Copper-catalyzed enantioselective propargylic amination of nonaromatic propargylic esters with amines

The enantioselective propargylic amination of propargylic pentafluorobenzoates bearing an alkyl group at the propargylic position with amines in the presence of catalytic amounts of a copper complex and an optically active diphosphine such as BINAP has been found to give the corresponding propargylic amines in good yields with high enantioselectivity.     

Use of the MALDI BioTyper system with MALDI–TOF mass spectrometry for rapid identification of microorganisms

In a clinical diagnosis microbiology laboratory, the current method of identifying bacterial isolates is based mainly on phenotypic characteristics, for example growth pattern on different media, colony morphology, Gram stain, and various biochemical reactions. These techniques collectively enable great accuracy in identifying most bacterial isolates, but are costly and time-consuming. In our clinical microbiology laboratory, we prospectively assessed the ability of matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI–TOF MS) to identify bacterial strains that were routinely isolated from clinical samples. Bacterial colonies obtained from a total of 468 strains of 92 bacterial species isolated at the Department of Clinical Laboratory at Chiba University were directly placed on target MALDI plates followed by addition of CHCA matrix solution. The plates were then subjected to MALDI–TOF MS measurement and the microorganisms were identified by pattern matching with the libraries in the BioTyper 2.0 software. Identification success at the species and genus levels was 91.7% (429/468) and 97.0% (454/468), respectively. MALDI–TOF MS is a rapid, simple, and high-throughput proteomic technique for identification of a variety of bacterial species. Because colony-to-colony differences and effects of culture duration on the results are minimal, it can be implemented in a conventional laboratory setting. Although for some pathogens, preanalytical processes should be refined, and the current database should be improved to obtain more accurate results, the MALDI–TOF MS based method performs, in general, as well as conventional methods and is a promising technology in clinical laboratories.     

Design and stereoselective synthesis of four peptide nucleic acid monomers with cyclic structures in backbone

Four isomers of the monomer of peptide nucleic acid (PNA) were derived from (2S,4R)‐4‐hydroxyproline; they had different stereochemistries at the C² and C⁴ positions in the pyrrolidine ring. These different backbone conformations corresponding to four different stereochemistries were realized through a combination of inversions at the C² and the C⁴ positions in pyrrolidine ring. The obtained backbone frameworks were reacted with N‐benzoyl thymine to give the corresponding PNA monomers. Spectroscopic comparison of the resultant monomers confirmed their stereochemistries. J. Heterocyclic Chem., (2011).     

Vesicle growth and deformation in a surfactant solution below the Krafft temperature

We have studied vesicle growth and deformation in aqueous solutions of nonionic surfactant C(16)E(7) below the Krafft temperature by means of an optical microscope. It has been found that vesicles become larger by fusing together, and that the growth rate is slower than that of the unilamellar vesicle or emulsion systems due to the multilamellar structures of shells in a vesicle. The deformation of the vesicles depends on the temperature quench depth, and we found the transformation from spherical vesicles to string-like domains at a certain quench-temperature. From the small angle X-ray scattering and confocal microscope experiments, it can be deduced that the deformation of vesicles would be induced by osmotic pressure due to the micellar concentration difference between inside and outside of vesicles.     

Langmuir monolayers of a cholesterol-armed cyclen complex that can control enantioselectivity of amino acid recognition by surface pressure

The cholesterol-armed cyclen Na(+) complex formed stable Langmuir monolayers at the air-water interface. The π-A isotherm displayed a reasonable limiting molecular area of ～1.57 nm(2) and the areas expanded when amino acids were dissolved in water, indicating the efficient accommodation in the monolayers. Brewster angle microscopy (BAM) images exhibited almost no defects of the compressed Langmuir monolayers regardless of the presence of amino acids. Based on the idea that the increase in the limiting molecular areas corresponds to the amount of the adsorbed amino acid, the binding constants of three enantiomeric amino acids, namely valine (Val), leucine (Leu), and phenylalanine (Phe), were calculated at different surface pressures. Remarkably, a surface pressure dependent enantioselectivity of amino acid recognition was observed. Upon compression of the monolayers, the binding constants of amino acids increased accompanying an inversion of chiral selectivity from the D- to L-form in the case of Val and, conversely, from L- to D-form in the case of Phe.     

The effect of Cl...π interactions on the conformations of 4‐chloro‐5‐(2‐phenoxyethoxy)phthalonitrile and 4‐chloro‐5‐[2‐(pentafluorophenoxy)ethoxy]phthalonitrile

4‐Chloro‐5‐(2‐phenoxyethoxy)phthalonitrile, C₁₆H₁₁ClN₂O₂, (I), and 4‐chloro‐5‐[2‐(pentafluorophenoxy)ethoxy]phthalonitrile, C₁₆H₆ClF₅N₂O₂, (II), show different types of electrostatic interaction. In (I), the phenoxy and phthalonitrile (benzene‐1,2‐dicarbonitrile) moieties are well separated in an open conformation and intermolecular C—H...π interactions are observed in the crystal packing. On the other hand, in (II), the pentafluorophenoxy moiety interacts closely with the Cl atom to form a folded conformation containing an intramolecular halogen–π interaction.     

In situ measurement of crystallization of oxide thin films during irradiation with pulsed UV laser in chemical solution deposition process

The epitaxial and polycrystalline growth of lanthanum strontium manganite films on single crystalline strontium titanate and lanthanum aluminate substrates, respectively, under the irradiation with XeCl lasers in the excimer laser-assisted metal organic deposition (ELAMOD) process have been previously reported. In order to investigate the growth phenomena, we monitored the thermal radiation from the sample surfaces irradiated with a pulsed ultraviolet laser in situ with near-infrared sensors. The cooling of the lanthanum strontium manganite films on strontium titanate substrates was significantly slower than that of films on lanthanum aluminate substrates. A similar behavior was also observed by the numerical simulation study. This difference in the cooling decay curves may play an important role in the mode by which crystal growth occurs in the ELAMOD process.     

Synthesis of acetic acid from methanol alone by homogeneous metal complex catalyst. Part 4. In-situ formation of catalyst species and halogen effect in the RuCl3·3H2O–SnX2 (X=F, Cl, Br, I) composite system

Highly selective formation of methyl acetate has been found possible from methanol alone using the catalyst generated in situ from RuCl₃·3H₂O and SnCl₂ as well as SnX₂ (X=F, Br, I). The reaction did not occur in the absence of SnCl₂ added and the optimum [Sn]/[Ru] ratio appeared at about 16. The halogen effect showed the order of SnF₂>SnCl₂>SnBr₂>SnI₂, which indicates the importance of cationic character of Ru(II) center to facilitate its electrophilic interaction with β-hydrogen of Ru–OCH₃ intermediate in the rate-limiting dehydrogenation step.     

Oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with dinuclear‐type copper(II) catalyst

The oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with the novel dinuclear‐type copper(II) catalysts successfully produced poly(2,3‐dihydroxy‐1,4‐naphthylene). For example, the MeOH‐insoluble polymer with a number average molecular weight of 4.4 × 10³ from the polymerization using the complex of CuCl₂ and N,N′‐bis(2‐morpholinoethyl)‐p‐xylylenediamine ( p ‐ 1 ) at room temperature under an O₂ atmosphere followed by acetylation of the hydroxyl groups was obtained in 63% yield. The structures of the tetraamine ligands and the counter anion of the copper(II) salts significantly influenced the catalyst activity. The polymerization of 2,2′‐dimethoxy‐1,1′‐binaphthalene‐3,3′‐diol with the 2CuCl₂‐ p ‐ 1 catalyst, however, resulted in a lower yield. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1635–1640, 2005