a complicated reaction with many parallel and consecutive steps; in addition, one of the reactants, lactose, is also subject to another reaction, namely isomerization followed by degradation. The kinetics can be tackled by kinetic, multiresponse modelling, and this approach is illustrated. It appears that the temperature dependence of the (early) Maillard reaction is lower than for the simultaneously occurring isomerization reactions of lactose. The use of several components formed in the Maillard reaction to evaluate the heat intensity given to milk is discussed.     

Forty years of furosine - forty years of using Maillard reaction products as indicators of the nutritional quality of foods

The Maillard reaction products (MRPs) most widely used as markers of the nutritional quality of foods are furosine, N(epsilon)-carboxymethyllysine (CML), hydroxymethylfurfural, pyrraline, pentosidine and pronyl-lysine. One of the MRPs identified first was furosine, which was quantified in foods 40 years ago as a chemical indicator of the Amadori compound N(epsilon)-fructoselysine. Since then, furosine has gained broad attention by food chemists and biomedical researchers, as its formation upon heat treatment is well characterised. Moreover, it represents the Amadori products from early Maillard reactions in which amino acids react with reducing carbohydrates, resulting in a loss of their availability. This is of importance for the essential amino acid lysine, which is also the limiting amino acid in many proteins. In order to evaluate the nutritional quality of a protein, the concomitant analysis of free - and nutritionally available - lysine and the amount of lysine reacted to form the respective MRP is essential, even for mildly processed foods. The other chemical markers of heat treatment such as CML, pyrraline, pentosidine or pronyl-lysine seem to be useful markers of the advanced stages of Maillard reactions. Compared to the conditions in which furosine is formed, these compounds are generated under more severe conditions of heat treatment. However, the concentrations analysed are significantly lower than those of furosine. Therefore, the nutritional evaluation of a food protein should include not only furosine, but also other chemical markers of heat treatment such as, for example, CML, pyrraline and pentosidine.     

Metabolic transit of Amadori products.

In several studies, the absorption and urinary excretion of free and protein bound Amadori products were measured in rats and humans. Both, in vitro tests with everted intestinal sac preparations and in vivo experiments, showed that there is no active intestinal transport of these compounds but an absorption by diffusion. Trials with tissue slices have shown that there was an uptake into the cells of the liver, kidneys and muscles. Metabolism of Amadori products, if it exists in animals, tends to be very low. Micoorganisms in the large intestines decompose the Amadori products almost completely. The profile of urinary excretion of Amadori products after the ingestion of test meals showed a rapid elimination of the absorbed part, while the fecal output, although low because of the hind gut fermentation, persisted up to 3 days. Only 1-3% of the ingested amounts of protein bound Amadori products were recovered in the urine, which suggests a low absorption rate.     

Browning reactions of Heyns rearrangement products

The browning rate of Heyns rearrangement products at 110°C under free access of oxygen is slower that that of Amadori rearrangement products. The maximum browning rate was observed at pH = 8.0. The browning was accelerated by Fe(III) and Cu(II) ions. The presence of Fe(II) ions, propyl gallate, and rutin caused lag periods but had no pronounced effect during the subsequent browning. Hydrogen peroxide bleached the melanoidin pigments but did not destroy the browning precursors. Sulphites inhibited the browning reaction. Fluorescence spectra differed from those of the respective Amadori products.     

The Strecker Degradation of Amino Acids: Newer Avenues for Flavor Formation

Newer aspects of the Strecker degradation related to foods are examined in terms of currently accepted mechanisms and isolated reaction intermediates. Emphasis is placed on Strecker and Strecker-like reactions between amino acids and lipid oxidation products, and terpenes or o-quinones as potential sources of novel flavor compounds. In addition, reactions are described in which Strecker aldehydes are formed directly from Amadori compounds instead of via amino acid/carbonyl reactions.     

Heat-induced decomposition of disaccharide Amadori compounds in quasi-water-free reaction conditions]

The thermally induced decomposition of disaccharide Amadori compounds has been compared to those of monosaccharide ones under almost water-free conditions. The structure of the synthesized maltulosyl compound has been proved to be 4C1-alpha-D-glucopyranosyl- (1----4)-2C5-beta-D-fructopyranosylglycine by 1H- and 13C-NMR spectroscopy. The decomposition of Amadori compounds has been used to study the kinetics of the browning reaction. Compared to fructosylglycine and maltotriulosylglycine, the browning of the disaccharide is faster. Curie point pyrolysis at 300 degrees C and investigation of the pyrolysate by gas chromatography/mass spectrometry have shown that the disaccharide component influences the thermal process. Furanes and furanones have been detected as predominant degradation products, the main one being 2(5H)-furanone. For the first time, we suggest a reaction pathway for the formation of these products via the Maillard reaction which includes 1,6-anhydroglucose.     

Interactions of fluoroquinolone antibacterial agents with aqueous chlorine: reaction kinetics, mechanisms, and transformation pathways

Kinetics, products, and mechanistic aspects of reactions between free available chlorine (HOCl/OCl-), ciprofloxacin (CF), and enrofloxacin (EF) were extensively investigated to elucidate the behavior of fluoroquinolone antibacterial agents during water chlorination processes. Although the molecular structures of these two substrates differ only with respect to degree of N(4) amine alkylation, CF and EF exhibit markedly different HOCl reaction kinetics and transformation pathways. HOCI reacts very rapidly at CF's secondary N(4) amine, forming a chloramine intermediate that spontaneously decays in aqueous solution by concerted piperazine fragmentation. In contrast, HOCl reacts relatively slowly at EF's tertiary N(4) amine, apparently forming a highly reactive chlorammonium intermediate (R3N-(4)Cl+) that can catalytically halogenate EF or other substrates present in solution. Flumequine, a fluoroquinolone that lacks the characteristic piperazine ring, exhibits no apparent reactivity toward HOCI but appears to undergo facile halodecarboxylation in the presence of R3N(4)-Cl+ species derived from EF. Measured reaction kinetics were validated in real water matrixes by modeling CF and EF losses in the presence of free chlorine residuals. Combined chlorine (CC) kinetics were determined under selected conditions to evaluate the potential significance of reactions with chloramines. CF's rapid kinetics in direct reactions with HOCl, and relatively high reactivity toward CC, indicate that secondary amine-containing fluoroquinolones should be readily transformed during chlorination of real waters, whether applied chlorine doses are present as free or combined residuals. However, EF's slower HOCl reaction kinetics, recalcitrance toward CC, and participation in the catalytic halogenation cycle described herein suggest that tertiary amine-containing fluoroquinolones will be comparatively stable during most full-scale water chlorination processes.     

The Comparison of the Contents of Sugar,Amadori, and Heyns Compounds in Fresh and Black Garlic

Black garlic is produced through thermal processing and is used as a healthy food throughout the world. Compared with fresh garlic, there are obvious changes in the color, taste, and biological functions of black garlic. To analyze and explain these changes, the contents of water‐soluble sugars, fructan, and the key intermediate compounds (Heyns and Amadori) of the Maillard reaction in fresh raw garlic and black garlic were investigated, which were important to control and to evaluate the quality of black garlic. The results showed that the fructan contents in the black garlics were decreased by more than 84.6% compared with the fresh raw garlics, which translated into changes in the fructose and glucose contents. The water‐soluble sugar content was drastically increased by values ranging from 187.79% to 790.96%. Therefore, the taste of the black garlic became very sweet. The sucrose content in black garlic was almost equivalent to fresh garlic. The Amadori and Heyns compounds were analyzed by HPLC‐MS/MS in multiple reaction monitoring mode using the different characteristic fragment ions of Heyns and Amadori compounds. The total content of the 3 main Amadori and 3 Heyns compounds in black garlic ranged from 762.53 to 280.56 μg/g, which was 40 to 100‐fold higher than the values in fresh raw garlic. This result was significant proof that the Maillard reaction in black garlic mainly utilized fructose and glucose, with some amino acids.     

赖氨酸Amadori和Heyns化合物热裂解产物对烟草风味的影响研究

  目的  比较赖氨酸Amadori和Heyns化合物的热解产物及对其烟草风味的影响。  方法  以赖氨酸和葡萄糖或果糖为原料,以偏重亚硫酸钠为催化剂、甲醇和冰醋酸为溶剂,分别合成赖氨酸的Amadori和Heyns化合物,采用在线热裂解-气相色谱/质谱联用技术(Py-GC/MS)对比了2种化合物的热解产物差异,并通过感官评吸实验比较了二者对卷烟风味的影响。  结果  （1）赖氨酸Amadori和Heyns化合物热解均能产生醛酮类、呋喃类、吡啶类、吡嗪类及吡咯类香味物质,同一类别产物的相对含量有较大差异。（2）赖氨酸Heyns化合物热解得到的风味成分数量更多。（3）赖氨酸Amadori化合物和Heyns化合物对卷烟的主要作用为增香、增浓和降低刺激,并使烟气更加流畅顺滑,赖氨酸Heyns化合物增加了卷烟白肋烟特征。  结论  赖氨酸Amadori化合物和Heyns化合物的热解产物不同,对卷烟风味的影响存在差异。      

Effect of Amadori rearrangement products on the non-enzymic browning in model systems

The Amadori product was prepared from D-glucose and L-alanine after Hashiba. The browning process was investigated by determining the absorbance at 520 nm, in aqueous solutions at 110 °C for 5–8 h. Because of the limited access of oxygen and its low solubility in the reaction medium, the browning proceeded after zeroth order kinetics with the maximum browning rate at pH = 8–9. The browning rate remained unaffected by additions of sodium sulphite, rutin. propyl gallate (except when present at high levels), iron(III)chloride or copper(II)chloride but decreased in presence of L-cysteine or iron(II)chloride. Hydrogen peroxide bleached the pigment but did not inhibit the subsequent browning of reaction products. Under experimental conditions the solution of Amadori product did not darken with substantially greater rate than the solution of D-glucose and L-alanine. Lower additions of D-glucose to the solution of Amadori product moderately increased the reaction rate while additions of L-alanine or L-hydroxyproline moderately decreased the browning rate.     

Effect of digestive process on Maillard reaction indexes and antioxidant properties of breakfast cereals

Extrusion, drying and toasting are the most representative manufacturing processes suffered by breakfast cereals, conjugating thermal/moisture conditions that allow the Maillard reaction (MR) and caramelisation development, as well as the destruction of thermally labile antioxidant compounds. However, other compounds – like Amadori products and hydroxymethylfurfural (HMF) – are originated from the MR and caramelisation, showing different biological activities, as the antioxidant activity. But breakfast cereals are ingested and then affected by the digestive process, and so that the aim of this work was to analyse the effects of the digestion on the bioaccessibility of certain MR products (Amadori compound and HMF) and on the antioxidant activity of corn-based breakfast cereals, using a standardized in vitro gastrointestinal digestion. After digestion approx. 90% HMF remained soluble, but in some cases HMF distribution between soluble/insoluble fractions was higher than the initial HMF measured in the raw cereal, suggesting a release of initially bound Amadori products and its conversion to HMF during the digestion process. The Amadori compound was uniformly distributed between both fractions. The antioxidant activity of the soluble fraction was always higher than that from the raw cereal in any of the antioxidant method employed; therefore the digestion increased the solubility of the antioxidant compounds.     

Evaluation of heat and oxidative damage during storage of processed tomato products. I. Study of heat damage indices

The evolution of heat damage during storage of tomato pulp, puree and paste was studied by accelerated aging tests. Heat damage indices—5‐hydroxymethyl‐2‐furfural (HMF), furosine and colour changes (ΔE)—were evaluated for tomato products stored at 30, 40 and 50 °C for up to 90 days. Furosine and ΔE values increased following pseudo‐zero‐order kinetics, and the higher the solid content of the products, the higher were the rate constant values. HMF formation followed pseudo‐first‐order kinetics in tomato pulp and pseudo‐zero‐order kinetics in puree and paste samples. Data show that heat damage reactions in tomato products proceed even at room temperature, and the kinetic model provided can be used to predict changes occurring during shelf‐life. © 2002 Society of Chemical Industry     

Glycidyl Fatty Acid Esters in Refined Edible Oils: A Review on Formation,Occurrence, Analysis,and Elimination Methods

Glycidyl fatty acid esters (GEs), one of the main contaminants in processed oils, are mainly formed during the deodorization step in the refining process of edible oils and therefore occur in almost all refined edible oils. GEs are potential carcinogens, due to the fact that they readily hydrolyze into the free form glycidol in the gastrointestinal tract, which has been found to induce tumors in various rat tissues. Furthermore, glycidol has already been identified as a “possible human carcinogen’’ (group 2A) by the Intl. Agency for Research on Cancer (IARC). Therefore, significant effort has been devoted to inhibit and eliminate the formation of GEs. The aim of this review is to provide a comprehensive summary on the following topics: (i) GE occurrence data for different edible oils and oil‐based food products, (ii) precursors of GEs, (iii) factors influencing the formation of GEs, (iv) potential reaction mechanisms involving the leaving group and reaction intermediates, and (v) analytical methods, including the indirect and direct methods. More importantly, the various elimination methods for GEs in refined edible oils are being reviewed with focus on 3 aspects: (i) inhibition and removal of reactants, (ii) modification of reactive conditions, and (iii) elimination of GE products.     

Application of Chromatographic Techniques in the Detection and Identification of Constituents Formed during Food Frying: A Review

Frying is one of the most popular food processing methods. However, many physicochemical reactions occur during frying, forming complex products in both the frying oil and the fried food. Chromatographic techniques have been successfully applied to characterize the products formed during food‐frying or during a simulated frying process. In this review, the specific products analyzed by gas chromatography (GC) and high‐performance liquid chromatography (HPLC) are elucidated in detail. The most studied components are polar compounds (such as volatile compounds, hydrolysis products, oxidized triacylglycerol [TAG] decomposition products, oxidized TAG monomers, sterol oxides, oxygenated TAG polymers, and acrylamide) and nonpolar compounds (such as cyclic fatty acid monomers and trans isomers), which are classified based on their polarity. However, the definite structures of TAG polymers and sterol oxides, and polymers analyzed by GC or HPLC‐based methods are only investigated in modeled reactions. Furthermore, some of the sample pretreatments and chromatographic methods are only used to analyze the known products. A number of earlier trace amounts of undetected products need to be investigated by more effective detection techniques. The development of multidimensional chromatographic techniques and elaborate mass spectrometry detectors makes composition analysis possible for the food‐frying process, which may effectively promote the development of quality monitoring and nutrition evaluation for the fried foods.     

Studies on the formation of furosine and pyridosine during acid hydrolysis of different Amadori products of lysine

The behavior of different lysine Amadori compounds during acid hydrolysis was investigated in order to determine the molar yield of furosine and the other hydrolysis products. Based on this, the conversion factors for calculating the content of Amadori compound and lysine modification before hydrolysis can be derived. For that purpose, the peptide-bound Amadori compounds N^k-(1-deoxy-D-fructosyl)-, N^k-(1-deoxy-D-tagatosyl)-, N^k-(1-deoxy-D-lactulosyl)- and N^k-(1-deoxy-D-maltulosyl)hippuryllysine as well as free N^k-(1-deoxy-D-fructosyl)lysine were synthesized. For isolation of peptide-bound Amadori compounds, an optimized enzyme-enhanced reversed phase-high pressure liquid chromatography procedure was developed. Pyridosine and N^k-(carboxymethyl)hippuryllysine were synthesized as reference materials. After acid hydrolysis with 6 M hydrochloric acid the, molar yields of furosine were determined to be 32% for fructosyllysine, 34% for lactulosyl- and maltulosyllysine and 42% for tagatosyllysine. Hydrolysis with 8 M hydrochloric acid resulted in a higher yield of furosine for Amadori compounds containing a fructosyl-moiety, 46% for fructosyllysine, 50% for lactulosyllysine and 51% for maltulosyllysine. Compared with this, the molar yield for furosine was not affected by concentration of hydrochloric acid in the case of tagatosyllysine. Based on these conversion factors a reliable calculation of the amount of Amadori compound or lysine modification and with it the evaluation of the progress of the "early" Maillard reaction in foods and biological samples is possible via the quantification of lysine and furosine after acid hydrolysis.     

A review of the kinetics of degradation of inosine monophosphate in some species of fish during chilled storage

A literature search was made for data on the concentrations of inosine monophosphate (IMP) and its degradation products, inosine (Ino) and hypoxanthine (Hx), in the flesh of vertebrate fish during storage in ice. Twenty‐one publications containing data for forty‐five species were selected for review. A mathematical model was developed for analysing the data by assuming that the kinetics of degradation of IMP could be modelled as consecutive first order reactions. The model was fitted to the data and in about half of the cases examined in the review the data suggested that IMP and degradation products were lost by leaching and the kinetic model was extended to allow for this loss. In all of the cases reviewed the mathematical model was a good fit to the experimental data and the reaction rates for the reactions are tabulated in the paper. In all species the concentration of IMP decreased as a first order reaction, but for thirteen of the species examined the enzyme model of IMP to Ino to Hx did not fit the data in that either Ino or Hx did not accumulate in the muscle. There were only a few examples of replications of storage trials within species and comparison of the outcomes of these replications suggested that season or, in the case of farmed fish, genetic stock or cultural practices might influence initial IMP concentrations or reaction rates.