Gas-liquid chromatography of lipids,carbohydrates and amino acids

Gas-liquid chromatography is primarily a powerful separating tool. Compounds can be trapped as they emerge from the GLC apparatus for analysis by mass spectrometry and infrared or ultraviolet spectrophotometry, or the emerging separated components may flow directly into one of these instruments making positive identification of the components possible. Quantitative analyses of fats and oils are possible when certain requirements are observed. A combination of fatty acid, triglyceride and sterol analyses offers promise of a rapid means for the identification of fats and oils and their admixture or adulteration. Progress has been made on the preparation of derivatives of carbohydrates and amino acids such that these compounds may soon be analyzed as readily by GLC as lipids are today. Presented at the AOCS-AACC Joint Meeting, Washington, D.C., April 1968. E. Utiliz. Res. Dev. Div., ARS, USDA.     

氨基树脂制备聚脲多元醇

将三聚氰胺进行改性制备氨基树脂即多元胺溶液,再将氨基树脂用于制备聚脲多元醇(PHD),并对其合成原理、合成工艺及其关键影响因素等进行了研究。用红外光谱、NDJ-1型旋转式黏度计、LG10-24型离心机、透射电镜(TEM)、热重分析(TG)等对聚脲分散体进行测试与表征。     

Variation among and within mountain birch trees in foliage phenols,carbohydrates, and amino acids,and in growth ofEpirrita autumnata larvae

Leaf quality of the mountain birch (Betula pubescens ssp.tortuosa) for herbivores was studied at several hierarchical levels: among trees, among ramets within trees, among branches within ramets, and among short shoots within branches. The experimental units at each level were chosen randomly. The indices of leaf quality were the growth rate of the larvae of a geometrid,Epirrita autumnata, and certain biochemical traits of the leaves (total phenolics and individual phenolic compounds, total carbohydrates and individual sugars, free and protein-bound amino acids). We also discuss relationships between larval growth rate and biochemical foliage traits. Larval growth rates during two successive years correlated positively at the level of tree, the ramet, and the branch, indicating that the relationships in leaf quality remained constant between seasons both among and within trees. The distribution of variation at different hierarchical levels depended on the trait in question. In the case of larval growth rate, ramets and short shoots accounted for most of the explained variation. In the case of biochemical compounds, trees accounted for most of the variance in the content of total phenolics and individual low-molecular-weight phenolics. In the content of carbohydrates (total carbohydrates, starch, fructose, glucose, and sucrose) and amino acids, variation among branches was generally larger than variation among trees. Variation among ramets was low for most compounds. No single leaf trait played a paramount role in larval growth. Secondary compounds, represented by phenolic compounds, or primary metabolites, particularly sugars, may both be important in determining the suitability of birch leaves for larvae. If phenols are causally more important, genet-specific analyses of foliage chemistry are needed. If sugars are of primary importance, within-genet sampling and analysis of foliage chemistry are necessary.     

玉米化工醇重组分中有机羧酸络合萃取过程

采用络合萃取技术,以磷酸三丁酯(TBP)为络合剂进行玉米化工醇重组分络合萃取有机羧酸过程研究。探讨了萃取剂浓度、稀释剂的选择、萃取时间、油水比(O/W)、釜残液酸度、萃取级数对萃取平衡常数(D)的影响。结果表明,经四级萃取后,玉米化工醇重组分中有机酸萃取率可达90.7%。     

Supernovae, neutrinos and the chirality of amino acids

A mechanism for creating an enantioenrichment in the amino acids, the building blocks of the proteins, that involves global selection of one handedness by interactions between the amino acids and neutrinos from core-collapse supernovae is defined. The chiral selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the (14)N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. It also requires an asymmetric distribution of neutrinos emitted from the supernova. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth's proteinaceous amino acids.     

Synthesis of new polyester polyols from epoxidized vegetable oils and biobased acids

Biobased polyols were synthesized from reaction between epoxidized soybean oil and lactic, glycolic, or acetic acids. Polyols were characterized by NMR, alcohol and acid titration, and SEC. These analyses allowed to determine an average hydroxyl functionality between 4 and 5, with an oligomer content close to 50 wt%. Synthesized polyols were formulated with isocyanate to yield polyurethanes (PUs). Thermal and mechanical properties of obtained materials showed that synthesized polyols lead to rigid and brittle material with Young moduli higher than 900 N/mm² at RT and with T_g values around 50°C. Practical application: The products of the chemistry described in this contribution, i.e.: polyol from vegetable oils and lactic, glycolic, or acetic acids, provide biobased building blocks for further PUs syntheses by reaction with diisocyanates. The obtained PUs are partially biobased and may be applied as binders and coatings.     

Lipid modification of proteins and their membrane transport

An effective method for artificial attachment of lipid anchorsto water-soluble proteins has been developed. To this end, aprotein molecule is modified in a system of reversed micellesby a water-insoluble reagent, e.g. fatty acid chloride. Fattyacylated proteins acquire an ability to translocate across lipidmembranes and penetrate intact cells. This principle of impartingtransmembrane properties to water-soluble proteins makes itpossible to realize in vivo a direct transport of antibodiesacross the hemato-encephalic barrier into the brain and to developa method for virus suppression by fatty acylated anti-viralantibodies capable of penetrating infected cells. The effectof a drastic increase in the biological activity of exogenousprotein factors, e.g. Staphylococcus aureus enterotoxin A, asa result of their artificial fatty acylation has been discovered.The above-mentioned phenomena are discussed in relation to thein vivo data, indicating that post-translational modificationof proteins by fatty acids and phospholipids is very widespreadin nature and evidently plays an important role in protein transportand sorting. In this connection, lipid modification of proteinsis regarded as a possible general step of protein transportin vivo.     

Reaction of gossypol with amino acids and other amino compounds

The reactions of gossypol with certain amino acids and other amino compounds have been studied spectroscopically with respect to the effect of time and pH in the range from 5.7 to 7.5 at 37 C. The rate of reaction of gossypol with amino acids increases with increase in pH and has been shown to be related to the distance of the amino group from the carboxyl group within the molecule. Reaction products of gossypol with amino acids and other amino compounds were subjected to various purification procedures and analysis to determine combination ratios. In addition to the expected gossypol-to-amino compound ratio of 1:2, dictated by the formation of Schiff base-type bonds with the two aldehyde groups of gossypol, compounds with ratios of 1:3 and 1:4 were isolated. These results indicate that each of the two aldehyde groups of gossypol can react with two amino groups under the conditions studied. Deceased March 9, 1969.     

生物基化工醇重组分中多元醇的分离提取

采用络合萃取与分子蒸馏相结合的方法,对生物基化工醇重组分中的多元醇进行了分离研究。考察了络合剂与萃取剂的配比、萃取时间、萃取温度对重组分中多元醇萃取效果的影响,并对分子蒸馏在不同温度下所得馏分进行分析。结果表明,经络合萃取后,结合分子蒸馏的技术,利用气相色谱和质谱分析,有利于生物基化工醇重组分中多元醇的分离。     

Preparation, characterization, and surface and biological properties of N-stearoyl amino acids

Several lipoamino acids were synthesized, in which n-octadecanoic acid (stearic acid) was coupled with the α-amino group of an amino acid. The products were characterized and their identities confirmed by advanced analytical techniques like Fourier transform infrared ¹H nuclear magnentic resonance spectroscopy, and differential scanning, calorimetry. Their surface properties, such as critical micelle concentration (CMC) and foaming properties, biodegradability, and antimicrobial activity were also evaluated. The N-stearoyl amino acids (NSA) had low CMC values, and some of them showed good foaming properties. They were screened for antimicrobial activity against the gram-positive bacteria Staphylococcus aureus, Micrococcus luteus, and Bacillus cerceus, the gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa, and the yeast Candida albicans. All the compounds inhibited at least one of these organisms. N-Stearoyl proline was the most effective, the order of antimicrobial activity being aromatic NSA> acidic NSA>basic NSA. However, the effective inhibition by all the compounds indicates the desirability of more thorough investigation and suggests that some of these compounds may have potential utility as biostatic additives in commercial products. All NSA are highly biodegradable and can readily be removed under conditions of normal secondary sewage treatment.     

Formation of dityrosine and other fluorescent amino acids by reaction of amino acids with lipid hydroperoxides

Formation of fluorescence by the reaction of various amino acids with lipid hydroperoxides,i.e., linoleic acid 13-monohydroperoxide, methyl linoleate 13-monohydroperoxide and phosphatidylcholine hydroperoxide, in the presence of methemoglobin was investigated. Two types of fluorescence were produced: fluorescent dityrosine (3,3′-dityrosine) from tyrosine, and unidentified fluorophores with α- and ε-amino groups of various amino acids. While the former was stable after treatment with borohydride, the latter fluorophores were readily destroyed. The rate of dityrosine formation was rapid, and the yield of dityrosine was dependent on the concentrations of tyrosine and the lipid hydroperoxides. Butylated hydroxytoluene and tocopherol inhibited the formation of dityrosine, but did not affect the formation of fluorophores on the amino groups. Dityrosine appears to be formed by radical reaction of the lipid hydroperoxides, while the other fluorophores seem to be created by nonradical mechanisms.     

Extended summaries international conference on the enzymatic synthesis and modification of carbohydrates

The following are summaries of papers presented at the International Conference on the Enzymatic Synthesis and Modification of Carbohydrates held on 1–3 July 1992 at Radcliffe House, University of Warwick, UK. The papers published here are entirely the responsibility of the authors and do not reflect the views of the Editorial Board of the Journal of Chemical Technology and Biotechnology.     

Mechanochemical modification of peat humic acids

It was demonstrated that the mechanochemical modification of humic acids in the presence of iron oxyhydroxides facilitated the occurrence of solid-phase reactions due to an increase in the concentrations of phenol, carboxyl, and methoxy groups and quinoid fragments. The modified humic acids possessed an increased catalytic activity caused by the presence of quinoid fragments, phenol hydroxyls, and the humic complexes of transition metals.     

Effect of temperature on soybean seed constituents: Oil,protein, moisture,fatty acids,amino acids and sugars

Soybean plants were grown at day/night temperatures of 24/19 C until the beginning of seed development, and then transferred to 5 different temperature regimes (18/13, 24/19, 27/22, 30/25 and 33/28 C) in the CSIRO phytotron. Mature seeds that developed under these conditions were analyzed for variances in composition. Fatty acid composition was strongly affected by temperature: linolenic and linoleic acids decreased markedly whereas oleic acid increased as the temperature increased; palmitic and stearic acids remained unchanged. Oil content was positively correlated with temperature, and protein content increased at the highest temperature. Of the sugars analyzed, sucrose concentration decreased by 56% with a 15 C increase in temperature, and stachyose showed a slight reduction; other sugars remained unchanged. Amino acid composition was generally stable; however, methionine increased with increased temperature during seed development. Moisture content was unaffected.     

Comparative nutritional value for amino acids,oligopeptides and soybean protein

In recent years our view on the absorption of protein digestion products has undergone a radical change. We now believe that intralumen hydrolysis of intake proteins to free amino acids is only partial. It has thus been hypothesized that partial protein hydrolysates or oligopeptide mixtures are nutritionally superior to corresponding amino acid mixtures. With this consideration for a background, we developed a sophisticated technique of protease-catalyzed modification of soy protein to produce enzymatically modified proteins (EMP) having different levels of covalently attached methionine. We also carried out feeding tests with protein-malnourished rats, with the result that for their recovery from a state of malnutrition, an EMP containing peptide-bound methionine at 3% was significantly more effective than the corresponding amino acid mixture and even the soy protein itself. Discussions stress the importance of applying such a technique to production of an oligopeptide rather than a free amino acid nitrogen source as a foodstuff for therapeutic use.     

Electroenzymatic strategies for deracemization, stereoinversion and asymmetric synthesis of amino acids

A combination of a selective enzymatic oxidation with an unselective electrochemical reduction step was applied for deracemization, stereoinversion and asymmetric synthesis of l-leucine (starting from racemic leucine, d-leucine or 4-methyl-2-oxovaleric acid) in a batch reactor. d-Amino acid oxidase (d-AAO) from Trigonopsis variabilis was used as enzyme. Reaction conditions for the electrochemical and enzymatic reactions were investigated separately and finally combined to an electroenzymatic synthesis, yielding 3.5 mmol L⁻¹ d⁻¹ of l-leucine (ee 91%).