Catalytic activation of nucleophile precursors with metal acetates in alcohol media and applications to enantioselective Michael addition reactions

Nickel(II) acetate tetrahydrate works as catalyst to activate nucleophile precursors in Michael addition reactions. Use of alcohol media is essential for the high catalytic activation of nucleophile precursors. Catalytic enantioselective reactions using a chiral nickel(II) acetate tetrahydrate between dimedone and α,β-unsaturated amide acceptors provide a useful synthetic access to enantiomers of enol lactones through the carbon-carbon bond formation.     

Side chain liquid crystal poly(fumarate)s bearing tolane‐based mesogens

Cyanotolane or fluorotolane mesogens were for the first time introduced into the fumarate monomer under basic conditions. All fumarate monomers undergo radical polymerization in benzene in the presence of dimethyl 2,2′‐azobis(isobutyrate) as an initiator at 60 °C, affording the corresponding poly(fumarate)s with a molecular weight (M_n) of ～ 10⁴ and an exceptionally narrow polydispersity. The phase behaviors of the fumarate monomers and the correspoding poly(fumarate)s were comprehensively investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X‐ray diffraction (XRD) analysis. For the fumarate monomers, fluorotolane derivatives were prone to form higher‐order liquid crystal phases such as a smectic phase, while cyanotolane derivatives tended to show a wide mesophase temperature range, depending on the alkyl chain spacer length. Very surprisingly, these features dramatically weakened when they were polymerized. The mesophase temperature ranges became narrow and completely disappeared for the poly(fumarate)s with a shorter alkyl chain spacer. A nematic phase representing lower‐order arrangements became a predominant liquid crystal phase for the poly(fumarate) carrying cyanotolane mesogens. Only the poly(fumarate) carrying fluorotolane mesogens with a longer alkyl chain spacer displayed the characteristic XRD patterns of the smectic B phase. The transient photocurrent measurements of the fumarate monomer with cyanotolane mesogens displayed a hole mobility of the order of 10^?4–10^?5 cm² V^?1 s^?1 at room temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5101–5114, 2008     

First observation of the point spread function of optical transition radiation

We represent the first experimental observation of the point spread function (PSF) of optical transition radiation (OTR) performed at KEK-Accelerator Test Facility extraction line. We have demonstrated that the PSF vertical polarization component has a central minimum with a two lobe distribution. However, the distribution width varied significantly with wavelength. We assume that we observed a severe effect from spherical or chromatic aberrations which are not taken into account in any existing theoretical model. We believe that the result of this work will encourage theoreticians to continue developing the theory as it is important for various transition radiation applications. Nonuniform distribution of the OTR PSF creates an opportunity for developing a submicrometer transverse beam size monitor.     

Phase-shifting mask design for interference exposure of chirp blazed grating

An interference exposure system using a phase-shifting mask was proposed for generating periodic sawtooth optical intensity profile with chirp in period. Multiple space-harmonic waves are launched from the mask by diffraction, and the sawtooth optical intensity is formed by interference based on Fourier synthesis after propagation through an air gap. The design concept merely utilizing positive diffraction-order harmonics with tilt illumination of an exposure light and a design algorithm based on time-reversed configuration for calculating required phase shift amount were proposed and discussed. A phase-shifting mask for a blazed grating of very high chirp rate was designed to demonstrate its potential and feasibility. The grating period changes from 2.2 to 3.1 μm gradually within 0.3 mm length. Sawtooth-like optical intensity profile was confirmed by theoretical simulation as well as preliminary experimental results.     

Evaluations of vertical resolution of conductive polymer three-dimensional microstructures photofabricated in transparent polymer sheet

Conductive polymer three-dimensional microstructures were photofabricated utilizing the two-photon absorption of a sensitizer dye. The resulting three-dimensional structures were excised from the transparent polymer sheet using a micro-manipulator. The processing precisions for the vertical direction of the conductive polymer three-dimensional microstructure obtained in the transparent polymer sheet were evaluated in the present study. As a result, for the configurations of the obtained polypyrrole line deposition, the line height/line width ratios were around 5: 1; this ratio is higher than that of other UV resin works (h: w 2:4–3: 1) and the cross section distortion is not negligible for maintaining the higher reproducibility of the photofabrication.     

Singular orbital magnetism of graphene

The origin of the singular diamagnetic susceptibility at the Dirac point is probed through the study of effects of band-gap opening and spatially varying magnetic field. In the presence of a band gap, the susceptibility is nonzero only inside the band gap and exhibits a discrete jump at the band edges down to zero in the conduction and valence bands. The jump height is understood in terms of the pseudo-spin paramagnetism arising from valley degree of freedom. In spatially varying magnetic field with wave vector q, the susceptibility becomes nonzero only in a finite energy region containing the Dirac point, determined by q. This behavior is understood in terms of electronic states numerically calculated in periodic magnetic field.     

Ab initio molecular orbital study on three feasible mechanisms for substitution of the vinylic carbon in F2C=C(OMs)BMe3−

A substitution on 2,2-difluorovinylic carbon was investigated by using ab initio molecular orbital calculations. Three feasible mechanisms, which are the S_N1-like, the S_N2-type and the addition-elimination mechanisms, were ex- amined for a model borate, 2,2-difluoro-1-mesyloxyvinyl(trimethyl)borate. Four TSs were obtained depending on the position of Li⁺ around the vinylborate although activation energies in the gas phase are rather high (ca. 30–40 kcal mol⁻¹) in comparison with that expected from the experimental conditions. It was confirmed at the SCRF-IPCM calculations that the solvent effect reduces the acti- vation energy of one S_N2-type mechanism very much (4. l kcal mol⁻¹ at the B3LYP/6-31+G^*//RHF/6-31+G^/s* level of theory) while those for the other mechanisms do not change very much. Therefore, the S_N2-type mechanism is applicable to the substitution reaction observed for the vinylborate.     

Emittance measurement & optimization for the photocathode RF gun with laser profile shaping

The Laser Undulator Compact X-ray source(LUCX) is a test bench for a compact high brightness X-ray generator,based on inverse Compton Scattering at KEK,which requires high intensity multi-bunch trains with low transverse emittance.A photocathode RF gun with emittance compensation solenoid is used as an electron source.Much endeavor has been made to increase the beam intensity in the multi-bunch trains.The cavity of the RF gun is tuned into an unbalanced field in order to reduce space charge effects,so that the field gradient on the cathode surface is relatively higher when the forward RF power into gun cavity is not high enough.A laser profile shaper is employed to convert the driving laser profile from Gaussian into uniform.In this research we seek to find the optimized operational conditions for the decrease of the transverse emittance.With the uniform driving laser and the unbalanced RF gun,the RMS transverse emittance of a 1 nC bunch has been improved effectively from 5.46 πmm.mrad to 3.66 πmm.mrad.     

Erratum to "Aerosol pollution in China: Present and future impact on environment"

PARTICUOLOGY regrets that the above paper was mistakenly classified as a ‘Review’ rather than an ‘Invited paper’ when originally published in volume 7, issue 6, 426–431.     

First observation of a smectic A-cholesteric phase transition in a thermotropic liquid crystal consisting of a rigid-rod helical polysilane

A smectic A-cholesteric phase transition for a rigid-rod helical polymer, poly[n-decyl-(S)-2-methylbutylsilane] (PD2MBS), with a narrow molecular weight distribution, has been observed for the first time. Polarizing optical microscopy showed that the fan-shaped texture of the smectic A phase turned into the characteristic planar texture of the cholesteric phase upon heating. The positive CD band, which corresponds to the reflection band of the cholesteric phase, gradually decreased in intensity within a range 30°C below the transition temperature on cooling, while the peak maximum shifted towards shorter wavelengths. It was concluded that the system has a very wide temperature region over which the cholesteric-smectic A phase transition occurs and in which the cholesteric pitch varies with temperature.