Enantiomeric Composition Of Amino Acids Research Articles

Chiral Fluorescent Probes for Determination of Both Concentration and Enantiomeric Composition of Amino Acids

Chiral Fluorescent Probes for Determination of Both Concentration and Enantiomeric Composition of Amino Acids

Simultaneous Discrimination and Quantification of Enantiomeric Amino Acids under Physiological Conditions by Chiral 19F NMR Tag.

Enantiomeric analysis is of great significance in chemistry, chemical biology and pharmaceutical research. We herein propose a chiral 19F NMR tag containing an amino reactive NHS group to discriminate the enantiomeric amino acids under physiological conditions by NMR spectroscopy. The chiral 19F NMR tag readily forms stable amide products with the amino acids in aqueous solution. The stereospecific chemistry of enantiomeric amino acids is discriminated by a stereogenic carbon bonded with a 19F atom and is therefore decoded by the 19F reporter and manifested in the distinct 19F chemical shift. The chemical shift difference (ΔΔδ) of the chiral 19F NMR tag derived enantiomeric amino acids variants has a broad chemical shift range between -1.13 to 1.68 ppm, indicating the high sensitivity of the chiral 19F NMR tag to the stereospecific environment surrounding the individual amino acids. The distinguishable chemical shift produced by the chiral 19F NMR tag permits simultaneous discrimination and quantification of the enantiomeric amino acids in a mixture. The high fidelity of the chiral 19F NMR tag affords high-accuracy determination of the enantiomeric composition of amino acids by simple 1D NMR under physiological conditions.

Semiquantitative Visual Chiral Assay with a Pseudoenantiomeric Fluorescent Sensor Pair.

A new red-light-emitting fluorescent probe (R)-5 was synthesized. In the presence of Zn2+, this compound was found to exhibit good enantioselective fluorescence enhancement at λ = 655 nm when treated with a variety of amino acids in aqueous solution. This probe in combination with a green-light-emitting probe (S)-4 that has enantioselective fluorescence enhancement at λ = 505 nm has formed a pseudoenantiomeric sensor pair because of their opposite enantioselectivities. This sensor pair can simultaneously detect both enantiomers of a chiral amino acid at two very different wavelengths (Δ = 150 nm). It was used to visually and semiquantitatively determine the enantiomeric compositions of amino acids. For example, when a 1:1 mixture of (R)-5 and (S)-4 was treated with Zn(OAc)2 and histidine samples of 0-100% [d-His], the color of the mixtures changed from green to yellow, orange, and red under a UV lamp (365 nm), which allowed a quick quantification of [d-His]%. This is the first example of using fluorescence to visually quantify the enantiomeric composition of chiral compounds.

Autofluorescence of Amyloids Determined by Enantiomeric Composition of Peptides.

Amyloid fibrils are peptide or protein aggregates possessing a cross-β-sheet structure. They possess intrinsic fluorescence property, which is still not fully understood. Herein, we compare structural and optical properties of fibrils formed from L- and D-enantiomers of the (105–115) fragment of transthyretin (TTR) and from their racemic mixture. Our results show that autofluorescence of fibrils obtained from enantiomers differs from that of fibrils from the racemic mixture. In order to elucidate the origin of observed differences, we analyzed the structure and morphology of fibrils and showed how variations in β-sheet organization influence optical properties of fibrils. We clarified the contribution of aromatic rings and the amyloid backbone to the final blue-green emission of fibrils. This work demonstrates how enantiomeric composition of amino acids allows us to modulate the self-assembly and final morphology of well-defined fibrillar bionanostructures with optical properties controlled by supramolecular organization.

Excitation of One Fluorescent Probe at Two Different Wavelengths to Determine the Concentration and Enantiomeric Composition of Amino Acids.

When a novel fluorescent probe made of BINOL and coumarin is excited at λ1 = 365 nm in a neutral buffer solution, it shows fluorescence enhancement at 465 nm in the presence of an amino acid with a very small difference between the two enantiomers. When excited at λ2 = 467 nm, it shows highly enantioselective fluorescence enhancement at 534 nm. This allows the determination of both concentration and enantiomeric composition of amino acids.

Simultaneous Determination of Concentration and Enantiomeric Composition of Amino Acids in Aqueous Solution by Using a Tetrabromobinaphthyl Dialdehyde Probe.

3,3'-Diformyl-1,1'-bi-2-naphthol or its methoxymethyl-protected derivative is found to undergo a highly selective reaction with excess bromine in CH2 Cl2 at reflux to give the novel 5,5',6,6'-tetrabrominated product (S)- or (R)-2. The observed electrophilic substitution at the 5,5'-positons of an optically active binaphthyl compound is unprecedented. Unlike unbrominated 3,3'-diformyl-1,1'-bi-2-naphthol, which is not suitable for fluorescent recognition in water, compound (S)-2, in combination with Zn2+ , exhibits a highly enantioselective fluorescent response toward amino acids in aqueous solution (HEPES buffer, pH 7.4). It is further found that the condensation product of (R)-2 with tryptophan, (R)-3, shows dual-responsive emissions toward amino acids; the short wavelength (λ1 =350 nm) emission is sensitive to the concentration of the substrate regardless of the chiral configuration and the long wavelength (λ2 >500 nm) emission is highly enantioselective. Thus, the use of (R)-3 allows the simultaneous determination of the concentration and enantiomeric composition of an amino acid sample from one fluorescence measurement.

Biphasic Enantioselective Fluorescent Recognition of Amino Acids by a Fluorophilic Probe

A fluorophilic fluorescent probe based on a perfluoroalkyl-substituted bis(binaphthyl) compound was designed and synthesized. It displayed a highly enantioselective fluorescence response toward structurally diverse amino acids in a biphasic fluorous/aqueous system with enantiomeric fluorescent enhancement ratio (ef; ΔID /ΔIL ) values up to 45.2 (histidine). It can be used to determine the enantiomeric compositions of amino acids and also allows the amino acid enantiomers to be visually discriminated. NMR and mass-spectroscopic investigations provided insights into the observed high enantioselectivity. This biphasic fluorescent recognition was used to determine the enantiomeric composition of the crude phenylalanine products generated by an enzyme-catalyzed asymmetric hydrolysis under various reaction conditions. The fluorous-phase-based fluorescence measurement under the biphasic conditions was able to minimize the interference of other reaction components and thus has potential in asymmetric reaction screening.

The amino acid composition of the Sutter's Mill CM2 carbonaceous chondrite

AbstractWe determined the abundances and enantiomeric compositions of amino acids in Sutter's Mill fragment #2 (designated SM2) recovered prior to heavy rains that fell April 25–26, 2012, and two other meteorite fragments, SM12 and SM51, that were recovered postrain. We also determined the abundance, enantiomeric, and isotopic compositions of amino acids in soil from the recovery site of fragment SM51. The three meteorite stones experienced terrestrial amino acid contamination, as evidenced by the low d/l ratios of several proteinogenic amino acids. The d/l ratios were higher in SM2 than in SM12 and SM51, consistent with rain introducing additional l‐amino acid contaminants to SM12 and SM51. Higher percentages of glycine, β‐alanine, and γ‐amino‐n‐butyric acid were observed in free form in SM2 and SM51 compared with the soil, suggesting that these free amino acids may be indigenous. Trace levels of d+l‐β‐aminoisobutyric acid (β‐AIB) observed in all three meteorites are not easily explained as terrestrial contamination, as β‐AIB is rare on Earth and was not detected in the soil. Bulk carbon and nitrogen and isotopic ratios of the SM samples and the soil also indicate terrestrial contamination, as does compound‐specific isotopic analysis of the amino acids in the soil. The amino acid abundances in SM2, the most pristine SM meteorite analyzed here, are approximately 20‐fold lower than in the Murchison CM2 carbonaceous chondrite. This may be due to thermal metamorphism in the Sutter's Mill parent body at temperatures greater than observed for other aqueously altered CM2 meteorites.

Fast mass spectrometry-based enantiomeric excess determination of proteinogenic amino acids

A rapid determination of the enantiomeric excess of proteinogenic amino acids is of great importance in various fields of chemical and biologic research and industries. Owing to their different biologic effects, enantiomers are interesting research subjects in drug development for the design of new and more efficient pharmaceuticals. Usually, the enantiomeric composition of amino acids is determined by conventional analytical methods such as liquid or gas chromatography or capillary electrophoresis. These analytical techniques do not fulfill the requirements of high-throughput screening due to their relative long analysis times. The method presented allows a fast analysis of chiral amino acids without previous time consuming chromatographic separation. The analytical measurements base on parallel kinetic resolution with pseudoenantiomeric mass tagged auxiliaries and were carried out by mass spectrometry with electrospray ionization. All 19 chiral proteinogenic amino acids were tested and Pro, Ser, Trp, His, and Glu were selected as model substrates for verification measurements. The enantiomeric excesses of amino acids with non-polar and aliphatic side chains as well as Trp and Phe (aromatic side chains) were determined with maximum deviations of the expected value less than or equal to 10ee%. Ser, Cys, His, Glu, and Asp were determined with deviations lower or equal to 14ee% and the enantiomeric excess of Tyr were calculated with 17ee% deviation. The total screening process is fully automated from the sample pretreatment to the data processing. The method presented enables fast measurement times about 1.38 min per sample and is applicable in the scope of high-throughput screenings.

Unusual nonterrestrial l‐proteinogenic amino acid excesses in the Tagish Lake meteorite

Abstract– The distribution and isotopic and enantiomeric compositions of amino acids found in three distinct fragments of the Tagish Lake C2‐type carbonaceous chondrite were investigated via liquid chromatography with fluorescence detection and time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. Large l‐enantiomeric excesses (lee ∼ 43–59%) of the α‐hydrogen aspartic and glutamic amino acids were measured in Tagish Lake, whereas alanine, another α‐hydrogen protein amino acid, was found to be nearly racemic (d ≈ l) using both techniques. Carbon isotope measurements of d‐ and l‐aspartic acid and d‐ and l‐alanine in Tagish Lake fall well outside of the terrestrial range and indicate that the measured aspartic acid enantioenrichment is indigenous to the meteorite. Alternate explanations for the l‐excesses of aspartic acid such as interference from other compounds present in the sample, analytical biases, or terrestrial amino acid contamination were investigated and rejected. These results can be explained by differences in the solid–solution phase behavior of aspartic acid, which can form conglomerate enantiopure solids during crystallization, and alanine, which can only form racemic crystals. Amplification of a small initial l‐enantiomer excess during aqueous alteration on the meteorite parent body could have led to the large l‐enrichments observed for aspartic acid and other conglomerate amino acids in Tagish Lake. The detection of nonterrestrial l‐proteinogenic amino acid excesses in the Tagish Lake meteorite provides support for the hypothesis that significant enantiomeric enrichments for some amino acids could form by abiotic processes prior to the emergence of life.

The effects of parent body processes on amino acids in carbonaceous chondrites

Abstract– To investigate the effect of parent body processes on the abundance, distribution, and enantiomeric composition of amino acids in carbonaceous chondrites, the water extracts from nine different powdered CI, CM, and CR carbonaceous chondrites were analyzed for amino acids by ultra performance liquid chromatography-fluorescence detection and time-of-flight mass spectrometry (UPLC-FD/ToF-MS). Four aqueously altered type 1 carbonaceous chondrites including Orgueil (CI1), Meteorite Hills (MET) 01070 (CM1), Scott Glacier (SCO) 06043 (CM1), and Grosvenor Mountains (GRO) 95577 (CR1) were analyzed using this technique for the first time. Analyses of these meteorites revealed low levels of two- to five-carbon acyclic amino alkanoic acids with concentrations ranging from approximately 1 to 2,700 parts-per-billion (ppb). The type 1 carbonaceous chondrites have a distinct distribution of the five-carbon (C5) amino acids with much higher relative abundances of the γ- and δ-amino acids compared to the type 2 and type 3 carbonaceous chondrites, which are dominated by α-amino acids. Much higher amino acid abundances were found in the CM2 chondrites Murchison, Lonewolf Nunataks (LON) 94102, and Lewis Cliffs (LEW) 90500, the CR2 Elephant Moraine (EET) 92042, and the CR3 Queen Alexandra Range (QUE) 99177. For example, α-aminoisobutyric acid (α-AIB) and isovaline were approximately 100 to 1000 times more abundant in the type 2 and 3 chondrites compared to the more aqueously altered type 1 chondrites. Most of the chiral amino acids identified in these meteorites were racemic, indicating an extraterrestrial abiotic origin. However, nonracemic isovaline was observed in the aqueously altered carbonaceous chondrites Murchison, Orgueil, SCO 06043, and GRO 95577 with l-isovaline excesses ranging from approximately 11 to 19%, whereas the most pristine, unaltered carbonaceous chondrites analyzed in this study had no detectable l-isovaline excesses. These results are consistent with the theory that aqueous alteration played an important role in amplification of small initial left handed isovaline excesses on the parent bodies.

Determination of Enantiomeric Compositions of Amino Acids by Near-Infrared Spectrometry through Complexation with Carbohydrate

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionORIGINAL ARTICLEThis notice is a correctionDetermination of Enantiomeric Compositions of Amino Acids by Near-Infrared Spectrometry through Complexation with CarbohydrateChieu D. Tran, Victor I. Grishko, and Daniel OliveiraCite this: Anal. Chem. 2004, 76, 7, 2157Publication Date (Web):February 27, 2004Publication History Published online27 February 2004Published inissue 1 April 2004https://doi.org/10.1021/ac0400313Copyright © 2004 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views261Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (10 KB) Get e-Alerts Get e-Alerts

Determination of enantiomeric compositions of amino acids by near-infrared spectrometry through complexation with carbohydrate.

A new method has been developed for the determination of enantiomeric compositions of a variety of compounds. The method is based on the use of the near-infrared technique to measure diastereomeric interactions between an added carbohydrate compound with both enantiomeric forms of an analyte followed by partial least-squares analysis of the data. The fact that the method works well with all three macrocyclic carbohydrates with different cavity size (i.e., alpha-, beta-, and gamma-cyclodextrin) as well as with sucrose, which is a linear carbohydrate, clearly demonstrates that it is not necessary to have inclusion complex formation in order to produce effective diastereomeric interactions. Rather, a simple adsorption of the analyte onto a carbohydrate is sufficient. Since inclusion complex formation is not a requisite, this method is not limited to the amino acid studies here but is rather universal and sensitive as it can, in principle, be used to determine enantiomeric compositions for all types of compounds with only microgram concentration and enantiomeric excess as low as 1.5%, in water or in a mixture of water and organic solvent. Furthermore, it does not rely on the use of rather expensive carbohydrates such as cyclodextrins but is equally as effective even with a simple and inexpensive carbohydrate such as sucrose.

Simultaneous analysis of enantiomeric composition of amino acids and N-acetyl-amino acids by enantioselective chromatography.

Among the three chiral columns, CHIROBIOTIC T, CHIRLPAK WH, and CHIRALCEL OD-R, tested for the separation of racemic amino acids and N-acetyl-amino acids, only CHIROBIOTIC T chiral column which is based on covalently bonded amphoteric glycopeptide, teicoplanin, as the stationary phase ligand could be successfully developed to enantiomerically separate racemic amino acids and N-acetyl amino acids simultaneously. This method can be used to determine the enantiomeric composition of amino acids and N-acetyl-amino acids in the catalysis of D-aminoacylase or L-aminoacylase and the conversion rate of N-acylamino acid racemases.

ChemInform Abstract: The Radiolysis and Radioracemization of Poly‐L‐leucines

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The Radiolysis and Radioracemization of Poly-l-Leucines

The brief history of the discovery of radioracemization, the racemization of an optically active substance induced by ionizing radiation, is reviewed. Our early studies involving the radiolysis and radioracemization of D- and L-leucine using gamma radiation from a 111-TBq 60Co gamma-ray source are described briefly, as are later experiments involving other protein amino acids and their salts, as well as the nonprotein amino acid, isovaline. The implications of the results of such studies for the Vester-Ulbricht mechanism which proposes longitudinally polarized beta radiation as the origin of molecular chirality, for the cosmological question of the enantiomeric compositions of amino acids in the Murchison meteorite, and for the use of D/L ratios of amino acids for geochronological and geothermal estimates are reviewed briefly. These past radiolysis-radio- racemization studies have involved only monomeric amino acids. The present research, extending such investigations to two homochiral L-leucine polypeptides, (L-Leu)10 and (L-Leu)78, was undertaken to see if a polymer of an amino acid might be more stable to radiolysis and radioracemization than the corresponding monomer. It was found that these polypeptides were more stable to radiolysis than was the leucine monomer, but that the extents of radioracemization in all samples were comparable.

Evaluation of the enantiomeric composition of amino acids in tobacco.

Despite the fact that several studies have reported the concentrations of various free amino acids in tobacco, their enantiomeric composition is unknown. Both the absolute and enantiomeric compositions of proline, alanine, asparagine, aspartic acid, valine, methionine, leucine,and phenylalanine were determined for three strains of tobacco leaf, three types of smokeless tobacco, and six different blended filtered and nonfiltered reference cigarettes. Some of the highest levels of D-amino acids ever found in agricultural products were observed. Possible mechanisms for the production of these D-amino acids are considered. The relevance of D-amino acids in tobacco is discussed.

Distribution and enantiomeric composition of amino acids in the Murchison meteorite

Early determinations of the amino acid distribution in water extracts of the Murchison meteorite revealed unusual amino acids, including isovaline (Ival), α-aminoisobutyric acid (α-Aiba) and pseudoleucine (Ple), as well as common ones such as glycine (Gly), alanine (Ala) and glutamic acid (Glu)1–10. Amino acids that could be resolved into their respective D- and L-enantiomers were reported to be racemic (see, for example, refs 1, 3, 5), although small sample size might have hindered the precise determination of D/L values. Using improved chromatographic and mass spectrometric procedures we have now been able to amplify and resolve the partially racemized amino acids, Glu, aspartic acid (Asp), proline (Pro), leucine (Leu) and Ala, in an interior sample of a Murchison meteorite stone. Water-extractable amino acids were more racemized than those recovered by digesting the water-extracted meteorite in 6M HC1. The amino acid composition of this stone was similar to previous reports1–8, including the absence of tyrosine (Tyr), methionine (Met), phenylalanine (Phe) and only minor traces of serine (Ser) and threonine (Thr)9. Serine and Thr are usually considered to be terrestrial contaminations. This is the first report of amino acids in a carbonaceous meteorite which, based on currently accepted criteria, appear to be indigenous but for unknown reasons are not racemic. Confirmation of these findings by other investigators suggests that further examination of amino acids in clean carbonaceous meteorites could be beneficial.

Alanine enantiomeric ratio in the combined amino acid fraction in seawater

In deep ocean waters the concentrations of free amino acids are very close to blank levels, while surface waters contain only very low quantities1,2. However, the concentration of ‘combined’ amino acids (whoch occur at all ocean depths in significant quantities) is roughly 10 times that of free amino acids1,2. These combined amino acids are bound in some sort of polymeric material and are released only on hydrolysis in strong acid. The combined amino acid material apparently has a substantial D-aspartic acid content; the D/L aspartic acid ratio in the combined amino acid fraction, isolated from water from the Sargasso Sea, is ∼0.4 at all depths2. It has been suggested that combined amino acids were not actually part of the dissolved organic material in the oceans but were components of bacteria that passed through the filter used in the initial seawater-processing step2,3. Although in most organisms only the L-enantiomers of the amino acids are present, becateria contain several D-amino acids in then cell-wall proteins4. To verify the bacterial explanation we have carried out investigations into the enantiomeric composition of amino acids, besides aspartic acid, in the combined fraction. We measured the alanine enan-tiomeric ratio in seawater samples from three stations in the Pacific Ocean. Alanine was chosen because it is one of the more abundant components of the combined amino acid fraction in the oceans1,2, and because D-alanine is a major component of bacterial cell-wall proteins4.