Diaminosuccinic Acid Research Articles

Optical Resolution of 1,2-Diamino Compounds Using Advanced Marfey's Method

Advanced Marfey's method was successfully applied to the optical resolution of 1,2-diaminoethane compounds. The elution behavior of 1,2-diphenylethylene-1,2-diamine and 1,2-bis(2-methylphenyl)ethylene-1,2-diamine derivatized with L- and D-FDLA was carefully investigated and the following regularity was found: 1) The (S,S)-isomers are eluted prior to the (R,R)-isomer; 2) The (R,R)- and meso-isomers are closely eluted; 3) There is no difference between the retention time of both the L- and D-derivatives of the meso-isomer; 4) This regularity is fundamentally consistent with that of diamino acids such as diaminopimelic acid and diaminosuccinic acid. Finally, it was confirmed that this method along with the DL-FDLA method could be applicable for the determination of the absolute configuration of 1,2-diaminoethane compounds because the method can definitely determine it by the elution order.

A Convenient and Highly Productive Aminohydroxylation Protocol Employing an Osmium‐Diamine Catalyst.

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A Convenient and Highly Productive Aminohydroxylation Protocol Employing an Osmium‐Diamine Catalyst

AbstractIn situ generated osmium‐diamine chelates from 2,3‐diaminopropionic acid or diaminosuccinic acid represent efficient catalysts for the highly productive aminohydroxylation of alkenes. The reaction can be employed with various osmium salts and successful catalyst recycling was demonstrated for a representative example. The catalyst design derives from the general structural features of recently investigated osmium complexes from alkene diamination reactions.

A short diastereoselective synthesis of orthogonally protected diaminosuccinic acid derivatives.

Homogeneous, Rh-catalyzed hydrogenation of heteromeric olefinic glycine dimers presents an efficient route to diastereomerically pure, orthogonally protected diaminosuccinic acid derivatives depending on the double bond geometry of the starting material. The products were obtained as racemates.

Cis-dichloro(diaminosuccinate diethyl ester)palladium (II) as Pd(II)/Pt(II) model compound for dna-binding and antitumor properties: Solution equilibria of their aqua-, hydroxo-, and/or chloro-species

Cis-Dichloro(diaminosuccinic acid)palladium(II), cis-[Pd(H 2dasa)Cl 2] (I), or cis-dichloro(diaminosuccinate diethyl ester)palladium(II), cis-[Pd(Et 2dasa)Cl 2] (II) reacts with two equivalents of AgClO 4 to give insoluble Pd(dasa) or an aqueous solution of [Pd(Et 2dasa)(H 2O) 2](ClO 4) 2, respectively. Three solutions of this salt were titrated with NaOH(I = NaClO 4 (0.15M),37°C), and 133 E(H +) data (3.5 5 pH ≤ 7) were treated by SUPERQUAD to fit log β pqr of cis-aquahydroxo( pqr = 10 − 1, −5.25(3)) and di-μ,-hydroxo-species (20 − 2, −6.55(1)). At pH > 7 the ester hydrolysis prevents the calculation of log β 10−2 for the cis-dihydroxo-complex. Another three solutions of such salt were titrated (I = 0.15M (NaClO 4), 37°C) with NaOH and NaCl simultaneously using two potentiometric systems (which measure H + or Cl −). From 147 E(H +) and E(Cl −) data pairs and the above fixed log β pqr, SUPERQUAD calculations yield log β pqr for cis-chloro-aqua (pqr = 110,3.65(1)), cis-chloro-hydroxo (11 − 1, −2.68 (4)), and cis-dichloro-species (120,5.86(3)). Simulated and experimental titrations are in good agreement. Circular dichroism spectra of native DNA and drug:DNA complexes suggest that cis-Pd(H 2dasa) and cis-Pd(Et 2dasa) chelate moieties induce an opening and rotation of the stacked bases in the double helix. This finding is explained by the abundance of each one and of the total neutral and charged species of II in the tested CD solution.

Cis-Dichloro-palladium(II) complexes with diaminosuccinic acid and its diethyl ester: Synthesis, molecular structure, and preliminary DNA-binding and antitumor studies

The reactions of K 2PdCl 4 with meso-diaminosuccinic acid (H 2dasa) in 0.1 M HCl or its diethyl ester dihydrochloride Et 2dasa·2HCl in neutralized aqueous solution yield cis-[Pd(H 2dasa)Cl 2](I) and cis-[Pd(Et 2dasa)Cl 2](II), respectively. These products were characterized by elemental analysis, IR spectroscopy, and TG-DTA thermal analysis. The crystal of II is monoclinic, space group C2/c ( a = 14.292(5), b = 14.636(5), c = 13.435(5) Å, β = 98.08(2)°, Z = 8, R = 0.041 and wR = 0.06). The Pd(II) atom exhibits a roughly square planar coordination with two PdN bonds (Et 2dasa) (2.014(2) and 2.049(7) Å) and two cis-imposed PdCl bonds (2.294(2) and 2.303(2) Å). Compound I reacts with 2,2′-bipyridine in neutral aqueous solution to give [Pd(2,2′-bipy)(dasa)]·3H 2O(III) in a process of cis-chloride substitution by 2,2′-bipy as a model N-heterocyclic chelating entity. The molecular and crystal structure of III is also reported. It was observed that both cis-dichloro-Pd(II) complexes having Pd(H 2dasa) (acidic) and Pd(Et 2dasa)(esterified) chelate entities induce conformational changes in the covalent closed circular (ccc) form of pUC8 plasmid. Both compounds were assayed for antitumor activity in vitro against MDA-MB 468 and HL-60 human cancer cell lines. The results show that compounds I and II have values of ID 50 lower than those of K 2PdCl 4, and also lower than those of diaminoacid ligands (meso-diaminosuccinic acid and meso-diaminosuccinate diethyl ester). Thus it is likely that the imposed cis-coordination of the chelating H 2dasa or Et 2dasa to the Pd(II) center increases the biological activity of these palladium(II) complexes.

A new synthesis ofβ-fluoroaspartic acid

β-Fluoroaspartic acid, a new amino acid, was synthesized by a diazotization of diaminosuccinic acid in liquid hydrogen fluoride.

Biomolecules from HCN

The mechanism of the condensation of dilute aqueous solutions of HCN and the products formed by these reactions have been investigated. The initial HCN condensation reactions yield3, a compound which is readily oxidized to4. A similar oxidation of5 to6 was also observed. Urea is formed on hydrolysis of4. The oxidation-reduction products formed from HCN may be in part a consequence of the oxidation of3. It has been established by combination GC/MS that the amino acids glycine, diaminosuccinic acid, α-amino-isobutyric acid, aspartic acid, alanine and isoleucine are released on acid hydrolysis of the ‘HCN polymer’. Hydantoin (7), 5,5-dimethylhydantoin (8) and 5-carboxymethyldenehydantoin (10) are also released on acid hydrolysis of the HCN condensation products. The direct conversion of the dicarbonyl derivative, of diaminosuccinic acid to orotic acid via10 at pH 8 has been observed. This conversion suggests a direct route to pyrimidines from HCN.

Asparaginase: STEREOCHEMISTRY OF THE ACTIVE CENTER AS DETERMINED BY CIRCULAR DICHROISM OF SUBSTRATES

Abstract Large Cotton effects associated with the π → π* and n → π* transitions of asparaginase substrates have been shown in substrates containing a 2nd asymmetrical carbon atom at the β position, diaminosuccinic acid monoamide and β-methylasparagine. Hydrolysis of the amide bond is accompanied by large changes in the rotatory strength of these transitions. These substrates have four possible isomers, l-l, d-d, l-d, and d-l. From the signs of the Cotton effects appearing on hydrolysis of mixtures of these isomers it can be determined which isomer is hydrolyzed. The enzyme has an almost absolute stereospecificity for the l-d isomer which defines the three-dimensional arrangement of the protein groups interacting with the substituents on the α carbon and the catalytic groups adjacent to the β-amide within rather narrow limits. While the l-l isomer of diaminosuccinic acid monoamide is not detectably hydrolyzed, the l-l isomer of β-methylasparagine is attacked at a rate 0.2 to 0.3% of that observed for l-asparagine, suggesting that a β-CH3 group can be accommodated in this configuration while a β-NH2 cannot.

Effect of ionizing radiation and U.V. light on N-acetylglycine in the presence of ammonia.

Aqueous solutions of 1-14C-N-acetylglycine and ammonia were irradiated with 7.5 MeV fast electrons,60Co γ-rays, and u.v. light (low pressure mercury lamp). The products and their hydrolyzates were separated by electrophoresis, paper chromatography, and ion exchange chromatography. Among the main reactions are: decarboxylations, aminations yielding diglycine, dimerizations giving rise to diaminosuccinic acid, succinic acid, aspartic acid, β-aspartylglycine, β-alanylglycine, and the N-acetyl derivatives of these compounds. Methylations yield α-alanine, and a reductive transacetylation yields threonine. The results are briefly discussed with respect to the effect of different concentrations and the use of different qualities of radiation. The results also point to a possible pathway to the prebiotic origin of a number of biologically important micromolecules, including oligopeptides. The results indicate, however, that a prebiotic formation of polypeptides or protein-like macromolecules by the action of ionizing radiations or u.v. light upon aqueous solutions of monomers is unlikely under the conditions of this investigation.

Radiation Chemical Reactions in Aqueous Oxygenated and Oxygen-Free Solutions of Aliphatic Dipeptides and Tripeptides

The first exact studies on the radiation chemistry of the peptide bond were performed by Garrison et al. (1, 2), who irradiated N-acylamino acids (N-acetylglycine and N-acetylalanine). A reaction mechanism was suggested for the radiolysis of the peptide bond in oxygenated and oxygen-free solutions based on the yields and types of products observed. The fundamental reactions found by Garrison and Weeks in oxygenated solutions of acetyl. glycine were cleavage of the peptide bond under formation of the amide of the N-terminal and the carbonyl derivative of the C-terminal amino acid (the keto acid). In oxygen-free solutions they observed similar cleavage products of the peptide bond besides recombination on C-2, yielding diaminosuccinic acid and aspartic acid from irradiated acetyl glycine (recombination of the acetic and glycine radicals or of two glycine radicals), diaminosuccinic acid being the major product. Hatano (3) compared the G(NH3) yield from several peptides in oxygenated solutions (2 X 105 R) and found decreasing values with increasing chain length of the amino acid participating in the peptide bond (Gly Gly, G = 4.02; Ala Leu, G = 1.05). In irradiated alanyl valine solutions he found formation of a-ketoisovaleric acid as well as of pyruvic acid, contradicting Garrison's observations. Simultaneous and independent experiments were carried out in our laboratory with leucyl glycyl glycine, leucyl glycine, and glycyl leucine (4) and a series of other peptides based on our previous work on the radiation chemistry of higher aliphatic amino acids (5-10), which established a very detailed radiolytic mechanism of these compounds in oxygenated and oxygen-free solutions. Our present studies aimed at elucidation of the effects of the peptide bond on the radiolysis of the amino acids and vice versa, since the results could contribute information on the radiolytic reactions of proteins. In this paper the products of radiolysis of eleven dipeptides and tripeptides were determined before and after hydrolysis of the solutions irradiated in the presence and in the absence of oxygen. The results show that there is an essential difference in the radiation chemical reactions in oxygenated and in oxygen-free solutions.

Radiolysis of Aqueous Solutions of Glycine

A detailed mechanism for the radiolysis of the glycine-water system is developed. The treatment is based on the various literature sources and on new experimental findings which are described. It is proposed that the indirect action of radiation on glycine in oxygenfree solution results in formation of the free-radical intermediates CH/sub 2/COOH and NH/sub 2/CHCCOH. Although most of these ultimately yield acetic acid and glyoxylic acid, respectively, it is concluded that some undergo radical-radical reaction to yield succinic acid, aspartic acid, and diaminosuccinic acid. Effects of oxygen, glycine concentration, and pH are discussed. (auth)

Inhibition of enzymic transamination of aspartic acid by hydroxyaspartate, 2,3-diaminosuccinate and 2,3-diaminopropionate

An extract of acetone powder of pig kidney mitochondria, which is rich in aspartic- a-ketoglutaric acid transaminase, also catalyzes the transamination of hydroxyaspartate. This second reaction is much slower than the first one. Hydroxyaspartic acid is a competitive inhibitor of the transamination of aspartate and a-ketoglutarate. Diaminopropionic and diaminosuccinic acids also inhibit transamination of aspartate. The inhibition by diaminopropionic acid is non-competitive. The inhibition by diaminosuccinic acid is a combination of competitive and non-competitive type.

Resolution by means of a Micro-organism of Racemic Diaminosuccinic Acid and Determination of its Configuration

THE chemical structure of diaminosuccinic acid is analogous to aspartic acid, asparagine, C4-dicarboxylic acids and the other biologically important substances. The acid, however, has not yet been found in Nature, and so has never been fully investigated. In 1925, racemic acid was resolved into its antipodes by Kuhn1, through the morphine salt of N,N′-dibenzoyl diaminosuccinic acid; [α]20 D = − 18.9° (10 per cent hydrochloric acid). Suzuki and Suzuki2 found, during the course of an investigation on the behaviour of micro-organisms towards the acid, that Micrococcus ureae was capable of growing on a medium containing the racemic acid as the sole source of nitrogen, and that about half the amount of racemic acid always remained even after full growth. From these observations the authors considered that the micro-organism preferentially assimilated one of the two optical isomers, and that a non-utilizable antipode could perhaps be isolated from the medium.