The nature of europium ion in carbonate solution and polarographic determination of micro amounts of europium

The nature of the complex europium carbonate ion in concentrated carbonate solution was studied polarographically. A polarographic method for the determination of micro amounts of europium ion in the presence of diverse ions (and especially lanthanides) was developed.     

Direct counting of submicrometer-sized photosynthetic apparatus dispersed in medium at cryogenic temperature by confocal laser fluorescence microscopy: estimation of the number of bacteriochlorophyll c in single light-harvesting antenna complexes chlorosomes of green photosynthetic bacteria

The number of pigments in single light-harvesting complexes (chlorosomes) were calculated by imaging single chlorosomes in a frozen buffer at cryogenic temperature with a confocal laser fluorescence microscope and pigment extraction. Chlorosomes were isolated from two types of green photosynthetic bacteria Chlorobium (Chl.) tepidum and Chloroflexus (Cfl.) aurantiacus and were individually imaged in the frozen medium. Each fluorescence spot observed mainly came from a single chlorosome and was ascribable to self-aggregates of bacteriochlorophyll (BChl) c molecules as core parts of chlorosomes. A three-dimensional distribution of fluorescence of single chlorosomes was analyzed, and the number of chlorosomes in a volume of 54,000 microm(3) was counted directly. On the basis of the results, averaged numbers of the BChl c molecules contained in a single chlorosome of Chl. tepidum and Cfl. aurantiacus were determined to be 1.4 x 10(5) and 9.6 x 10(4), respectively. The present numbers are almost comparable to those estimated by other methods (Martinez-Planells et al., Photosynth. Res. 2002, 71, 83 and Monta?o et al., Biophys. J. 2003, 85, 2560).     

Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment

A combination of nuclear resonance vibrational spectroscopy (NRVS), FTIR spectroscopy, and DFT calculations was used to observe and characterize Fe?H/D bending modes in CrHydA1 [FeFe]‐hydrogenase Cys‐to‐Ser variant C169S. Mutagenesis of cysteine to serine at position 169 changes the functional group adjacent to the H‐cluster from a ‐SH to ‐OH, thus altering the proton transfer pathway. The catalytic activity of C169S is significantly reduced compared to that of native CrHydA1, presumably owing to less efficient proton transfer to the H‐cluster. This mutation enabled effective capture of a hydride/deuteride intermediate and facilitated direct detection of the Fe?H/D normal modes. We observed a significant shift to higher frequency in an Fe?H bending mode of the C169S variant, as compared to previous findings with reconstituted native and oxadithiolate (ODT)‐substituted CrHydA1. On the basis of DFT calculations, we propose that this shift is caused by the stronger interaction of the ‐OH group of C169S with the bridgehead ‐NH‐ moiety of the active site, as compared to that of the ‐SH group of C169 in the native enzyme.     

Mass balance method for purity assay of phthalic acid esters: development of primary reference materials as traceability sources in the Japan Calibration Service System

Purity assay of high-purity materials (HPMs) of phthalic acid esters (PAEs) was carried out by means of a mass balance method. In this method, chromatographic methods such as gas chromatography-flame ionization detector (GC-FID) and/or high-performance liquid chromatography (HPLC) in combination with other methods such as Karl-Fischer (KF) titration and vacuum evaporation (VE) were applied. The sum of the impurities estimated by these methods allowed the estimation of the purity of the main component by difference. Seven PAEs with varying side chain structures and levels of impurities were analysed on a systematic way in which impurities were classified into several groups in terms of their abundance, availability of qualitative information and availability of authentic compounds, etc. The absolute quantity of each impurity was determined by GC-FID and/or HPLC based on the calibration made by the authentic compounds of impurities whenever available. The purities in mass fraction of these PAEs were certified at the National Metrology Institute of Japan (NMIJ), and the PAEs were registered as primary reference materials playing an essential role in linking the metrological traceability of the Japan Calibration Service System (JCSS) to the International System of Units (SI).     

Structural disorder and diffusional pathway of oxide ions in a doped Pr2NiO4-based mixed conductor

MEM nuclear density analysis from neutron diffraction data measured in situ at 1015.6 degrees C has indicated the two-dimensional network of curved O2-O3-O2 oxide-ion diffusion paths on the (Pr,La)-O layer in a K2NiF4-type structured oxide-ionic and electronic mixed conductor (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+delta.     

Synthesis of bis(N-heterocyclic carbene) palladium complexes derived from (S,S)-1,2-bis(1-hydroxypropyl)benzene

New o-xylylene-linked bis(benzimidazolium) salts were synthesized in six-steps from C₂-symmetric chiral 1,4-diol, 1,2-bis(1-hydroxypropyl)benzene, as a starting material. The silver complex of bis(benzimidazol-2-ylidene) was obtained on treatment of bis(benzimidazolium) salt with silver oxide. The reaction of the silver bis-NHC with [PdCl₂(PhCN)₂] afforded the bis-NHC complex of palladium. The X-ray diffraction studies on Pd complexes revealed that these complexes have distorted square planar geometry around the Pd center coordinating the NHC ligand in mutually cis-position. The arene ring of o-xylylene unit hanged over the Pd center and thus these complexes showed C₁-symmetric structures. The variable temperature NMR spectroscopy revealed that these Pd complexes showed fluxional behavior between C₁- and C₂-symmetric structures in solution state.     

Characterization of a synthetic peroxodiiron(III) protein model complex by nuclear resonance vibrational spectroscopy

The vibrational spectrum of an η(1),η(1)-1,2-peroxodiiron(III) complex was measured by nuclear resonance vibrational spectroscopy and fit using an empirical force field analysis. Isotopic (18)O(2) labelling studies revealed a feature involving motion of the {Fe(2)(O(2))}(4+) core that was not previously observed by resonance Raman spectroscopy.     

Reactivities of Stable Rotamers: XLIV. Ring-Opening Reactions of 1-(9-Fluorenyl)-2-(2-methyl-2-oxiranyl)naphthalene Rotamers With Acids and the Structure of Oxiranes

X-ray crystallography of the ap-form of the 1-(9-fluorenyl)-2-(2-methyl-2-oxiranyl)naphthalene has revealed that the carbon atom of the oxirane which is connected to the naphthyl group in this compound is almost planar. The specific structural features of the epoxy ring in this compound are caused by sterical effects and by the presence of a -system in the immediate vicinity of the oxirane ring. Certain differences have been found also in reactivity of rotational isomers of 2-X-substituted 1-[1-(9-fluorenyl)-2-naphthyl]ethyl cations (X = O, S, Se). At X = O arose more deprotonation product from the -position of the oxygen than in reactions of sulfur and selenium-containing analogs. Reactions of epoxides with zinc chloride almost exclusively gave the corresponding aldehydes.     

Determination of ppb levels of tryptophan derivatives by capillary electrophoresis with homogeneous liquid-liquid extraction and sweeping method

Tryptophan (Trp) derivatives were selectively separated from 24 kinds of amino acid mixture solutions. Capillary electrophoresis (CE) with UV detection using the described pretreatment system was able to separate and determine 4 kinds of Trp derivatives: 5-hydroxy L-tryptophan, 5-methyl L-tryptophan, 1-methyl L-tryptophan and L-tryptophan. The pretreatment system used a combination of a homogeneous liquid-liquid extraction and a sweeping method, the two are different kinds of powerful preconcentration/separation methods. Trp derivatives were thus separated by two different separation systems. First, these derivatives were selectively extracted at 57-100% by a homogeneous liquid-liquid extraction; secondly, they were respectively separated by micellar electrokinetic chromatography (MEKC) with a sweeping effect. The detection limits following complete separation of the Trp derivatives were 10(-8) mol l(-1) levels, respectively. The proposed method provided a more than 10-fold the improvement in sensitivity compared with fluorescence labeling/fluorophotometric analysis; the proposed method was also applied to the component analysis of nutritious medicine.     

Practical and Scalable Organic Reactions with Flow Microwave Apparatus

Microwave irradiation has been used for accelerating organic reactions as a heating method and has been proven to be useful in laboratory scale organic synthesis. The major drawback of microwave chemistry is the difficulty in scaling up, mainly because of the low penetration depth of microwaves. The combination of microwave chemistry and flow chemistry is considered to overcome the problem in scaling up of microwave‐assisted organic reactions, and some flow microwave systems have been developed in both academic and industrial communities. In this context, we have demonstrated the scale‐up of fundamental organic reactions using a novel flow microwave system developed by the academic‐industrial alliance between the University of Shizuoka, Advanced Industrial Science and Technology, and SAIDA FDS. In this Personal Account, we summarize the recent progress of our scalable microwave‐assisted continuous synthesis using the SAIDA flow microwave apparatus.