Synthesis of glutamate by reductive amination of 2-oxoglutarate with the combination of hydrogenase and glutamate dehydrogenase

Glutamate synthesis by reductive amination of 2-oxoglutarate was performed by the combination of NADH regeneration system and glutamate dehydrogenase (GluDH). The conversion of 2-oxoglutamate to glutamate was 98% after 3 h, and the turnover number of NAD⁺was 17.     

Density functional theory investigation of Eu(III) complexes with beta-diketonates and phosphine oxides: model complexes of fluorescence compounds for ultraviolet LED devices

The density functional theory was employed to investigate Eu(III) complexes with three beta-diketonates and two phosphine oxides (complex M1: Eu(bdk)3(TPPO)2, complex M2: Eu(bdk)3(TMPO)2, and complex M3: Eu(bdk)3(TPPO)(TMPO)) deemed to be the model complexes of the fluorescence compounds for the ultraviolet LED devices we have recently developed. For each complex, two minimum energy points corresponding to two different optimized geometries (structures A and B) have been found, and the difference of the energy between two minimum energy points is found to be quite small (less than 1 kcal/mol). Vertical excitation energies and oscillator strengths for each complex at two optimized geometries have been obtained by the time-dependent density functional theory, and the character of the excited states has been investigated. For complex M3, the absorption edge is red-shifted, and the oscillator strengths are relatively large. The efficiency of intersystem crossing and energy transfer from the triplet excited state to the Eu(III) ion is considered by calculating DeltaE(ISC) (the energy difference between the first singlet excited state and the first triplet excited state) and DeltaE(ET) (the difference between the excitation energy of the complex for the first triplet excited state and the emission energy of the Eu(III) ion for 5D to 7F).     

Synthesis of alanine and leucine by reductive amination of 2-oxoic acid with combination of hydrogenase and dehydrogenase

Alanine synthesis by reductive amination of pyruvate was performed by the combination of NADH regeneration system and alanine dehydrogenase (AlaDH). The conversion of pyruvate to alanine was 99% after 1 h. Leucine synthesis was also carried out by the combination of NADH regeneration system and leucine dehydrogenase (LeuDH). The conversion of 4-methyl-2-oxovalerate to leucine was 60% after 1.5 h.     

Resonance Raman spectra of tris(acetylacetonato)iron(III) and ruthenium(III) complexes and their solvent effect

The resonance Raman spectra of tris(acetylacetonatoiron(III)) and ruthenium(III) complexes in various solvents and in water-acetonitrile (W-AN) mixtures were measured. The resonance Raman spectra of both complexes indicated peaks near 460 and around 1580 cm^–1. Thev(C-O) peak (around 1580 cm^–1) is shifted to low frequency with an increase in the dielectric constant _T of the solvents, whereas thev(M-O) (M=Fe and Ru, near 460 cm^–1) are constant, independent of _T. It implies that the C-O bond in the acac^– ligand is lengthened by the polarizability effect of the solvents, while both the Fe-O and Ru-O bonds, which are located in the inside of the complexes, are not influenced by the solvents indicating that the interaction does not depend on the properties of individual solvent molecules but on those of the aggregate.     

Extraction equilibria for the 4-(2-Pyridylazo)-Resorcinol-Nickel(II)-Quaternary-Ammonium salt system

The extraction equilibria of nickel(II)-PAR complexes with tetradecyldimethylbenzylammonium chloride(Q⁺Cl^?) are investigated. Two kinds of nickel complex are extracted by chloroform: Ni(HR)₂,nQ⁺Cl^?₍₀₎(?⁵⁰⁰ = 3.73·10⁴l mol^?1cm^?1) at about pH 5 and 2Q⁺ NiR^2-_2(o)(?⁵⁰⁰ = 8.08·10⁴ l mol^?1 cm^?1) at above pH 8.5. The extraction constant for 2Q⁺ NiR^2-_2(o) was evaluated as [2Q⁺ NiR^2-₂]₀/[NiR^2-₂] [Q⁺]² = 10^11.16 at μ = 0.1 (Na₂SO₄. Synergic extraction studies of the Ni(HR)₂ species under slightly acidic conditions show that the species is Ni(HR)₂(H₂O)₂in auqeous solution and is extracted into chloroform as the adduct Ni(HR)₂(TBP)₂ (?⁵³⁵ = 3.57·10⁴ l mol^?1 cm^?1. Based on the extraction behavior of these complexes, the structures of the Ni²⁺—PAR complexes are discussed.     

Spectrophotometric studies on ion-pair extraction equilibria of the iron(ii) and iron(III) complexes with 4-(2-pyridylazo)resorcinol

The ion-pair extraction equilibria of the iron(II) and iron(III) chelates of 4-(2-pyridylazo)resorcinol (PAR, H(2)L) are described. The anionic chelates were extracted into chloroform with benzyldimethyltetradecylammonium chloride (QC1) as counter-ion. The extraction constants were estimated to be K(ex1)(Fe(II)) = [Q{Fe(II)(HL)L}](0)/[Q(+)][{Fe(II)(HL)L}(-)] = 10(8.59 +/- 0.11), K(ex2)(Fe(II)) = [Q(2){Fe(II)L(2)}](o)/ [Q(+)](2)[{Fe(II)L(2)}(2-)] = 10(12.17 +/- 0.10) and K(ex1)(Fe(III)) = [Q{Fe((III))L(2)}](o)/(Q(+)][{Fe(III)L(2)}(-)] = 10(6.78 +/- 0.15) at I = 0.10 and 20 degrees , where [ ](o) is concentration in the chloroform phase. Aggregation of Q{Fe(III)L(2)} in chloroform was observed and the dimerization constant (K(d) = [Q(2){Fe(III)L(2)}(2)](o)/[Q{Fe(III)L(2)}](o)(2)) was evaluated as log K(d) = 4.3 +/- 0.3 at 20 degrees . The neutral chelates of {Fe(II)(HL)(2)} and {Fe(III)(HL)L}, and the ion-pair of the cationic chelate, {Fe(III)(HL)(2)}ClO(4), were also extracted into chloroform or nitrobenzene. The relationship between the forms and extraction properties of the iron(II) and iron(III) PAR chelates are discussed in connection with those of the nickel(II) and cobalt(III) complexes. Correlation between the extraction equilibrium data and the elution behaviour of some PAR chelates in ion-pair reversed-phase partition chromatography is also discussed.     

Homoleptic cyclometalated iridium complexes with highly efficient red phosphorescence and application to organic light-emitting diode

Phosphorescence studies of a series of facial homoleptic cyclometalated iridium(III) complexes have been carried out. The complexes studied have the general structure Ir(III)(C-N)(3), where (C-N) is a monoanionic cyclometalating ligand: 2-(5-methylthiophen-2-yl)pyridinato, 2-(thiophen-2-yl)-5-trifluoromethylpyridinato, 2,5-di(thiophen-2-yl)pyridinato, 2,5-di(5-methylthiophen-2-yl)pyridinato, 2-(benzo[b]thiophen-2-yl)pyridinato, 2-(9,9-dimethyl-9H-fluoren-2-yl)pyridinato, 1-phenylisoquinolinato, 1-(thiophen-2-yl)isoquinolinato, or 1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinolinato. Luminescence properties of all the complexes at 298 K in toluene are as follows: quantum yields of phosphorescence Phi(p) = 0.08-0.29, emission peaks lambda(max) = 558-652 nm, and emission lifetimes tau = 0.74-4.7 micros. Bathochromic shifts of the Ir(thpy)(3) family [the complexes with 2-(thiophen-2-yl)pyridine derivatives] are observed by introducing appropriate substituents, e.g., methyl, trifluoromethyl, or thiophen-2-yl. However, Phi(p) of the red emissive complexes (lambda(max) > 600 nm) becomes small, caused by a significant decrease of the radiative rate constant, k(r). In contrast, the complexes with the 1-arylisoquinoline ligands are found to have marked red shifts of lambda(max) and very high Phi(p) (0.19-0.26). These complexes are found to possess dominantly (3)MLCT (metal-to-ligand charge transfer) excited states and have k(r) values approximately 1 order of magnitude larger than those of the Ir(thpy)(3) family. An organic light-emitting diode (OLED) device that uses Ir(1-phenylisoquinolinato)(3) as a phosphorescent dopant produces very high efficiency (external quantum efficiency eta(ex) = 10.3% and power efficiency 8.0 lm/W at 100 cd/m(2)) and pure-red emission with 1931 CIE (Commission Internationale de L'Eclairage) chromaticity coordinates (x = 0.68, y = 0.32).