The Use of A 25 Factorial Design to Study the Effect of Various Alcohols on the Paper Chromatographic Separation of Selected Amino Acids

Abstract

A 2⁵ factorial design was used to evaluate the effect of methanol, ethanol, propanol, butanol and pentanol on the paper chromatographic separation of Arginine, Threonine, Leucine, Histidine, and Tryptophan. The most significant effects occur for the alcohols themselves with an increasing effect with an increase in carbon chain length. The major interaction terms involve the combinations of butanol and pentanol with the other alcohols or with themselves.     

Analysis of Thermal Decomposition Patterns of Aromatic and Heteroaromatic Amino Acids

Abstract

Differential enthalpic analysis of the thermal degradation of aromatic and heteroaromatic amino acids provides thermograms which are characteristic of specific amino acids (e.g. phenylalanine, tyrosine, tryptophan or histidine). Curve resolution of the resulting thermograms suggests that a minimum of three reactions are involved in the degradation (within the temperature limits of 500–620 [ddot]K) and provides T_M values for each of these concurrent reactions.     

Stereoselective Aldol Reactions Catalyzed by Acyclic Amino Acids in Aqueous Micelles

The catalytic properties of all proteinogenic, acyclic amino acids for direct aldol reaction in H₂O, assisted by various surfactants, were investigated. The basic and neutral amino acids were shown to be efficient catalysts, giving rise to good‐to‐excellent yields of adducts (up to 95%), with moderate‐to‐good diastereoselectivities (up to 86%), L ‐arginine being the most‐effective catalyst. The syn/anti diastereoisomer ratio could be readily tuned by proper choice of the amino acid used. Also, the range of substrates that underwent the reaction was extended to less‐reactive aldehydes carrying electron‐donating Br substituents.     

胶束电动毛细管色谱分离氨基酸和磷酸化氨基酸

本文报道了胶束电动毛细管色谱分离、汞灯诱导荧光电荷耦合器件检测分析氨基酸和磷酸化氨基酸的 4-氟 - 7-硝基苯 - 2 - 口恶 - 1 ,3-丫唑衍生物。研究表明 ,在 p H9.35的 1 0 mmol/L硼砂和 1 0 mmol/L十二烷基硫酸钠的电泳缓冲介质中 ,5种氨基酸和 3种磷酸化氨基酸在 1 0 min内完全分离 ,检测灵敏度为 1 .2 1× 1 0 - 8～ 5 .2 1×1 0 - 8mol/L ,分离效率达 7.3× 1 0 5～ 3.0× 1 0 5/m理论塔板数 ,结果令人满意     

游离芳香氨基酸和半胱氨酸对光诱导高铁肌红蛋白还原的影响

肌红蛋白(Myoglobin,Mb)中血红素辅基不仅具有储氧功能,也能吸收特定波长的光而影响蛋白功能表达。实验发现,部分游离的氨基酸对光诱导高铁肌红蛋白(metM b,Fe(III)-Mb)的还原过程及还原程度都有重要作用,因此,本文采用紫外-可见吸收光谱、圆二色谱、三维荧光光谱法,在光照体系中加入拥挤试剂来模拟细胞内拥挤环境,研究芳香氨基酸[色氨酸(Trp)、苯丙氨酸(Phe)、酪氨酸(Tyr)、半胱氨酸(Cys)]对metM b还原的影响。结果表明,含-OH或-SH的氨基酸(Tyr、Cys)能使metM b发生较好的光还原,无-OH或-SH基团的氨基酸(Trp、Phe)对metM b的光还原作用较弱,氨基酸促进metM b光还原的整个过程可能是分子间电子转移的过程。metM b在拥挤环境聚蔗糖70(Ficoll 70)中的光诱导还原程度比在稀溶液中高,拥挤试剂Ficoll70对蛋白的二级结构起保护作用,能够稳定血红素微环境。     

葡萄酒中游离氨基酸的高效液相色谱法测定

采用邻苯二甲醛衍生化法衍生葡萄酒中的游离氨基酸，以反相高效液相色谱法对葡萄酒中１８种氨基酸进行了测定，方法简单、迅速，２５ｍｉｎ即可完成１８种氨基酸的分离。精密度及回收率实验结果令人满意。     

The Biosynthesis of Aromatic Amino Acids and its Regulation

Microorganisms synthesize the aromatic amino acids phenylalanine, tyrosine, and tryptophan, as well as the related compounds p-aminobenzoic acid, tetrahydrofolic acid, p-hydroxybenzoic acid, ubiquinone, vitamin K, and nicotinic acid, by a highly branched route passing through shikimic acid. The biosynthesis is not regulated in the same way in all the organisms studied. The regulation is strongly dependent on the ability of the enzymes involved to be resolved into isozymes, their ability to be inhibited, and their activation, repression, and induction.     

毛细管电泳高频电导法快速分离检测混合氨基酸

氨基酸(Am ino acids,AA s)是组成生物大分子的基本单元,与人的健康状况有极其密切的关系.在医学和生命科学研究中,微量氨基酸的分离检测具有重要意义.     

制药废液中氨基酸的分离与测定

为测定维生素 B12 制药厂排出的废液中氨基酸量,先在所取的废液样品中加入乙酸铅使其中蛋白质及其他大分子有机物产生沉淀并用离心法分离.上层澄清液中的氨基酸通过装有强酸性阳离子交换树脂的交换柱(25 cm×2.5 cm)予以分离,用1 mol·L-1 氨水将氨基酸从柱上洗脱.在所得洗脱液中用气相色谱-质谱及傅立叶变换红外光谱法对氨基酸进行定性及定量测定.     

用低交换容量聚苯乙烯型强酸性阳离子交换树脂柱色谱分离中性氨基酸

通过磺化苯乙烯 -二乙烯苯共聚物或商品化的聚苯乙烯型强酸性阳离子交换树脂 ( 0 0 1× 7)的逆磺化反应 ,得到一系列不同交换容量的聚苯乙烯型强酸性阳离子交换树脂 .研究了丙氨酸和缬氨酸及缬氨酸和亮氨酸在这些树脂柱上的色谱分离 .结果表明 ,用两种方法得到的树脂对丙氨酸和缬氨酸的色谱分离性能基本相同 ;同时中性氨基酸与聚苯乙烯型强酸性阳离子交换树脂之间的作用包括离子作用和疏水作用 ,且二者之间存在协同作用 .树脂的交换容量较低时对中性氨基酸有更好的分离性能     

The Study of UV and VIS Absorption Spectra of the Complexes of Amino Acids with Ninhydrin

Abstract

The analysis of amino acids with post column derivatization using ninhydrin is usually carried out with automatic analyzers at wavelengths of 570 nm (for the quantitation of α-amino acids) and 440 nm (for the imino acids), or at only one wavelength, 520 nm, for the total acid content. The α-amino acids are reported to give an absorption maximum at 570 nm, after complex formation with ninhydrin; and α-imino acids have a γ at 440 nm, 520 nm is a compromise wavelength.

This paper presents a study of the absorption of the complexes of amino acids with ninhydrin between 275 and 700 nm. Two new wavelengths are suggested for use, 290 and 404 nm.

In the near UV (290 nm) all the tested acids show a common absorption maximum and good sensitivities. In the visible region at 404 nm, the sensitivities of the α-amino acids are very similar to those observed at 570 nm. At 520 nm the αamino acids have the lowest sensitivities.

The α-imino acids (proline and oxyproline) show absorption maxima only at 290 nm; after that their sensitivities decrease with increasing wavelength.

The paper offers some practical hints on changing the detector wavelength, and to adapt the HPLC's detector to work at one of these two, newly suggested, bands (290 or 404 nm).     

Loading of Amino Acids onto RNA in a Putative RNA-Peptide World

RNA is a molecule that can both store genetic information and perform catalytic reactions. This observed dualism places RNA into the limelight of concepts about the origin of life. The RNA world concept argues that life started from self-replicating RNA molecules, which evolved toward increasingly complex structures. Recently, we demonstrated that RNA, with the help of conserved non-canonical nucleosides, which are also putative relics of an early RNA world, had the ability to grow peptides covalently connected to RNA nucleobases, creating RNA-peptide chimeras. It is conceivable that such molecules, which combined the information-coding properties of RNA with the catalytic potential of amino acid side chains, were once the structures from which life emerged. Herein, we report prebiotic chemistry that enabled the loading of both nucleosides and RNAs with amino acids as the first step toward RNA-based peptide synthesis in a putative RNA-peptide world.     

Creating a Defined Chirality in Amino Acids and Cyclic Dipeptides by Photochemical Deracemization

2,5-Diketopiperazines are cyclic dipeptides displaying a wide range of applications. Their enantioselective preparation has now been found possible from the respective racemates by a photochemical deracemization (53 examples, 74 % to quantitative yield, 71–99 % ee). A chiral benzophenone catalyst in concert with irradiation at λ=366 nm enables to establish the configuration at the stereogenic carbon atom C6 at will. If other stereogenic centers are present in the diketopiperazines they remain unaffected and a stereochemical editing is possible at a single position. Consecutive reactions, including the conversion into N-aryl or N-alkyl amino acids or the reduction to piperazines, occur without compromising the newly created stereogenic center. Transient absorption spectroscopy revealed that the benzophenone catalyst processes one enantiomer of the 2,5-diketopiperazines preferentially and enables a reversible hydrogen atom transfer that is responsible for the deracemization process. The remarkably long lifetime of the protonated ketyl radical implies a yet unprecedented mode of action.     

Synthesis and Characterization of Extended Bis(terpyridine)ruthenium Amino Acids

(Oligopyridine)ruthenium(II) complexes have been widely used in dye sensitized solar cells and other sophisticated optical devices due to their outstanding photophysical properties and their chemical stability. Herein, we describe the longitudinal extension of our previously reported bis(terpyridine)ruthenium(II) amino acid [Ru(tpy–NH₂)(tpy–COOH)]²⁺ (tpy = 4′‐substituted 2,2′:6′,2″‐terpyridine) by insertion of para‐phenylene spacers –C₆H₄– between the terpyridine and the functional groups. The influence of the para‐phenylene spacer on the absorption and emission properties is investigated using UV/Vis absorption and emission spectroscopy and is discussed within a qualitative molecular orbital picture.     

Oxathiaphospholane Approach to the Synthesis of Conjugates of Amino Acids Methyl Esters with Nucleosides

Based upon 1,3,2-oxathiaphospholane chemistry, 5'-O-derivatization of nucleosides with the O-methyl esters of amino acids was performed and corresponding conjugates were obtained in satisfactory yield.     

纳滤膜分离技术分离纯化多肽和氨基酸

综述了近十年来纳滤膜技术在氨基酸和多肽分离与纯化方面的研究进展。多肽和氨基酸的纳滤分离过程受溶液物化性质、氨基酸和多肽分子尺寸、所带电荷以及膜孔径、膜带电状态等多种因素的影响,建立该过程的分离机理模型、组合并优化分离条件是当前研究的热点。     

聚丙烯酰胺型配体交换色谱载体的合成及分离氨基酸

合成了以亲水性聚丙烯酰胺为骨架的含有可与铜离子形成五元环螯合物配位基团的螯合树脂,这些树脂的Cu~(2+)络合物作为配体交换色谱载体对中性氨基酸进行了分离,并与2种已知螯合树脂的Cu~(2+)络合物作为载体的色谱行为作了比较。本文合成的树脂具有最好的分高性能,研究了色谱条件对分离的影响,讨论了色谱分离机制。     

Complex Formation Reactions of Divinyltin(IV) Complexes with Amino Acids,Peptides, Dicarboxylic acids and Related Compounds

Complex formation equilibria of divinyltin(IV) with amino acids, peptides, and dicarboxylic acids have been investigated. Stoichiometry and stability constants for the complexes formed were determined at 25°C and ionic strength 0.1 M NaNO₃. The results showed the formation of ML, MLH, and ML₂ (organotin : ligand : hydrogen) complexes with amino acids. Peptides form ML complexes and the corresponding deprotonated amide species MLH_?1. In the latter species the binding with divinyltin(IV) occurs through the terminal amino group, carboxylate oxygen, and the amide nitrogen atoms (CO^? ₂, N^? _amide, NH₂). The results showed the formation of ML and ML₂ complexes with dicarboxylic acids. The concentration distribution of the complexes in solution was evaluated. The bonding sites of the divinyltin(IV) complex in solid state with oxalic acid was investigated by means of elemental analyses, FTIR, and mass spectra. Non-isothermal decomposition of the above complex has been studied and the result was statistically analyzed. The main steps were identified for the thermal decomposition reaction and each step proved to be a first order reaction. The kinetic parameters E _a and A were calculated for each step in the reaction. The thermodynamic functions H, G, and S* were calculated for each step of the reaction.     

Effects of Micellar Aggregates on the Kinetics and Mechanism of the Reaction between 4‐Nitrobenzenediazonium Ions and Some Amino Acids

We have explored the kinetics and mechanism of the reaction between 4‐nitrobenzenediazonium ions (4NBD), and the hydrophilic amino acids (AA) glycine and serine in the presence and absence of sodium dodecyl sulfate (SDS) micellar aggregates by means of UV/VIS spectroscopy. The observed rate constants k_obs were obtained by monitoring the disappearance of 4NBD with time at a suitable wavelength under pseudo‐first‐order conditions. In aqueous acid (buffer‐controlled) solution, in the absence of SDS, the dependence of k_obs on [AA] was obtained from the linear relationship found between the experimental rate constant and [AA]. At a fixed amino acid concentration, k_obs values show an inverse dependence on acidity in the range of pH 5–6, suggesting that the reaction takes place through the nonprotonated amino group of the amino acid. All kinetic evidence is consistent with an irreversible bimolecular reaction with k=2390±16 and 376±7 M ^?1 s^?1 for glycine and serine, respectively. Addition of SDS inhibits the reaction because of the micellar‐induced separation of reactants originated by the electrical barrier imposed by the SDS micelles; k_obs values are depressed by factors of 10 (glycine) and 6 (serine) on going from [SDS]=0 up to [SDS]=0.05M . The hypothesis of a micellar‐induced separation of the reactants was confirmed by ¹H‐NMR spectroscopy, which was employed to investigate the location of 4NBD in the micellar aggregate: the results showed that the aromatic ring of the arenediazonium ion is predominantly located in the vicinity of the C(β) atom of the surfactant chain, and hence the reactive ? N group is located in the Stern layer of the micellar aggregate. The kinetic results can be quantitatively interpreted in terms of the pseudophase kinetic model, allowing estimations of the association constant of 4NBD to the SDS micelles.     

Synthesis of Protected Dithiol Amino Acids for Potential Use in Peptide Chemistry

Two N-Fmoc and S,S′-protected α-amino acids were synthesized by introducing the derivatives of dithioether into a Tyrosine side chain under the Mitsunobu protocol using the diisopropylazodicarboxylate/triphenylphosphine (DIAD/TPP) system. These amino acids provide a potential use in peptide chemistry.