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1.
The color tone of melanoidins prepared from model systems by heating mixtures of 1 mmole amino acid or peptide and 1 mmole sugar in aqueous solution was investigated using ΔA (change of log absorbance per 100 mμ) as a parameter of color tone.

Amino acids and peptides were responsible for the color tone of melanoidins while sugar had no effect on the color tone. In addition, the color tone of melanoidin varied as the concentration ratio of amino acid to sugar changed. Melanoidins from tryptophan- and proline-xylose systems exhibited the lightest color tone. Melanoidins from peptides generally exhibited dark tones compared with those from amino acids.

Using the distribution pattern of color components fractionated by DEAE-cellulose chromatography, melanoidins have been classed into 4 groups based on the percentage of PI (non-adsorbed fraction on DEAE-cellulose): group 1, melanoidins containing 90 ~ 100% P1; group 2, 70~80% PI; group 3, 30~50% P1; group 4, less than 20% P1. Melanoidins derived from most amino acids examined, those from basic amino acids and proline, those from glutamic acid and glycine, and those from peptides and amino terminal monocarboxylic acids belonged to groups 2, 1, 3, and 4, respectively.

The color tone of each color component except for PI was generally very similar in most melanoidins. However, the color tone of P1 was variable. Therefore, melanoidin is composed of various color components having intrinsic color tones from yellowish-brown to dark brown and their color tone depends upon the variation of the amount of color components and upon the color tone of P1.  相似文献   

2.
Nondialyzable melanoidin formed in a model system of glucose and glycine was applied on thin layer gel electrofocusing in a polyacrylamide gel. The electrofocusing profile differed according to the reaction time: the pI of the melanoidin formed in the early stage of the reaction was less than 2.9 and, as the reaction progressed, the pI of the melanoidin formed gradually shifted to a less acidic value, from 2.9 to 3.3. Those from the xylose and glycine model system gave a similar profile to that of the glucose system.

Preparative separation of the nondialyzable melanoidin, which was formed by heating the glucose system for 7hr, was performed by flat-bed electrofocusing in Sephadex gel. At least 14 melanoidin bands were clearly electrofocused at a pH range of 2.7-3.3 and about 59% of the melanoidin applied remained unaffected by electrophoresis at the starting position. The major component of electrofocused melanoidin was pI 3.00, this being made up of 12.5% of the total amount of electrofocused melanoidin. The molecular weight of melanoidin affected by electrophoresis was about 25,000, regardless of the pI value of the melanoidin components. The reducing activity, estimated by the potassium ferricyanide method, showed that the lower the pI of melanoidin, the higher was the reducing activity.

The addition of hydrochloric acid to the melanoidin solution caused it to gradually become viscous and the melanoidin was precipitated below pH 3.0-3.5, corresponding approximately to ampholite. This feature can be used as a method to prepare nondialyzable melanoidin in a short time.  相似文献   

3.
The nondialyzable melanoidin prepared from glucose-ammonia system (kept in pH 5.3~6.0 during the reaction) was hydrolyzed. The hydrolyzate was fractionated by DEAE-cellulose column and Dowex 50 W column. Deoxyfructosazine and its 6-isomer were respectively isolated from main two fractions, and identified. Even on boiling the melanoidin in aqueous solution, these pyrazines as well as imidazoles and β-hydroxy pyridines in the melanoidin were liberated.

Furthermore, amounts of these heterocyclic compounds liberated from the nondialyzable melanoidin and the fractionated melanoidins (fractionated into five fractions on DEAE-cellulose column according to the method described previously) were examined.

The results obtained seem to suggest that these heterocyclic compounds are not present probably as a molecular skelton or an inclusion compound in the melanoidin, but as a small moiety of the melanoidin molecule with loose chemical bond.  相似文献   

4.
Proteinoids have been demonstrated as complexes of amino acid polymers with melanoidin pigments. Some physico-chemical properties of proteinoid pigments were studied in comparison with the standard melanoidins. Proteinoid pigments were able to enhance oxidoreduction and hydrolysis reactions, and their activity was comparable with the activity of the corresponding polyamino acid components or even of the entire proteinoids. The pigmented proteinoids had relatively strong ESR signal indicating the presence of free radicals into melanoidin components. Hypothetical participation of proteinoid melanoidin pigments in prebiotic evolution is discussed.  相似文献   

5.
Melanoidins are the high molecular weight brown end products of the Maillard reaction. They are formed during heat processing of foods like coffee, bread, malt, and beef. A chemical definition of these food polymers is still impossible, despite several efforts to determine their structure. In the last years, the interest in research on melanoidins has increased due to their biological activities. Coffee brew is one of the main sources of melanoidins in human diet. Various melanoidin fractions were obtained by applying chromatographic separation techniques or specific isolation procedures, allowing, a partial view on structural features and diversity of coffee brew melanoidins. Different melanoidin populations can be found with respect to total carbohydrate contents and their structural features. In this paper, the recent advances in research on coffee melanoidin structures and formation mechanisms are reviewed. The participation of hydroxycinnamates in melanoidin formation, especially true for coffee melanoidins, is a hypothesis older than three decades, but only recently more consistent data have been obtained for their presence. Although the role of hydroxycinnamates in melanoidin formation is not yet completely understood, it was demonstrated that the interaction between phenolic compounds and melanoidins can be of non-covalent or of covalent nature. The most likely linkage point is through the protein fragments incorporated in the coffee melanoidin during the roasting process, although carbohydrates, such as arabinose, seem to be possible binding sites for the chlorogenic acid derivatives on these brown structures, too.  相似文献   

6.
Typha angustifolia was evaluated for various heavy metals (Cu, Pb, Ni, Fe, Mn, and Zn) bioremediation potential from aqueous solution containing variable concentrations of phenol (100–800 mg l?1) and melanoidin (2500–8500 Co–Pt) at 20, 40, and 60 days. The concentration of phenol (200–400 mg l?1) along with melanoidin 2500 Co–Pt showed optimum for phytoremediation of tested heavy metals, while, higher concentrations of melanoidin (5600–8500 Co–Pt) showed toxic effect on T. angustifolia along with phenol. Phenol and melanoidin showed adverse effect on T. angustifolia of up to 20 days incubation, but this leads to induction of peroxidase and ascorbic acid activity to cope with adverse conditions. Subsequently, as pollutants were decreased along with plant growth, peroxidase and ascorbic acid also declined. However, with reduction of peroxidase, catalase level was increased. The Cu, Zn, and Ni were accumulated at maximum in all tested conditions. The TEM observations of T. angustifolia showed clotted deposition of metals and shrinkage of cell in root, breakdown of spongy and palisade parenchyma of leaves at higher concentration of phenol (100 mg l?1) and melanoidin (5500 Co–Pt). Thus, this study concluded that T. angustifolia could be a potential phytoremediator for heavy metals from metal, melanoidin, and phenol containing industrial wastewater at optimized condition.  相似文献   

7.
Summary

Wheat bran contains several ester-linked dehydrodimers of ferulic acid, which were detected and quantified after sequential alkaline hydrolysis. The major dimers released were: trans-5-[(E)-2-carboxyvinyl]-2-(4-hydroxy-3-methoxy-phenyl)-7-methoxy-2,3-dihydrobenzofuran-3-carboxylic acid (5–8-BendiFA), (Z)-β-(4-[(E)-2-carboxyvinyl]-2-methoxy-phenoxy)-4-hydroxy-3-methoxycinnamic acid (8-O-4-diFA) and (E,E)-4,4′-dihydroxy-5,5′-dimethoxy-3,3′-bicinnamic acid (5–5-diFA). trans-7-hydroxy-1-(4-hydroxy-3methoxyphenyl)-6-methoxy-1,2-dihydro-naphthalene-2,3-dicarboxylic acid (8–8-diFA cyclic form) and 4,4′-dihydroxy-3,3′-dimethoxy-β,β'-bicinnamic acid (8–8-diFA non cyclic form) were not detected. One of the most abundant dimers, 8-O-4-diFA, was purified from de-starched wheat bran after alkaline hydrolysis and preparative HPLC. The resultant product was identical to the chemically synthesised 8-O-4-dimer by TLC and HPLC as confirmed by 1H-NMR and mass spectrometry. The absorption maxima and absorption coefficients for the synthetic compound in ethanol were: λmax: 323 nm, λmin: 258 nm, ελmax (M?1cm?1): 24800 ± 2100 and ε280 (M?1cm?1): 19700 ± 1100. The antioxidant properties of 8-O-4-diFA were assessed using: (a) inhibition of ascorbate/iron-induced peroxidation of phosphatidylcholine liposomes and; (b) scavenging of the radical cation of 2,2′-azinobis (3-ethyl-benzothiazoline-6-sulphonate) (ABTS) relative to the water-soluble vitamin E analogue, Trolox C. The 8-O-4-diFA was a better antioxidant than ferulic acid in both lipid and aqueous phases. This is the first report of the antioxidant activity of a natural diferulate obtained from a plant.  相似文献   

8.
The Nd+3, Ho+3 and Eu+3 compounds with glycine, alanine and glutamic acid were synthesized and obtained as monocrystals.Absorption spectra in the range 8000–35 500 cm?1 were measured along the crystallographic axes at room temperature on a Cary 14 spectrophotometerLuminescence spectra were recorded at the same temperature in the range 9000–16 600 cm?1.Intensities of the ff transitions were analyzed on the basis of the Judd theory, taking the dependence of intensity on the crystallographic axis position into account.Considerable differences in hypersensitive transitions in crystals with alanine, glycine and glutamic acid, whose symmetry changed from triclinic to monoclinic, were explained in terms of differences in the MeO distances.  相似文献   

9.
The hydrolyzate of the melanoidin prepared from glucose-ammonia system (kept in pH 5.3~6.0 during the reaction) was fractionated into the two fractions of non-adsorbate and adsorbate on Amberlite IR-120 (H+-form). In the present paper, the adsorbed fraction (Fraction B) was examined.

Paper chromatographic examination of the Fraction B indicated the presence of at least eight compounds positive to diazotized sulphanilic acid reagent. The two compounds of them (indicated orange and orange-yellow color) were isolated and identified as 2-methyl-5-hydroxy-pyridine and 2-hydroxymethyl-5-hydroxy-pyridine, respectively.

It is probable that these compounds would loosely be bound as a small moiety in the melanoidin molecule.  相似文献   

10.
The effect of melanoidin, prepared with a D-glucose and glycine system, on cholesterol metabolism in rats was examined. Male rats of the Wistar strain weighing ca. 140 g were fed a high-cholesterol diet supplemented with nondialyzable melanoidin for three weeks. The dietary melanoidin suppressed elevation of the cholesterol level in both plasma and liver, while the cholesterol levels in feces and the contents of the caecum decreased unexpectedly. Neutral steroids other than cholesterol also decreased. However, chromatograhy of fecal steroids indicated that melanoidin markedly affected the intestinal metabolism of neutral steroids, including cholesterol. On the other hand, the fecal recovery of radioactivity from orally ingested 26 [27]-14C cholesterol was promoted by the added melanoidin, although the radioactive species were not identified. This suggested that the cholesterol level decreased due to the interference of melanoidin in the intestinal absorption of cholesterol.  相似文献   

11.
Nondiffusable melanoidin obtained from a glycine-xylose system was heated in aqueous media, and the resulting chemical changes, as affected by the presence of oxygen, pH value, temperature and the addition of transitional metals, were investigated.

Melanoidin, when heated at 90°C in an aqueous solution, caused remarkable discolorization accompanied by the development of fluorescence, oxygen consumption and a noticeable variation of reductone content. Heated melanoidin became polydispersive in molecular weight on gel filtration chromatograms. There appeared reductones, ninhydrin-positive substances, fluorescent substances, aromatic amines, aliphatic carbonyls, and aliphatic primary amines and/or methylene groups in diffusâtes of melanoidin heated in various media.

An increase in pH value favored oxidative discolorization, while an increase in the concentration of transitional metals except Mn2+ restrained the discolorization. In the absence of oxygen, heated melanoidin brought about a slight strengthening of color and the accumulation of reductones ca. fifteen times more than the initial level, while in the presence of oxygen the increase of reductone content at the early period was followed by a rapid decrease.

According to the results obtained, the ambivalent reactivity of melanoidin, i.e. polymerization (colorization) and depolymerization (discolorization), was discussed in relation to influencing factors. A mechanism for the production of reductones in heated melanoidin was also proposed.  相似文献   

12.
Peptic hydrolyzate of soy protein was submitted to the plastein reaction with α-chymotrypsin under the following condition: substrate concentration, 20%; enzyme-substrate ratio by weight, 1/100; reaction pH, 7.0; and reaction temperature, 37°C. The plastein yield resulting from the plastein reaction for 24 hr was found to depend on the degree of hydrolysis of the substrate (per cent ratio between nitrogen amount in 10% trichloroacetic acid soluble nitrogen and that in whole hydrolyzate); the optimum degree of hydrolysis for the highest plastein yield seemed to lie around 80%. A turbidity appeared in the process of the plastein reaction, whose intensity was correlative to the plastein yield. The peptic hydrolyzate of soy protein per se had bitterness and its magnitude decreased with increasing plastein yield.

As a result of the plastein reaction applied for 24 hr to the hydrolyzate whose degree of hydrolysis was 80%, the average molecular weight estimated by the change in amino nitrogen content increased by approximately three times. The molecular weight distribution pattern obtained by gel filtration supported the above result. The total amount of amino acids liberated from the plastein reaction product by its treatment with either leucine aminopeptidase or carboxypeptidase A was significantly less than that liberated from the original hydrolyzate by its similar treatment. This result also supports the formation of higher-molecular protein-like substances by the plastein reaction. Deuteration study followed by IR spectrometry showed the occurrence of peptide bond formation, i.e. decrease in ionized carboxyl group at 1575 cm?1 and increase in deuterated amide at 1450 cm?1, even at the earlier stages of the plastein reaction.  相似文献   

13.
ABSTRACT

FT-IR and FT-Raman spectra of 2,2′-bipyridine-3,3′-dicarboxylic acid (B3DA), 2,2′-bipyridine-4,4′-dicarboxylic acid (B4DA) and 2,2′-bipyridine-5,5′-dicarboxylic acid (B5DA) were recorded and analysed. The quantum chemical calculations of the title compounds begin with barrier potentials at different rotation angles around the C–C′ and C–Cα bonds in order to arrive conformation of lowest energy using DFT employing B3LYP functional with 6-311++G(d,p) basis set. This confirmation was further optimised to get the global minimum geometry. The vibrational frequencies along with IR, Raman intensities were computed, the rms error between observed and calculated frequencies were 11.2 cm?1, 10.2 cm?1 and 12.2 cm?1 for B3DA, B4DA, and B5DA. An 87-element modified valence force field is derived by solving the inverse vibrational problem using Wilson’s GF matrix method. This force field is refined using 163 observed fundamentals employing in overlay least-squares technique. The average error between computed and experimental frequencies was found as 12.85 cm?1 using potential energy distribution (PED) and eigenvectors. By using the gauge-independent atomic orbital (GIAO) method calculate the 1H and 13C NMR chemical shifts of the molecules and compared with experimental results. The first-order hyperpolarisability, HOMO and LUMO energies, molecular electrostatic potential (MESP) and natural orbital analysis (NBO) of titled compounds were evaluated using DFT.  相似文献   

14.
Far-infrared spectra of poly-L -alanines having the α-helical conformation and the β-form structure were measured. The spectra of glycine–L -alanine copolymer, silk fibroin, and copoly-D ,L -alanines with different D :L compositions were also measured. In addition to the bands so far reported, four bands at 190, 107, 120, and 90 cm?1were found for the α-helix conformation and the two bands at 442 and 247 cm?1 were found for the β form. The 442 cm?1 band consists of the parallel 432 cm?1 and perpendicular 445 cm?1 bands. The 247 cm?1 band is well defined and has strong dichroism parallel to the direction of stretching. These two bands appear also for silk fibroin and glycine–L -alanine copolymer. All the far-infrared bands of copoly-D ,L -alanines can be interpreted as α-helix bands, the three peaks at 580, 478, and 420 cm?1 being ascribed to the D -residue incorporated into the right-handed α-helix or to the L -residue in the left-handed α-helix.  相似文献   

15.
During one growing period, 5-year-old spruce trees (Picea abies L., Karst.) were exposed in environmental chambers to elevated concentrations of carbon dioxide (750 cm3 m?3) and ozone (008 cm3 m?3) as single variables or in combination. Control concentrations of the gases were 350cm3 m?3CO2 and 0.02 cm3 m ?3 ozone. To investigate whether an elevated CO2 concentration can prevent adverse ozone effects by reducing oxidative stress, the activities of the protective enzymes superoxide dismutase, catalase and peroxidase were determined. Furthermore, shoot biomass, pigment and protein contents of two needle age classes were investigated. Ozone caused pigment reduction and visible injury in the previous year's needles and growth reduction in the current year's shoots. In the presence of elevated concentrations of ozone and CO2, growth reduction in the current year's shoots was prevented, but emergence of visible damage in the previous year's needles was only delayed and pigment reduction was still found. Elevated concentrations of ozone or CO2 as single variables caused a significant reduction in the activities of superoxide dismutase and catalase in the current year's needles. Minimum activities of superoxide dismutase and catalase and decreased peroxidase activities were found in both needle age classes from spruce trees grown at enhanced concentrations of both CO2 and ozone. These results suggest a reduced tolerance to oxidative stress in spruce trees under conditions of elevated concentrations of both CO2 and ozone.  相似文献   

16.
Abstract

The results of Raman and Infrared (IR) spectroscopic investigations on the vibrational modes of dimethyl phosphorothioate (DMPS) anion, [(CH3O)2(POS)]?, are reported. Ab initio calculations of the vibrational modes, the IR and Raman spectra and the interatomic force constants of DMPS were performed. A normal mode calculation was performed and the results were used to calculate the potential energy distribution for the vibrational modes. This analysis shows that in DMPS the P-S stretching mode has a frequency of about 630 cm?1 and an angle bending mode involving the sulfur atom has a frequency of about 440 cm?1. The proposed vibrational mode assignments will serve as marker bands in the conformational studies of phosphorothioate oligonucleotides which play a central role in the novel antisense therapeutic paradigm.  相似文献   

17.
The absorption and excretion of melanoidins, a mixture of the low- and high-molecular weight components (LMM and HMM), and the LMM component prepared from a l-lysine^d-glucose system, at pH 7.4 and 9.0, respectively, and the effects of these melanoidins on cholesterol metabolism were examined in rats. Weanling male rats of the Wistar strain weighing about 50 g were fed diets containing 10% casein (10C) with 3% of a melanoidin or 25% casein (25C) with 4% of the melanoidin for 12 weeks, and the 25C diet including 3% of the melanoidin or LMM for 8 weeks. The growth and organ weights of the melanoidin-supplied groups were not different from those of the control ones. In rats given the melanoidin diets with both protein levels, the kidneys became dark brownish due to the accumulation of the melanoidin, though the accumulated amount was extremely small (nearly 0.5 mg/g wet kidney), and gel filtration chromatography of a water extract of the kidneys on Sephadex G-75 showed that the deposited melanoidin was the LMM component. Most of the ingested melanoidin, however, was excreted in the feces, and on comparison of the gel chromatographic patterns, the melanoidin groups were found to have more fecal LMM than the control ones. When rats were provided with LMM, HMM increased in their feces. The addition of melanoidin suppressed the level of plasma total cholesterol and elevated the fecal excretion of total lipids and total cholesterol. The urinary contents of protein and total creatinine did not differ from those in the control groups.  相似文献   

18.
Hydrolysis and absorption of glycylglycine and glycyl-L-leucine as well as absorption of glycine and leucine were studied in chronic experiments on rats with their isolated small intestine loop. Values of the “true” kinetic constants (with taking into account effect of the preepithelial layer) were determined to be as follows: (1) K t = 46.7 ± 4.0 and 2.15 ± 0.59 mM, J max = 0.74 ± 0.15 and 0.16 ± 0.03 μmol min?1 cm?1 (for transport of free glycine and leucine, respectively); (2) K t = 4.4 ± 0.6 and 4.8 ± 0.9 mM, J max = 0.24 ± 0.02 and 0.23 ± 0.02 μmol min?1 cm?1 (for transport of glycylglycine and glycyl-L-leucine, respectively); (3) K M = 5.4 ± 1.0 and 38.2 ± 4.4 mM, V max = 0.09 ± 0.02 and 0.24 ± 0.07 μmol min?1 cm?1 (for membrane hydrolysis of these dipeptides, respectively). According to our calculations, in the wide range of the initial glycylglycine concentrations (2.5–40 mM) a part of the peptide component in its total absorption accounts for 0.77–0.80. In the case of glycyl-L-leucine a part of the peptide component in the total glycine absorption decreases from 0.89 to 0.84, while in the total leucine absorption—from 0.86 to 0.71, the initial dipeptide concentration rising from 5 to 40 mM. The obtained results show that the peptide component prevails in absorption of the studied dipeptides in the rat small intestine, but its role is much lesser than what many authors believe. In the case of glycyl-L-leucine, the peptide component can achieve saturation in the range of high substrate concentrations, its part decreasing essentially to become compared with absorption of free amino acids formed as a result of the dipeptide membrane hydrolysis.  相似文献   

19.
The metabolism of labeled indole-3-acetic acid (IAA-2-14C) was investigated in Parthenocissus tricuspidata crown gall callus tissue. After 48 hours incubation, 85 to 90% of the supplied IAA was taken up by the tissue, and of that taken up, about 45% was conjugated with five amino acids. The conjugates found were aspartic and glutamic acid (minor ones) as well as glycine, alanine, and valine (major ones). The last four are being reported for the first time as metabolites of IAA. These conjugates were identified through their chromatographic properties, hydrolysis products, and their mass spectra. The possible significance of these amino acid conjugates is discussed.  相似文献   

20.
BACKGROUND: Extracellular urease proteins located on the surface of Helicobacter pylori are gastric mucin-targeted adhesins, which play an important role in infection and colonization to the host. In this study we have determined the inhibitory activity of a variety of melanoidins, protein-derived advanced Maillard reaction products, ubiquitously found in heat-treated foods, on urease-gastric mucin adhesion. In addition, we have determined the anticolonization effect of melanoidin I, prepared by the Maillard reaction between casein and lactose, in an animal model and in human subjects infected with this bacterium. METHODS: The inhibitory activity of each compound was determined by a competitive binding assay of labeled gastric mucin to plate-immobilized urease. Melanoidin I was used in an in vivo trial using euthymic hairless mice as an infection model. Melanoidin I was consumed for 8 weeks by subjects infected with H. pylori. The [(13)C] urease breath test and H. pylori-specific antigen in the stool (HpSA) test were performed on subjects at week 0 and week 8. RESULTS: A variety of food protein-derived melanoidins strongly inhibited urease-gastric mucin adhesion in the concentration range of 10 micro g/ml to 100 micro g/ml. In particular, melanoidin I significantly (p <.05) suppressed colonization of H. pylori in mice when given for 10 weeks via the diets. Eight weeks daily intake of 3 g melanoidin I significantly (p <.05) decreased the optical density of HpSA in subjects. CONCLUSION: Foods containing protein-derived melanoidins may be an alternative to antibiotic-based therapy to prevent H. pylori that combines safety, ease of administration and efficacy.  相似文献   

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