Rapid [Gamma]-amino acid synthesis and the inhibition of the growth and development of oblique banded leaf-roller larvae

The hypothesis that rapid y-aminobutyric acid (GABA) accumulation is a plant defense against phytophagous insects was investigated. Simulation of mechanical damage resulting from phytophagous insect activity increased soybean (Glycine max L.) leaf GABA 10- to 25-fold within 1 to 4 min. Pulverizing leaf tissue resulted in a value of 2. 15 (±O. 11 SE) ~mol GABA per gram fresh weight. Increasing the GABA levels in a synthetic diet from 1.6 to 2.6 Jlffiol GABA per gram fresh weight reduced the growth rates, developmental rates, total biomass (50% reduction), and survival rates (30% reduction) of cultured Oblique banded leaf-roller (OBLR) (Choristonellra rosacealla Harris) larvae. In field experiments OBLR larvae were found predominantly on young terminal leaves which have a reduced capacity to produce GABA in response to mechanical damage. Glutamate decarboxylase (GAD) is a cytosolic enzyme which catalyses the decarboxylation of L-Glu to GABA. GAD is a calmodulin binding enzyme whose activity is stimulated dramatically by increased cytosolic H+ or Ca2 + ion concentrations. Phytophagous insect activity will disrupt the cellular compartmentation of H+ and Ca2 +, activate GAD and subsequent GABA accumulation. In animals GABA is a major inhibitory neurotransmitter. The possible mechanisms resulting in GABA inhibited growth and development of insects are discussed.

Eucalyptus ESTs associated with resistance to herbicide inhibitors of aromatic and branched-chain amino acid synthesis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Organotin(IV) complexes derived from proteinogenic amino acid: Synthesis, structure and evaluation of larvicidal efficacy on Anopheles stephensi mosquito larvae

Five new organotin(IV) complexes of composition [Bz2SnL1]n (1), [Bz3SnL1HH2O] (2), [Me2SnL2H2O] (3), [Me2SnL3] (4) and [Bz3SnL3H]n (5) (where L1 = (2S)-2-([(E)-(4-hydroxypentan-2-ylidene)]amino)-4-methylpentanoate, L2 = (rac)-2-([(E)-1-(2-hydroxyphenyl)methylidene]amino)-4-methylpentanoate and L3 = (2S)- or (rac)-2-([(E)-1-(2-hydroxyphenyl)ethylidene]amino)-4-methylpentanoate) were synthesized and characterized using 1H NMR, 13C NMR, 119Sn NMR and infrared spectroscopic techniques. The crystal structure of 2 reveals a distorted trigonal-bipyramidal geometry around the tin atom where the oxygen atoms of the carboxylate ligand and a water ligand occupy the axial positions, while the three benzyl ligands are located at the equatorial positions. On the other hand, the analogous derivative of enantiopure L3H (5) consists of polymeric chains, in which the ligand-bridged tin atoms adopt the same trans-Bz3SnO2 trigonal-bipyramidal configuration and are now coordinated to a phenolic oxygen atom instead of H2O. In 2, the OH hydrogen of the ketoimine substituent has moved to the nearby nitrogen atom while in the salicylidene derivative 5, the OH is located almost midway between the phenolic oxygen atom and the nitrogen atom of the C=N group. For the dibenzyltin derivative 1, a polymeric chain structure is observed as a result of a long intermolecular SnO bond involving the exocyclic carbonyl oxygen atom from the tridentate ligand of a neighbouring tin-complex unit. The tin atom in this complex has distorted octahedral coordination geometry. In contrast, the racemic dimethyltin(IV) complexes 3 and 4 display discrete monomeric structures with a distorted octahedral- and trigonal-bipyramidal geometry, respectively. The structures show that the coordination mode of the Schiff base ligand depends primarily on the number of bulky benzyl ligands (R) at the tin atom, as indeed found in the structures of related complexes where R = phenyl. With three bulky R groups, the tridentate chelating O,N,O coordination mode is preferred, whereas with fewer or less bulky R ligands, only the carboxylate and hydroxy groups are involved, which leads to polymers. Larvicidal efficacies of two of the new tribenzyltin(IV) complexes (2 and 5) were assessed on the second larval instar of Anopheles stephensi mosquito larvae and compared with two triphenyltin(IV) analogues, [Ph3SnL1H]n and [Ph3SnL3H]n. The results demonstrate that the compounds containing Sn-Ph ligands are more effective than those with Sn-Bz ligands.

Synthesis of Unnatural C-2 Amino Acid Nucleosides Using NIS-Mediated Ring Opening of 1,2-Cyclopropane Carboxylated Sugar Derivatives

We have developed a general and efficient method for the stereoselective construction of pyrimidine-based pyranosyl C-2 amino acid nucleosides using NIS-mediated ring opening of 1,2-cyclopropanated sugar derivatives. This methodology has been successfully extended to the synthesis of furanosyl nucleosides, Which have potential applications in the development of novel, nontoxic antifungal therapeutics.

Synthesis, crystal structures and protease activity of amino acid Schiff base iron(III) complexes

Iron(III) complexes, (NHEt3)[Fe(III)(sal-met)(2)] and (NHEt3)[Fe(III)(sal-phe)(2)], of amino acid Schiffbase ligands, viz., N-salicylidene-L-methionine and N-salicylidene L-phenylalanine, have been prepared and their binding to bovine serum albumin (BSA) and photo-induced BSA cleavage activity have been investigated. The complexes are structurally characterized by single crystal X-ray crystallography. The crystal Structures of the discrete mononuclear rnonoanionic complexes show FeN2O4 octahedral coordination geometry in which the tridentate dianionic amino acid Schiff base ligand binds through phenolate and carboxylate oxygen and imine nitrogen atoms. The imine nitrogen atoms are trans to each other. The Fe-O and Fe-N bond distances range between 1.9 and 2.1 angstrom. The sal-met complex has two pendant thiomethyl groups. The high-spin iron(III) complexes (mu(eff) similar to 5.9 mu(B)) exhibit quasi-reversible Fe(III)/Fe(II) redox process near -0.6 V vs. SCE in water. These complexes display a visible electronic hand near 480 nm in tris-HCl buffer assignable to the phenolate-to-iron(III) charge transfer transition. The water soluble complexes bind to BSA giving binding constant values of similar to 10(5) M-1. The Complexes show non-specific oxidative cleavage of BSA protein on photo-irradiation with UV-A light of 365 nm.

Amino Acid Based MOFs: Synthesis, Structure, Single Crystal to Single Crystal Transformation, Magnetic and Related Studies in a Family of Cobalt and Nickel Aminoisophthales

Four new 5-aminoisophthalates of cobalt and nickel have been prepared employing hydro/solvothermal methods: [Co2(C8H5NO4)2(C4H4N2)(H2O)2]·3H2O (I), [Ni2(C8H5NO4)2(C4H4N2)(H2O)2]·3H2O (II), [Co2(H2O)(μ3-OH)2(C8H5NO4)] (III), and [Ni2(H2O)(μ3-OH)2(C8H5NO4)] (IV). Compounds I and II are isostructural, having anion-deficient CdCl2 related layers bridged by a pyrazine ligand, giving rise to a bilayer arrangement. Compounds III and IV have one-dimensional M−O(H)−M chains connected by the 5-aminoisophthalate units forming a three-dimensional structure. The coordinated as well as the lattice water molecules of I and II could be removed and inserted by simple heating−cooling cycles under the atmospheric conditions. The removal of the coordinated water molecule is accompanied by changes in the coordination environment around the M2+ (M = Co, Ni) and color of the samples (purple to blue, Co; green to dark yellow, Ni). This change has been examined by a variety of techniques that include in situ single crystal to single crystal transformation studies and in situ IR and UV−vis spectroscopic studies. Magnetic studies indicate antiferromagnetic behavior in I and II, a field-induced magnetism in III, and a canted antiferromagnetic behavior in IV.

Important role of the amino acid attached to tRNA in formylation and in initiation of protein synthesis in Escherichia coli

In attempts to convert an elongator tRNA to an initiator tRNA, we previously generated a mutant elongator methionine tRNA carrying an anticodon sequence change from CAU to CUA along with the two features important for activity of Escherichia coli initiator tRNA in initiation. This mutant tRNA (Mi:2 tRNA) was active in initiation in vivo but only when aminoacylated with methionine by overproduction of methionyl-tRNA synthetase. Here we show that the Mi:2 tRNA is normally aminoacylated in vivo with lysine and that the tRNA aminoacylated with lysine is a very poor substrate for formylation compared with the same tRNA aminoacylated with methionine. By introducing further changes at base pairs 4:69 and 5:68 in the acceptor stem of the Mi:2 tRNA to those found in the E. coli initiator tRNA, we show that change of the U4:A69 base pair to G4:C69 and overproduction of lysyl-tRNA synthetase and methionyl-tRNA transformylase results in partial formylation of the mutant tRNA and activity of the formyllysyl-tRNAs in initiation of protein synthesis. Thus, the G4:C69 base pair contributes toward formylation of the tRNA and protein synthesis in E. coli can be initiated with formyllysine. We also discuss the implications of these and other results on recognition of tRNAs by E. coli lysyl-tRNA synthetase and on competition in cells among aminoacyl-tRNA synthetases.

Dendritic encapsulation of amino acid-metal complexes. Synthesis and studies of dendron-functionalized L-tyrosine-metal (Zn-II, Co-II) complexes

This paper describes the synthesis, characterization and studies of dendrimers possessing an amino acid-metal complex as the core. Using Frechet-type polyaryl ether dendrons, L-tyrosine-metal (Zn-II and Co-II) complex cored dendrimers of 0-4 generations were synthesized. The metal complexation of the tyrosine unit at the focal point of these dendrons took place smoothly, in excellent yields, even though the sizes of the dendrons increase as the generations advance. Spectrophotometric titrations with CoII metal ion confirmed the formation of a 2 : 1 dendritic ligand to metal complex and the existence of a pseudotetrahedral geometry at the metal centre is also inferred. Cyclic voltammetric studies of dendrimer-Co-II complexes showed that while the electron transfer of Co-II to Co-I was facile for generations 0-2, such a process was difficult with generations 3 and 4, indicating a rigid encapsulation of the metal ion centre by proximal dendron groups. Further reduction of Co-I to Co-0 and the corresponding oxidation processes appear to be limited by adsorption at the surfaces of the electrodes.

Propargyloxycarbonyl (Poc) amino acid chlorides as efficient coupling reagents for the synthesis of 100% diastereopure peptides and resin bound tetrathiomolybdate as an effective deblocking agent for the Poc group

Synthesis of short peptides using propargyloxycarbonyl amino acid chlorides as effective coupling reagents and polymer supported tetrathiomolybdate as an efficient deblocking agent are reported.

The design and synthesis of redox core-alpha amino acid composites based on thiol-disulfide exchange mechanism and a comparative study of their zinc abstraction potential from [CCXX] boxes in proteins

The design and synthesis of agents that can abstract zinc from their [CCXX] (C=cysteine; X=cysteine/histidine) boxes by thioldisulfide exchange-having as control, the redox parities of the core sulfur ligands of the reagent and the enzyme, has been illustrated, and their efficiency demonstrated by monitoring the inhibition of the transcription of calf thymus DNA by E. coli RNA polymerase, which harbors two zinc atoms in their [CCXX] boxes of which one is exchangeable. Maximum inhibition possible with removal of the exchangeable zinc was seen with redox-sulfanilamide-glutamate composite. In sharp contrast, normal chelating agents (EDTA, phenanthroline) even in a thousand fold excess showed only marginal inhibition, thus supporting an exchange mechanism for the metal removal. (C) 2002 Elsevier Science Ltd. All rights reserved.

Part I. Synthesis of L-amino acid oxidase by a serine- or glycine-requiring strain of neurospora. Part II. Studies concerning multiple electrophoretic forms of tyrosinase in neurospora

Part I: Synthesis of L-Amino Acid Oxidase by a Serine- or Glycine-Requiring Strain of Neurospora

Wild-type cultures of Neurospora crassa growing on minimal medium contain low levels of L-amino acid oxidase, tyrosinase, and nicotinarnide adenine dinucleotide glycohydrase (NADase). The enzymes are derepressed by starvation and by a number of other conditions which are inhibitory to growth. L-amino acid oxidase is, in addition, induced by growth on amino acids. A mutant which produces large quantities of both L-amino acid oxidase and NADase when growing on minimal medium was investigated. Constitutive synthesis of L-amino acid oxidase was shown to be inherited as a single gene, called P110, which is separable from constitutive synthesis of NADase. P110 maps near the centromere on linkage group IV.

L-amino acid oxidase produced constitutively by P110 was partially purified and compared to partially purified L-amino acid oxidase produced by derepressed wild-type cultures. The enzymes are identical with respect to thermostability and molecular weight as judged by gel filtration.

The mutant P110 was shown to be an incompletely blocked auxotroph which requires serine or glycine. None of the enzymes involved in the synthesis of serine from 3-phosphoglyceric acid or glyceric acid was found to be deficient in the mutant, however. An investigation of the free intracellular amino acid pools of P110 indicated that the mutant is deficient in serine, glycine, and alanine, and accumulates threonine and homoserine.

The relationship between the amino acid requirement of P110 and its synthesis of L-amino acid oxidase is discussed.

Part II: Studies Concerning Multiple Electrophoretic Forms of Tyrosinase in Neurospora

Supernumerary bands shown by some crude tyrosinase preparations in paper electrophoresis were investigated. Genetic analysis indicated that the location of the extra bands is determined by the particular T allele present. The presence of supernumerary bands varies with the method used to derepress tyrosinase production, and with the duration of derepression. The extra bands are unstable and may convert to the major electrophoretic band, suggesting that they result from modification of a single protein. Attempts to isolate the supernumerary bands by continuous flow paper electrophoresis or density gradient zonal electrophoresis were unsuccessful.

Synthesis, structure characterization and biological activity of a novel amino acid salt (HAla)(8)(H3O)(10)[PMo12O40](6) center dot 22H(2)O

A novel compound was synthesized and characterized by means of elemental analysis, IR and UV spectra, TG, CV and single crystal X-ray diffraction. The compound crystallized in an orthorhombic space group C222 with a=1. 622 4(3) nm, b=3. 498 4(7) nm, c=1. 301 5(3) nm, V=7. 387 (3) nm(3), Z=6, R-1= 0. 037 3, wR(2)=0. 114 0. The Ala (Ala = alanine) molecules were protonated at the amino nitrogen N (1) and the C (2) of Ala group with the terminal oxygen atom O(15), O(14), O(26) and O(27) of the polyoxometalates participating in the hydrogen bond network. The anti-tumor activity of the title compound was estimated against Hela and Pc-3m cancer cells.

Synthesis and crystal structure of a novel amino-acid-containing polyoxometalate: K-6[Cu (Ala)(2) (H2O)(2)](2)[ CU4 (H2O)(2) (AsW9O34)(2)] center dot 16H(2)O

The novel amino-acid-containing polyoxometalate Ka(6) [Cu(Ala)(2) (H2O)(2)](2) [Cu-4 (H2O)(2) . (AsW9O34)(2)] . 16H(2)O was synthesized from the reaction of K-10[Cu-4(H2O)(2)(AsW9O34)(2)] . 20H(2)O with beta -alanine, Its structure has been determined by single crystal X-ray diffraction. It crystallizes in the triclinic space group P (1) over bar, with a=1. 196 3(2) nm, b=1. 536 5(3) nm, c=1. 591 4(3) nm, alpha =93. 97(3)degrees, beta= 110. 88(3)degrees, gamma =101. 07(3)degrees, V=2. 651 8(9) nm(3) and Z=1. Least-squares refinement of the structure leads to R and R-w factors of 0. 067 3 and 0. 162 8, respectively. An unusual structural feature of the compound is that the polyanion [Cu-4(H2O)(2) (AsW9O34)](10-) is linked with the amino-acid complex of Cu2+ by a mu -oxygen atom.

Synthesis and utilization of guanidine catalysts for applications directed towards the preparation of butenolide and modified amino acid derivatives

Development of guanidine catalysts is explored through direct iminium chloride and amine coupling, alongside a 2-chloro-l,3-dimethyl-IH-imidazol-:-3-ium chloride (DMC) induced thiourea cyclization. Synthesized achiral catalyst N-(5Hdibenzo[ d,t][1,3]diazepin-6(7H)-ylidene)-3,5-bis(trifluoromethyl) aniline proved unsuccessful towards O-acyl migrations, however successfully catalyzed the vinylogous aldol reaction between dicbloro furanone and benzaldehyde. Incorporating chirality into the guanidine catalyst utilizing a (R)-phenylalaninol auxiliary, generating (R)-2-((5Hdibenzo[ d,t] [1,3 ]diazepin-6(7H)-ylidene ) amino )-3 -phenylpropan-l-ol, demonstrated enantioselectivity for a variety of adducts. Highest enantiomeric excess (ee) was afforded between dibromofuranone and p-chlorobenzaldehyde, affording the syn conformation in 96% ee and the anti in 54% ee, with an overall yield of30%. Attempts to increase asymmetric induction were focused on incorporation of axial chirality to the (R)phenylalaninol catalyst using binaphthyl diamine. Incorporation of (S)-binaphthyl exhibited destructive selectivity, whereas incorporation of (R)-binaphthyl demonstrated no effects on enantioselectivity. Current studies are being directed towards identifying the catalytic properties of asymmetric induction with further studies are being aimed towards increasing enantioselectivity by increasing backbone steric bulk.

Synthesis of a novel class of chiral polyaromatic amide dendrimers bearing an amino acid derived C-3-symmetric core

Chiral polyaromatic amide dendrimers incorporating a C-3-core have been prepared as potential catalysts for asymmetric reactions. (C) 2002 Elsevier Science Ltd. All rights reserved.