Characterization of melanoidins by IR spectroscopy—II. Melanoidins of galactose with arginine, isoleucine, lysine and valine

The infrared spectra of melanoidins which were prepared from galactose and neutral and basic amino acids (at various ratios) support in general the conclusion gained in Part I of this series. A striking resemblance in the IR spectra was obtained in melanoidins which were prepared from a high ratio of sugar to amino acids (Type 1). The imprint of the amino acids was observed only in type 2 melanoidins, which are enriched with amino acids.     

Thermal characterization of natural and synthetic humic substances

Thermogravimetric technique was used for the characterization of natural (humic) and synthetic (melanoidins) substances. The influence of pH on the thermal stability of humic substances was studied. A similarity in thermal behaviour of natural humic substances and of melanoidins (prepared from an excess of sugar) and the unique thermal properties of melanoidins (prepared from basic amino acids) was observed. Thermal behavior of natural and synthetic substances was compared with model compounds of sugar, peptide and kerogen types.     

Melanoidins—kerogen precursors and geochemical lipid sinks: a study using pyrolysis gas chromatography (PGC)

Melanoidins, acidic polymeric products of amino acid/sugar condensation reactions, are shown to be capable of reacting with and binding functionalized lipid molecules. Pyrolysis gas chromatography is used to monitor the inclusion of lipids (alcohols and acids) into, and to monitor the changes in composition caused by artificial diagenesis of, the melanoidins. Artificial diagenesis of the lipidcontaining melanoidins produces a material resembling kerogen. The possible role of melanoidins in the formation of kerogens is discussed as are internal transformations within kerogens during diagenesis.     

银在含氨基酸热液中的物理化学行为

考虑到银主要富集在中低温热液阶段，同时考虑到成矿溶液中氨基酸的存在及其不同类型，对含银矿物样品在中性、碱性和酸性氨基酸热液中的物理化学行为分别进行了实验研究。结果表明，含有酸性氨基酸（谷氨酸）的热水溶液，比仅含ＮａＣｌ的热卤水、含碱性氨基酸（赖氨酸）和中性氨基酸（氨基乙酸和氨基丙酸）的热水溶液，更有利于银的活化和迁移。实验同时表明，银与各氨基酸形成的易溶配位化合物的稳定性受到温度的强烈影响。在２５℃左右，是银－氨基酸配位化合物稳定存在的最适宜温度条件；在１００℃以上，随温度的逐渐升高，银在含氨基酸热液中的溶出量明显减少。表明银－氨基酸的配位化合物强烈地分解，而使银得以更多地沉积。银在含氨基酸热液中的这种物理化学行为，和铅在含有酸性氨基酸（谷氨酸）、铜在含有碱性氨基酸（赖氨酸）热液中的活化、迁移与沉积作用不无相似之处     

Amino acid adsorption by clay minerals in distilled water

The adsorption of 15 protein amino acids from dilute (~ 10 μM) distilled water solutions onto organic-free kaolinite and montmorillonite clay minerals (1 wt% suspensions) was determined at room temperature over a 48 hour period. The systems came to steady state within 2 hours. Basic (positively charged) amino acids were strongly adsorbed (40–80% removal) by both clay minerals. Neutral (uncharged) amino acids were taken up appreciably (10–15%) by montmorillonite, but little if any (<5%) by kaolinite. Acidic (negatively charged) amino acids were adsorbed (20–35%) only by kaolinite. These adsorption patterns appear to be related in part to electrostatic interactions between the clay mineral surfaces and the different amino acid types. The measured extents and selectivities of adsorption onto these clay minerals are sufficiently great to potentially affect the distributions and reactions of free amino acids in natural environments.     

Characterization of melanoidins by IR spectroscopy—I. Galactose-glycine melanoidins

A comparative IR spectral study was conducted with synthetic melanoidins which were prepared from various ratios of sugars and amino acids and a pseudomelanoidin which was prepared from sugar only. A significant resemblance was observed between the pseudomelanoidin and the melanoidin prepared from a high (9:1) sugar ratio (type 1). Another series of melanoidins (type 2) consists of those prepared from an “excess” of amino acid (9:1 and 1:1).Type 1 showed the presence of carbonyl and hydroxyl groups as well as aromatic vibrations. The same groups were detected in the spectrum of the pseudomelanoidin. These features were observed in a very low concentration in the type 2 melanoidins.Carboxylic groups are present in pseudomelanoidin and in both types of the melanoidins. However, the acid strength of this group is high in melanoidin of type 2, but low in type 1 and in the pseudomelanoidin.The nitrogen atom which is involved in the melanoidin structure is present as a tertiary amine.Heat treatment of KBr discs containing glycine, galactose and a mixture thereof revealed that galactose was converted into pseudomelanoidin; a mixture of galactose-glycine yielded the corresponding melanoidin of type 2; no reaction was observed with glycine.     

Carbon-13 cross polarized magic-angle samples spinning nuclear magnetic resonance of melanoidins

Melanoidins synthesized from amino-acids and sugars in various ratios and humic substances from Hula Basin (Israel) have been investigated by ¹³C-CP/MAS NMR spectroscopy. Most spectra indicated a significant similarity between melanoidins and humics. It is suggested that the Maillard reaction plays a more significant role in the formation of humic substances than the “traditional” theory based on a lignin source. Several heterocyclic and heteroaromatic moieties (mainly furanoid, hydroxy-alkyl-furanone and hydroxy-alkyl-cyclopentenone) have been considered as major “building blocks” of humic substances and melanoidins.Aromaticities calculated from NMR spectral data of SM (“sugar” enriched melanoidins) and AAM (amino acid enriched melanoidins) coincide remarkably with the aromaticities of terrestrial and marine humics, respectively.     

Amino acid abundances and stereochemistry in hydrothermally altered sediments from the Juan de Fuca Ridge, northeastern Pacific Ocean.

The Juan de Fuca Ridge is a hydrothermally active, sediment covered, spreading ridge situated a few hundred kilometres off the west coast of North America in the northeastern Pacific Ocean. Sediments from seven sites drilled during the Ocean Drilling Program (ODP) Legs 139 and 168 were analyzed for total hydrolyzable amino acids (THAA), individual amino acid distributions, total organic C (TOC) and total N (TN) contents. The aim was to evaluate the effects of hydrothermal stress on the decomposition and transformation of sedimentary amino acids. Hydrolyzable amino acids account for up to 3.3% of the total organic C content and up to 12% of the total N content of the upper sediments. The total amounts of amino acids decrease significantly with depth in all drilled holes. This trend is particularly pronounced in holes with a thermal gradient of around 0.6 degrees C/m or higher. The most abundant amino acids in shallow sediments are glycine, alanine, lysine, glutamic acid, valine and histidine. The changes in amino acid distributions in low temperature holes are characterized by increased relative abundances of non-protein beta-alanine and gamma-aminobutyric acid. In high temperature holes the amino acid compositions are characterized by high abundances of glycine, alanine, serine, ornithine and histidine at depth. D/L ratios of samples with amino acid distributions similar to those found in acid hydrolysates of kerogen, indicate that racemization rates of amino acids bound by condensation reactions may be diminished.     

Late Precambrian and Early Cambrian in the East European platform

Carbon suboxide polymers reacted with hydroxylamine and ammonia under UV irradiation in aqueous medium to form amino acids such as glycine, alanine, serine, threonine, aspartic acid and glutamic acid. This finding suggests that carbon suboxide is a new candidate as starting material for the synthesis of biomolecules on the primitive earth.     

Comparison of the experimental and theoretical production of biogas by monosaccharides,disaccharides, and amino acids

The estimation of biogas production from organic monomers is very important for the optimal design, configuration, and efficient evaluation of the anaerobic digestion processes in a digester. The theoretical estimation of the biogas potential that is most used is that of Buswell and Boyle. In this work, we found that this estimate was much exaggerated compared to the real biogas potential determined in practice. For monosaccharides, we noted that the biogas potential of glucose was very low compared to that of fructose, even though the two substrates have the same chemical composition and molecular mass. The same result was observed for the disaccharides lactose and maltose. The amino acid valine produced more biogas than the amino acid cysteine did. The experimental potential remained lower than the calculated potential. An important difference existed between the experimental biogas potential of the six monomers investigated and the theoretical biogas potential. This indicated that the calculation of the biogas potential by the stereochemical equation of Buswell and Boyle was overstated and did not take into consideration the isometric form, spatial configuration, and intermediate metabolite produced by the monosaccharides in the four steps of anaerobic digestion. For the disaccharides, the theoretical calculations did not take into account the nature of the molecular components in carbohydrate, type of glycosidic bond, and intermediate metabolites of substrates for anaerobic digestion. Finally, for the amino acids, it does not take into account the ramification of the atomic components and the chemical nature of atoms in amino acids.     

Interaction of organic compounds with calcium carbonate—III. Amino acid composition of sorbed layers

Nitrogenous organic compounds in sorbed surface layers and in calcified organic matter associated with calcium carbonate sediment particles consist of 40–50% amino acids, 2% amino sugars and 25% ammonia. In grain size classes > 20 μm these compounds are mainly contained in the calcified protein of carbonate secreting organisms but with smaller grain sizes—and consequently increased specific surface area—they are contained in sorbed layers at the mineral surface. The composition of the sorbed layer is characterized by a predominance of neutral amino acids, a relative enrichment of basic and weakly polar amino acids, and a deficiency of acidic amino acids in comparison with the proteinaceous matter of calcifying organisms. The respective abundances for sorbed and calcified matter are: 505 and 380 Res./ of neutral amino acids, 262 and 450 Res./1000 of acidic amino acids, 92 and 51 Res./l000 of basic amino acids, and 141 and 129 Res./1000 of weakly polar amino acids.The composition of the sorbed layer appears to be the result of sorption of proteinaceous matter from solution since it reflects the free and peptide-bound amino acid composition of seawater. The characteristic amino acid assemblage could also be the result of preferential decomposition of protein and subsequent enrichment of neutral and basic amino acids; however, sorption from solution appears more likely since the total amount of amino acids sorbed to calcium carbonate (0.58 mg m ^?2) corresponds closely to the amount of protein known to cover one m² of aqueous substrate in monolayer arrangement. Sorption from solution is further supported by the low arginine/ornithine ratios in both the sorbed layer and the natural dissolved organic matter. This process might lead to a characteristic amino acid spectrum in fine grained calcareous sediments that reflects the composition of the dissolved organic matter in seawater rather than that of the carbonate secreting proteinaceous matter.     

Mineralogical impact on organic nitrogen across a long-term soil chronosequence (0.3-4100 kyr)

Large portions of organic N (ON) in soil exist tightly associated with minerals. Mineral effects on the type of interactions, chemical composition, and stability of ON, however, are poorly understood. We investigated mineral-associated ON along a Hawaiian soil chronosequence (0.3-4100 kyr) formed in basaltic tephra under comparable climatic, topographic, and vegetation conditions. Mineral-organic associations were separated according to density (ρ > 1.6 g/cm³), characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge fine structure (NEXAFS) and analyzed for amino acid enantiomers and amino sugars. The ¹⁴C activity of mineral-bound OC was estimated by accelerator mass spectrometry. The close OC-ON relationship (r = 0.96) and XPS results suggest that ON exists incorporated in bulk mineral-bound OM and likely becomes associated with minerals as part of sorbing OM. The youngest site (0.3 kyr), with soils mainly composed of primary minerals (olivine, pyroxene, feldspar) and with little ON, contained the largest proportion of hydrolyzable amino sugars and amino acids but with a small share of acidic amino acids (aspartic acid, glutamic acid). In soils of the intermediate weathering stage (20-400 kyr), where poorly crystalline minerals and metal(hydroxide)-organic precipitates prevail, more mineral-associated ON was present, containing a smaller proportion of hydrolyzable amino sugars and amino acids due to the preferential accumulation of other OM components such as lignin-derived phenols. Acidic amino acids were more abundant, reflecting the strong association of acidic organic components with metal(hydroxide)-organic precipitates and variable-charge minerals. In the final weathering stage (1400-4100 kyr) with well-crystalline secondary Fe and Al (hydr)oxides and kaolin minerals, mineral-organic associations held less ON and were, relative to lignin phenols, depleted in hydrolyzable amino sugars and amino acids, particularly in acidic amino acids. XPS and NEXAFS analyses showed that the majority (59-78%) of the mineral-associated ON is peptide N while 18-34% was aromatic N. Amino sugar ratios and d-alanine suggest that mineral-associated ON comprises a significant portion of bacterial residues, particularly in the subsoil. With increasing ¹⁴C age, a larger portion of peptide N was non-hydrolyzable, suggesting the accumulation of refractory compounds with time. The constant d/l ratios of lysine in topsoils indicate fresh proteinous material, likely due to continuous sorption of or exchange with fresh N-containing compounds. The ¹⁴C and the d/l signature revealed a longer turnover of proteinous components strongly bound to minerals (not NaOH-NaF-extractable). This study provides evidence that interactions with minerals are important in the transformation and stabilization of soil ON. Mineral-associated ON in topsoils seems actively involved in the N cycling of the study ecosystems, accentuating N limitation at the 0.3-kyr site but increasing N availability at older sites.     

我国“北京人”、“兰田人”和“元谋人”产地骨化石中氨基酸的地球化学

氨基酸是生命物质中普遍存在的一类重要的有机化合物,它是构成蛋白质的“砖块”。一个最简单的氨基酸分子至少必须含有一个羧基和一个氨基的官能团。在生物的蛋白质中通常只包括有二十种氨基酸,叫做蛋白氨基酸。但是自然界还存在其它种类的氨基酸,因为它们一般不存在于蛋白质中,所以叫做非蛋白氨基酸。除了最简单的甘氨酸外,所有的氨基酸都含有一个以上的不对称的碳原子。含有一个不对称碳原子的氨基酸可以存在L和D型两种结构的对映体。所有的蛋白质氨基酸都属L构型。     

Non-racemic amino acids in the Murray and Murchison meteorites.

Small (1.0-9.2%) L-enantiomer excesses were found in six alpha-methyl-alpha-amino alkanoic acids from the Murchison (2.8-9.2%) and Murray (1.0-6.0%) carbonaceous chondrites by gas chromatography-mass spectroscopy of their N-trifluoroacetyl or N-pentafluoropropyl isopropyl esters. These amino acids [2-amino-2,3-dimethylpentanoic acid (both diastereomers), isovaline, alpha-methyl norvaline, alpha-methyl valine, and alpha-methyl norleucine] are either unknown or rare in the terrestrial biosphere. Enantiomeric excesses were either not observed in the four alpha-H-alpha-amino alkanoic acids analyzed (alpha-amino-n-butyric acid, norvaline, alanine, and valine) or were attributed to terrestrial contamination. The substantial excess of L-alanine reported by others was not found in the alanine in fractionated extracts of either meteorite. The enantiomeric excesses reported for the alpha-methyl amino acids may be the result of partial photoresolution of racemic mixtures caused by ultraviolet circularly polarized light in the presolar cloud. The alpha-methyl-alpha-amino alkanoic acids could have been significant in the origin of terrestrial homochirality given their resistance to racemization and the possibility for amplification of their enantiomeric excesses suggested by the strong tendency of their polymers to form chiral secondary structure.     

Summary and implications of reported amino acid concentrations in the Murchison meteorite

A study of literature reports of the concentrations of amino acids in extracts from the Murchison meteorite shows that many of the concentration ratios are constant. There are two possible interpretations of these ratios. One is that they are controlled by the pathways through which the amino acids formed, from which it follows that the amino acids are distributed in the same proportions throughout the meteorite. The other interpretation is that the ratios result from the analytical procedures used to extract the amino acids from the meteorite. These methods rely heavily on high-temperature (100 degrees C) aqueous extraction and subsequent high-temperature acid hydrolysis. A correlation was observed in the present study between the relative concentrations of several amino acids in the meteorite extracts and their relative aqueous solubilities at 100 degrees C (alanine, valine, leucine, isoleucine, norleucine, aspartic acid, glutamic acid and glycine). The extract solutions are dilute, and far from the saturation limits, but these correlations suggest that the sampling procedure affects directly the reported concentrations for these amino acids. Ratios of the concentration of serine to those of glycine are also constant but cannot be accounted for solely by relative solubilities, and, as suggested elsewhere, serine as well as phenylalanine and methionine may be terrestrial contaminants. Data for beta-alanine, alpha-aminobutyric acid, proline, sarcosine, alloisoleucine, beta-aminoisobutyric acid, beta-aminobutyric acid, and threonine also show constant abundances relative to glycine, but lack of solubility data at extraction conditions prohibits evaluating the extent of possible sampling bias for these amino acids. If the extraction process does not bias the results, and all extractable amino acids are removed from meteorite samples, then the properties of amino acids which control both their solubilities and their concentrations in the meteorite need to be established. The possibility of sampling bias needs to be tested experimentally before concluding that extraction is complete, and that the constant relative abundances indicate that the relative concentrations of amino acids are homogeneous in the meteorite.     

The Strecker synthesis as a source of amino acids in carbonaceous chondrites: deuterium retention during synthesis

Deuterium-enriched amino acids occur in the Murchison carbonaceous chondrite. Synthesis from D-enriched interstellar precursors by Strecker reactions during aqueous alteration of the parent body has been proposed. To test this hypothesis, we have measured the retention of deuterium in amino acids produced from HCN, NH3, and formaldehyde-D2, acetaldehyde-D4, and acetone-D6 in H2O. The isotopic label is 50% to 98% retained, with variations in retentivity depending on the amino acid and the reaction conditions. If amino acids, once formed on the parent body by the Strecker synthesis, lose no deuterium by subsequent exchange with water or H-bearing minerals, then the observed deuterium isotopic composition of Murchison amino acids represents as much as 50% or more of the enrichments inherited from their interstellar precursors. Imino diacids are prominent side products of the Strecker synthesis which have not been reported in carbonaceous chondrites. Under the conditions of the Strecker reaction using deuterium labeled aldehydes and ketones, unlabeled amino acids are also formed by an HCN polymerization route indicating multiple pathways for the synthesis of amino acids in meteorites.     

黄土高原红粘土与黄土古土壤粒度特征对比--红粘土风成成因的新证据

对黄土高原具有代表意义四个剖面的晚第三纪红粘土样品进行了粒度分析,并将结果与典型风成黄土古土壤样品的粒度特征进行详细对比,得到红粘土是风成成因的沉积学证据。结果表明,黄土高原红粘土与其上覆第四纪古土壤形成环境相似,红粘土是在相对于黄土堆积搬运风动力变幅小的条件下沉积的,在沉积之后受到较强的风化成壤改造作用。     

论晋北石炭二叠系紫色高岭石粘土的成因

晋北地区石炭二叠系煤层中与四号及九号煤伴生的含有机质的软质耐火粘土,即高岭石粘上,俗称紫矸或紫木节。对紫矸的成因过去有两种看法:(1)原生沉积的;(2)后期风化残积“由煤变来的”。笔者认为除这两个因素同时存在外,还与成岩后生作用中有机酸的淋滤和高岭石的重结晶、有序化等有关,尤其是后期风化表生作用使有机质氧化淋滤去SiO_2形成一水软铝石、褪色、溶蚀多孔、质地疏松,形成今日所见紫色高岭石粘土。     

Influence of organic-mineral aggregates on microbial degradation of the dinoflagellate Scrippsiella trochoidea

Aggregation of particulate organic matter (POM) and mineral grains may result in physical protection of organic matter (OM). To test this, phytoplankton cells of the dinoflagellate Scrippsiella trochoidea were inoculated with a natural bacterial assemblage and incubated with or without the clay montmorillonite. Within 5 h, aggregation of phytoplankton OM and clay resulted in transfer of the majority (∼80%) of OM into the >1.6 g cm⁻³ density fraction. Degradation of particulate organic carbon (POC), particulate nitrogen (PN), dissolved organic carbon (DOC), and dissolved and particulate total hydrolyzable amino acids (THAA), were modeled with a multi-G approach. Quantity of resistant OM was between two and four times larger during clay incubation relative to clay-free incubation. The two incubations did not exhibit significant differences in degradation state of particulate amino acids nor were there indications of preferential sorption of basic amino acids. The results suggest that a considerable fraction of phytoplankton OM can become resistant, at least on a timescale of weeks, mostly due to aggregation of POM and clay mineral grains.     

Kaolin-Kohlentonsteine im flözführenden Oberkarbon des Niederrheinisch-Westfälischen Steinkohlenreviers

Starting from general considerations of the rocks existing in the Ruhr Carboniferous and the mineral layers in coal seams, an informative review is given about the definition of clay stones and kaolin coal tonsteins as well as about the stratigraphic distribution of key horizons with special regard to the kaolin coal tonsteins. Information follows about the first evidence of individual kaolin coal tonsteins, their existence in the normal geologic columns and more recent stratigraphic sections as well as about the concentration of repositories. Besides, the kaolin coal tonsteins are characterized according to their macroscopic and microscopic external form. The paper reports about their material constituents (mineral components, trace elements, anorganic chemical constituents and organic substances in form of coal hydrates and amino acids). The paper closes with some statements about the importance and utilization of kaolin coal tonsteins to solve local and regional duties in mining geology.