Fundamental investigation of thermal properties of rare-earth beta-diketonates

The thermal properties of the rare-earth chelates of Htfa (trifluoroacetylacetone) and Hhfa (hexafluoroacetylacetone) have been investigated. Thermogravimetric curves were obtained by heating samples in the injection chamber of a gas chromatograph, both in an atmosphere of helium, and of helium containing ligand vapour. None of the chelates was completely vaporized in a helium atmosphere at temperatures up to about 240 degrees , but the tfa chelate of Lu and all the hfa chelates were completely vaporized in the atmosphere of helium containing ligand vapour. The vapour pressures and heats of vaporization of these chelates were also measured.     

Kinetic study of the electron-transfer oxidation of the phenolate anion of a vitamin E model by molecular oxygen generating superoxide anion in an aprotic medium

Electron-transfer reduction of molecular oxygen (O2) by the phenolate anion (1-) of a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), occurred to produce superoxide anion, which could be directly detected by a low-temperature EPR measurement. The rate of electron transfer from 1- to O2 was relatively slow, since this process is energetically unfavourable. The one-electron oxidation potential of 1- determined by cyclic voltammetric measurements is sufficiently negative to reduce 2,2-bis(4-tert-octylphenyl)-1-picrylhydrazyl radical (DOPPH*) to the corresponding one-electron reduced anion, DOPPH-, suggesting that 1- can also act as an efficient radical scavenger.     

Ratiometric direct detection of nitric oxide based on a novel signal-switching mechanism

A novel fluorescent probe, which could be the first example of a ratiometric molecular probe for direct monitoring of NO production, has been developed using a 'spin-exchange' mechanism.     

ESTIMATION OF AN INDEX OF HYDROPHOBICITY OF DNA INTERIOR USING 5-METHOXYPSORALEN AS A FLUORESCENT PROBE

The index of hydrophobicity of DNA interior was estimated by measuring fluorescence spectra of psoralen derivatives associated with DNA. The environment around 5-MOP associated with DNA was as hydrophobic (D_k = 34) as methanol, suggesting that the molecules reside at the space between the base-pairs in B-form DNA. This is also true for 8-MOP. Thus, planar and aromatic molecules of 5- and 8-MOP are more stable in the interior of DNA than in aqueous medium due to hydrophobic affinity.     

Enantioselective ester synthesis in the presence of optically active polymers

Enantiomer-differentiating ester syntheses from acid salts, chlorides, and an anhydride were studied in the presence of optically active polyamines. Enantiomer selection occurred in reactions of a racemic salt with an achiral alkyl bromide and vice versa, which is good evidence of the importance of activation of the carboxylate group by complexation of the counterion and activation of alkyl bromide by the formation of a quaternary salt with polyamine under solid–liquid, phase-transfer reaction conditions. Only small optical activity was observed in the products of acid anhydride or chloride with alcohol.     

Contribution of individual zinc ligands to metal binding and peptide folding of zinc finger peptides

Little is known about the contribution of individual zinc-ligating amino acid residues for coupling between zinc binding and protein folding in zinc finger domains. To understand such roles of each zinc ligand, four zinc finger mutant peptides corresponding to the second zinc finger domain of Sp1 were synthesized. In the mutant peptides, glycine was substituted for one of four zinc ligands. Their metal binding and folding properties were spectroscopically characterized and compared to those of the native zinc finger peptide. In particular, the electronic charge-transfer and d-d bands of the Co(II)-substituted peptide complexes were used to examine the metal coordination number and geometry. Fluorescence emission studies revealed that the mutant peptides are capable of binding zinc despite removing one ligand. Circular dichroism results clearly showed the induction of an alpha-helix by zinc binding. In addition, the structures of certain mutant zinc finger peptides were simulated by molecular dynamics calculation. The information indicates that His23 and the hydrophobic core formed between the alpha-helix and the beta-sheet play an essential role in alpha-helix induction. This report demonstrates that each ligand does not contribute equally to alpha-helix formation and coordination geometry in the zinc finger peptide.     

Total synthesis of (-)-stevastelin B

The total synthesis and an unambiguous structure confirmation of stevastelin B 1, a novel 15-membered cyclic depsipeptide, are described; the fatty acid moiety in 1, prepared stereoselectively from L-quebrachitol was converted into the amino carboxylic acid, whose macrolactamization by Shioiri's procedure effectively constructed the cyclic structure of 1.     

Gas chromatography of manganese(II) and manganese(III) trifluoroacetylacetonates by the ligand vapour technique

The thermal properties and gas Chromatographie behaviour of manganese(II) and manganese(III) trifluoroacetylacetonates (TFA) were investigated by using the ligand vapour technique. The two chelates, Mn(TFA); and Mn(TFA)₃, can be quantitatively eluted on a mixed-liquid phase (1.9% OV-17 ÷ 0.1% PEG-20M) at column temperatures above 210°C and 130–150°C, respectively; Mn(TFA)₃ is completely converted to Mn(TFA)₂ by thermal dissociation at column temperatures above 180°C and completely eluted as Mn(TFA)₂ above 210°C. The chelates can be determined separately within errors of about 1% after a preliminary extraction.