Infrared spectroscopy of Cu+(H2O)(n) and Ag+(H2O)(n): coordination and solvation of noble-metal ions

M(+)(H(2)O)(n) and M(+)(H(2)O)(n)Ar ions (M=Cu and Ag) are studied for exploring coordination and solvation structures of noble-metal ions. These species are produced in a laser-vaporization cluster source and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region using a triple quadrupole mass spectrometer. Density functional theory calculations are also carried out for analyzing the experimental IR spectra. Partially resolved rotational structure observed in the spectrum of Ag(+)(H(2)O)(1) x Ar indicates that the complex is quasilinear in an Ar-Ag(+)-O configuration with the H atoms symmetrically displaced off axis. The spectra of the Ar-tagged M(+)(H(2)O)(2) are consistent with twofold coordination with a linear O-M(+)-O arrangement for these ions, which is stabilized by the s-d hybridization in M(+). Hydrogen bonding between H(2)O molecules is absent in Ag(+)(H(2)O)(3) x Ar but detected in Cu(+)(H(2)O)(3) x Ar through characteristic changes in the position and intensity of the OH-stretch transitions. The third H(2)O attaches directly to Ag(+) in a tricoordinated form, while it occupies a hydrogen-bonding site in the second shell of the dicoordinated Cu(+). The preference of the tricoordination is attributable to the inefficient 5s-4d hybridization in Ag(+), in contrast to the extensive 4s-3d hybridization in Cu(+) which retains the dicoordination. This is most likely because the s-d energy gap of Ag(+) is much larger than that of Cu(+). The fourth H(2)O occupies the second shells of the tricoordinated Ag(+) and the dicoordinated Cu(+), as extensive hydrogen bonding is observed in M(+)(H(2)O)(4) x Ar. Interestingly, the Ag(+)(H(2)O)(4) x Ar ions adopt not only the tricoordinated form but also the dicoordinated forms, which are absent in Ag(+)(H(2)O)(3) x Ar but revived at n=4. Size dependent variations in the spectra of Cu(+)(H(2)O)(n) for n=5-7 provide evidence for the completion of the second shell at n=6, where the dicoordinated Cu(+)(H(2)O)(2) subunit is surrounded by four H(2)O molecules. The gas-phase coordination number of Cu(+) is 2 and the resulting linearly coordinated structure acts as the core of further solvation processes.     

Widely useful DMAP-catalyzed esterification under auxiliary base- and solvent-free conditions

With regard to atom economy and E-factor, catalytic condensation of carboxylic acids with equimolar amounts of alcohols is the most desirable. Although several highly active dehydration catalysts have been reported, more efficient alternatives are still strongly needed because the dehydrative esterification of tertiary alcohols, phenols, acid-sensitive alcohols, amino acids, and hardly soluble alcohols has never proceeded satisfactorily. Here we report new insights into the classical DMAP-catalyzed acylation of alcohols: surprisingly, only a 0.05-2 mol % of DMAP can efficiently promote acylation of alcohols with acid anhydrides under auxiliary base- and solvent-free conditions to give the corresponding esters in high yields. Furthermore, we achieved the recovery and reuse of commercially available polystyrene-supported DMAP without using any solvents. These serendipitous findings provide widely useful and environmentally benign esterification methods, which might be more practical and reliable than catalytic dehydrative condensation methods, in particular, for the less reactive alcohols which hardly condense with carboxylic acid directly.     

On tests for selection of variables and independence under multivariate regression models

The authors consider various procedures for testing the hypotheses of independence of two sets of variables and certain regression coefficients are zero under multivariate regression model. Various properties of these procedures and the asymptotic distributions associated with these procedures are also considered.     

Improved stability of organic field-effect transistor performance in oligothiophenes including β-isomers

Dialkyl quarter- and quinquethiophenes end-capped with β-connected thiophenes are prepared, and the field-effect transistor (FET) properties are investigated. Molecular orbital calculation as well as the redox and optical measurements indicate that the β-isomers have low-lying HOMO levels and large energy gaps compared with the α-isomers. Molecular packing of the dihexylquaterthiophene with β-isomers consists of a typical herringbone motif analogous to the α-isomers. In the single crystal, the alkyl chains are extending in the tilted directions from the core molecular plane, but straightly extending in the thin films, resulting in even more perpendicular molecular arrangement to the substrate than the α-isomers. These β-isomers show p-type FET performance comparable to the corresponding α-isomers, whereas all new oligothiophenes show air stability better than the corresponding α-isomers. In particular, dihexylquinquethiophene with β-isomers has shown significantly improved air stability maintained over 270 days. This stabilization effect is ascribed to the low-lying HOMO level and the dense packing realized by perpendicular molecular arrangement.     

Reduction of pulse-to-pulse fluctuation in laser pulse energy using the optical Kerr effect

An all-optical stabilization method of laser pulse energy is proposed using the optical Kerr effect (OKE). The method uses the OKE induced by a portion of the laser pulse as a power controller. The decrease (increase) in the throughput of the optical setup for OKE compensates for the increase (decrease) in pulse energy, thereby stabilizing the pulse-to-pulse fluctuation in pulse energy. The validity of this principle was proven by experiments with a femtosecond laser.     

Gelation of an amino acid ionic liquid by the addition of a phosphonium-type zwitterion

1-Ethyl-3-methylimidazolium leucine, a typical amino acid ionic liquid, turns into a thermotropic and ion conductive gel while retaining its ion pair upon adding a phosphonium-type zwitterion.     

Three-dimensional structures of OSW-1 and its congener

The 3D structures of an antitumor glycosylsterol OSW-1 and its closely related congener were investigated by NMR studies and an X-ray crystallographic analysis. The disaccharide moiety was found as a structural scaffold for the formation of a hydrophobic cluster by the biologically required functionalities.     

Surface roughness assisted 100 kHz femtosecond laser induced nanostructure formation on silicon surface

Spontaneous nanostructure formations on roughened and smooth silicon surface by the femtosecond laser irradiation with the repetition rate of 100 kHz were systematically studied. In addition to the widely accepted so-called coarse ripple, which has the period analogous to the wavelength of the laser beam and aligns perpendicularly to the electric field of the incident laser beam, the ripple which has the period similar to the wavelength of the incident laser beam but aligns parallel to the electric field of the laser beam was observed on the roughened surface for the lower fluence and the higher number of pulse irradiation. Furthermore, the ensemble of dots formed by the enhancement of the local electric field was found on the roughened surface. This structure is preferentially formed around the scratches aligned perpendicularly to the electric field of the laser beam. These novel nanostructures are considered to be peculiar to the femtosecond laser irradiation and open the possibilities for precise control of the spontaneous nanostructure formation by femtosecond laser irradiation.     

Finding coherent cyclic orders in strong digraphs

A cyclic order in the vertex set of a digraph is said to be coherent if any arc is contained in a directed cycle whose winding number is one. This notion plays a key role in the proof by Bessy and Thomassé (2004) of a conjecture of Gallai (1964) on covering the vertex set by directed cycles. This paper presents an efficient algorithm for finding a coherent cyclic order in a strongly connected digraph, based on a theorem of Knuth (1974). With the aid of ear decomposition, the algorithm runs in O(nm) time, where n is the number of vertices and m is the number of arcs. This is as fast as testing if a given cyclic order is coherent.     

Synthesis of 4‐styrylphthalhydrazides and their chemiluminescence reaction. Emitters and chemiluminescence efficiency highly dependent on electronic nature of styryl goups

A series of 4‐styrylphthalhydrazides were synthesized and their chemiluminescence reactions were investigated. The chemiluminescence quantum yields as well as the emitters were variable depending on the electronic nature of the terminal substituents attached on the styryl groups. It was revealed that the excited phtha‐late ions were the emitters when they were highly fluorescent, while the energy transfer chemiluminescence from the excited phthalate ions to the phthalhydrazide anions took place when the fluorescence of the corresponding phthalate ions were very weakly fluorescent.