Dilatometric study of monovalent counter-ion association with carboxylates

Volume changes accompanying the protonation of mono-, di- and poly-carboxylates in water were measured at 25° using the circulation dilatometer. The carboxylates include alkali metal and tetra-alkylammonium (TAA) salts of acetic, pivalic, glutaric acid and samples of poly(methacrylic acid) (PMA) having various molecular weights and degrees of stereoregularity. It was found that TAA counter-cation exerts specific influence on the differential molar volume change on protonation of the pivalate and PMA in contrast to the absence of such specificity in the corresponding alkali metal salts. These results were interpreted by the proposed association of the hydrophobic ammonium cation with the carboxylate anions. Volume contraction is accompanied by the association. It was also proposed, on the basis of these findings, that alkali metal counter-ion is not likely to be ‘site bound’ by the respective charges of PMA. PMA configuration has a minor effect on the volume change.     

Structural and electrochemical studies of novel bis(mu-methoxo)diiron complexes: observation of Fe(III)Fe(IV) and Fe(IV)Fe(IV) states resonating with phenoxyl radicals

Novel diiron complexes with an Fe2(mu-OMe)2 core were studied as models of the active site of nonheme iron-containing enzymes. X-ray crystal structures of the complexes showed the existence of two types of ligand folding-parallel and twisted-both of which have four virtually equivalent phenolato groups sticking out from the Fe2O2 rhombic plane. Cyclic voltammetry measurements revealed two or more distinct redox waves in a region of relatively high potential, in addition to known Fe(II)/Fe(III) redox waves in a region of lower potential. These new peaks were assigned to the high-valence state of iron atoms, that is, Fe(III)Fe(IV) and Fe(IV)Fe(IV), resonating with the phenoxyl radical(s). The split width of the redox waves ranged from 0.14 to 0.20 eV, which may be a measure of the electronic interaction of the phenolate groups through the Fe2(mu-OMe)2 core.     

Rhodamine B amine as a highly sensitive fluorescence derivatization reagent for saccharides in reversed-phase liquid chromatography

6-Rhodamine B amine functions as a highly sensitive fluorescence derivatization reagent for mono- and oligosaccharides; it reacts with the reducing end of saccharides under acidic conditions. The fluorescent derivatives of five monosaccharides can be separated within 25 min by reversed-phase liquid chromatography with isocratic elution. The detection limits (S/N = 3) for mono-, di-, and oligosaccharides are 7-51, 13, and 9-35 fmol/20 microl injection, which correspond to analyte concentrations of 35-255, 65, 45-175 nM, respectively. We have applied this derivatization method successfully to the analysis of the components of oligosaccharides in glycoproteins (ribonuclease B and fetuin) following their acidic or enzymatic hydrolysis. The results from these analyses are in good agreements with the reported values established previously.     

Effects of gamma-irradiation on CO2 fixation and

To investigate the possibility of ¹⁴CO₂ fixation using microorganisms in a high-dose area, the photosynthetic activity (specific production rate: SPR) and cellular proliferation (colony forming unit: CFU) of Euglena gracilis Z irradiated with gamma-rays at a dose of 0 to 500 Gy were determined. The dose responses of SPR and CFU suggested that it was possible to operate a CO₂ fixation system of Euglena up to 100 Gy. Even at a dose of 500 Gy, about half of the photosynthetic activity under non-irradiated condition was considered possible.     

3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxo-qinoxaline-2-carbonyl azide as a highly sensitive fluorescence derivatization reagent for primary,secondary and tertiary alcohols in high-performance liquid chromatography

3,4-Dhydro-6,7-dimethoxy-4-methyl-3-oxo-quinoxaline-2-carbonyl azide is a highly senstive fluorescence derivatization reagent for primary, secondary and tertiary alcohols for high-performance liquid chromatography. Reaction conditions are optimized with benzyl alcohol, n-hexanol, cyclohexanol and 2-methyl-2-butanol. The reagent reacts with the alcohols in benzene to produce the corresponding fluorescent carbamic acid esters, which can be separated on a reversed-phase column YMC Pack C₈ with aqueous methanol as eluent. the detection limits for the alchols are 2–5 fmol per 10-μl njection. The reagent also reacts with hydroxysteroids with primary, secondary and/or tertiary alcoholic group(s) to form fluorescent derivatives. Hydroxycarboxylic acids and phenols do not give any chromatographic peaks.     

A novel synthesis of α-hydroxy- and α,α′-dihydroxyketone from α-iodo and α,α′-diiodo ketone using photoirradiation

A novel reaction of α-iodo ketone (α-iodocycloalkanone, α-iodo-β-alkoxy ester, and α-iodoacyclicketone) with irradiation under a high-pressure mercury lamp gave the corresponding α-hydroxyketone in good yields. In the case of α,α′-diiodo ketone, α,α′-dihydroxyketone which little has been reported until now was obtained. This reaction affords a new, clean and convenient synthetic method for α-hydroxy- and α,α′-dihydroxyketone.     

High-performance liquid chromatography of biogenic amines in the corpus cardiacum of the American cockroach, Periplaneta americana

The simultaneous determination of biogenic amines in the corpus cardiacum of the American cockroach, Periplaneta americana, was carried out using high-performance liquid chromatography with a Neurochem neurochemical analyser. Vanillic acid, dopamine, octopamine and tyramine were detected. Tyrosine and tryptophan were also detected at high levels. Octopamine levels in the corpus cardiacum were increased on injection of an acetone solution. The biological function of the biogenic amines detected is discussed.     

Asymmetric crystallization of bisguanidinobenzene derivatives

We show that the mono-N-methylated and -ethylated derivatives of the achiral compound bisguanidinobenzene undergo spontaneous asymmetric crystallization into a chiral form with chiral space group P2₁2₁2₁. The absolute configurations of the chiral crystals were determined by X-ray crystallography and correlated with circular dichroism (CD) spectra recorded in the solid state. The corresponding protonated and isopropylated derivatives, by contrast, afforded achiral crystals.     

Synthesis and properties of the first stable silylene-isocyanide complexes

The first stable silylene-isocyanide complexes, [Tbt(Mes)SiCNAr] (5 c: Ar=Tip, 5 d: Ar=Tbt, 5 e: Ar=Mes*; Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes=mesityl, Tip=2,4,6-triisopropylphenyl, Mes*=2,4,6-tri-tert-butylphenyl) were successfully synthesized by the reaction of a kinetically stabilized disilene, [Tbt(Mes)Si=Si(Mes)Tbt] (1), with bulky isocyanides, ArNC (3c-e). The spectroscopic data of 5 c-e and theoretical calculations for a model molecule indicated that 5 c-e are not classical cumulative compounds but the first stable silylene-Lewis base complexes. The reactions of 5 c-e with triethylsilane and 1,3-dienes gave the corresponding silylene adducts, and they underwent isocyanide-exchange reactions in the presence of another isocyanide at room temperature. These results indicate dissociation of complexes 5 c-e to the corresponding silylene 2 and isocyanides 3 c-e under very mild conditions. The reaction of 5 c with methanol gave the MeOH adduct 16, [Tbt(Mes)SiHC(OMe)NTip], which has a hydrogen atom on the silicon atom. This regioselectivity can be explained in terms of the contribution of zwitterionic resonance structures D and E, which have an anion on the silicon atom. This result indicates that 5 c is not a classical cumulene having Si=C double bonds that should react with methanol to give adducts bearing a methoxyl group on the silicon atom. Although the reactions of 5 c-e with electrophilic reagents such as methanol, hydrogen chloride, and methyl iodide gave the formal silylene adducts, the studies on the reaction mechanism by trapping experiments and the observation of the intermediate suggested that the reaction mainly or partially proceeds by initial nucleophilic attack of the silicon atom, as is the case in the formation of 16 in the reaction of 5 c with methanol. It was revealed that 5 c-e show the nucleophilicity of the silicon atom, most likely resulting from the contribution of the zwitterionic resonance structures D and E.     

Structures and stabilities of 3d-transition metal-benzene organometallic clusters

In the gas phase, we have successfully synthesized organometallic clusters, M_n(benzene)_m (M=3d transition metal atoms), by using a laser vaporization method. The measurements of mass spectra and ionization energies (E_i) have revealed that the organometallic clusters can take two types of structures; layered sandwich structures (m = n + 1) and metal clusters saturatedly covered with benzenes. For early transition metals of Sc, Ti, and V, only the multiple decker sandwich structure clusters were preferentially produced, in which benzene and metal atoms are alternately piled up. For late transition metals of Co and Ni, the metal clusters saturatedly surrounded by benzenes were also produced as well as the sandwich clusters. Furthermore, the E_is of M₁(benzene)₂ (M = Sc-Ni) were systematically measured and their electronic properties will be discussed.