Synthesis of a Pentacene‐Type Silaborin via Double Dehydrogenative Cyclization of 1,4‐Diboryl‐2,5‐disilylbenzene

A new pentacene‐type silaborin, in which three benzene rings are bridged by silicon and boron atoms, has been synthesized and characterized by using NMR spectroscopy and X‐ray crystallographic analysis. The precursor, 1,4‐bis(dimesitylboryl)‐2,5‐bis(phenylsilyl)benzene ( 4 ), was prepared by stepwise introduction of a silyl group and a boryl group to a benzene ring starting from 1,4‐dibromobenzene. Double cyclization of 4 proceeds by a H‐Mes exchange and a B‐H/C‐H dehydrogenative condensation to afford pentacene‐type silaborin 5 . X‐ray crystal structure analysis reveals that 5 adopts a bent structure rather than a planar one. UV/Vis spectra and DFT calculations for 5 reveal a lowering of the LUMO energy level compared with corresponding anthracene‐type 3 .     

Interaction of Short Laser Pulses in Wavelength Range from Infrared to X‐ray with Metals,Semiconductors, and Dielectrics

Laser‐matter interaction is defined by an electronic band structure of condensed matter and frequency ω_L of electromagnetic radiation. In the range of moderate fluences, the energy absorbed by electrons from radiation finally thermalizes in the ion thermal energy. The thermalization processes are different for optical as compared with X‐ray quanta and for metals relative to semiconductors and dielectrics, since the light absorption and electron‐electron, electron‐ion dynamics are sensitive to the electron population in a conduction band and the width of a forbidden gap. Although the thermalization processes are different, the final state is simply a heated matter. Laser heating creates powerful stresses in a target if duration of a laser pulse τ_L is short in acoustic time scale. Nucleation and material removal take place under such stresses. Such way of removal is called here the spallative ablation. Thus the spallative ablation is an ablation mechanism universally important for qualitatively different materials and quanta (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Metabolism of tetrahydrobiopterin: Its relevance in monoaminergic neurons and neurological disorders

(6R)‐L‐erythro‐5,6,7,8‐tetrahydrobiopterin (BH4) is an essential cofactor for aromatic amino acid hydroxylases, such as phenylalanine hydroxylase (PAH), tyrosine hydroxylase (TH), tryptophan hydroxylase, and nitric oxide synthase, which catalyze physiologically important reactions in mammals. The biosynthesis and metabolism of BH4 is usually studied mostly in the liver and only slightly in the brain, as the BH4 level in the liver is relatively high because BH4 is required for the reaction of PAH. We found that GTP (guanosine triphosphate) cyclohydrolase I, an enzyme for the biosynthesis of BH4, is a causative gene for DOPA (3,4‐dihydroxyphenylalanine)‐responsive dystonia (also called Segawa's disease), and that partial deficiency of BH4 leads to the dysfunction of the nigrostriatal dopaminergic neurons without hyperphenylalaninemia. We analyzed BH4‐deficient mice that were produced by disruption of a BH4‐synthesizing gene by a gene‐knockout technique. We found that the protein amount of TH was highly dependent on the amount of BH4, especially in nerve terminals. Our research suggests that BH4 metabolism in the brain should be different from that in the liver, and that altered metabolism of BH4 should lead to neuropsychiatric disorders including Parkinson's disease. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 378–385; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20166     

Analysis of one-and two-particle spectra at RHIC based on a hydrodynamical model

We calculate the one-particle hadronic spectra and correlation functions of pions based on a hydrodynamical model. Parameters in the model are so chosen that the one-particle spectra reproduce experimental results of √s= 130 AGeV Au + Au collisions at RHIC. Based on the numerical solution, we discuss the space-time evolution of the fluid. Two-pion correlation functions are also discussed. Our numerical solution suggests the formation of the quark-gluon plasma with large volume and low net baryon density.     

Organic crystals growth for optical channel waveguides

Optical channel waveguides of meta-nitroaniline (m-NA) crystal, which has potential applications to nonlinear optical devices, have been fabricated on glass substrates having fine grooves. The crystal growth was performed by zone-melting, scanning a CO₂ laser beam along the grooves filled with the polycrystal m-NA. Optical and X-ray observations showed that zone-melting changed the polycrystalline state to a single crystalline state with the 〈001〉 direction along the groove. The scattering loss for a 5 mm-long m-NA crystal waveguide (100 μm both in width and in depth) was found to decrease from 50 dB to 2.5 dB with this process.     

Study on 1,3,5‐Triazine Chemistry in Dehydrocondensation: Gauche Effect on the Generation of Active Triazinylammonium Species

The reaction of 2‐chloro‐4,6‐dimethoxy‐1,3,5‐triazine (CDMT) with various nitrogen‐containing compounds, particularly tertiary amines (tert‐amines), has been studied for the preparation of 2‐(4,6‐dimethoxy‐1,3,5‐triazinyl)trialkylammonium salts [DMT‐Am(s)]. DMT‐Ams derived from aliphatic tert‐amines exhibited activity for the dehydrocondensation between a carboxylic acid and an amine to form an amide in a model reaction. Based on a conformational analysis of DMT‐Ams and tert‐amines by NMR and X‐ray diffraction methods, we concluded that a β‐alkyl group maintained in a gauche relationship with the nitrogen lone pair of tert‐amines significantly hinders the approach of CDMT to the nitrogen. Thus, trimethylamine and quinuclidine without such alkyl groups readily react with CDMT whereas triethylamine, possessing two or three such gauche β‐alkyl groups in the stable conformations, does not react at all. The theory of “gauche β‐alkyl group effect” proposed here provides useful guidelines for the preparation of DMT‐Ams possessing various tertiary amine moieties. An investigation of the dehydrocondensation activity of tert‐amines in a CDMT/tert‐amine system that involves in situ generation of DMT‐Am, showed that the gauche effect of the β‐alkyl group becomes quite pronounced; the yield of the amide decreases significantly with tert‐amines possessing an unavoidable gauche β‐alkyl group. Thus, the tert‐amine/CDMT systems are useful for judging whether tert‐amines can readily react with CDMT without isolation of DMT‐Ams.     

Observations of surface modifications induced by the multiple pulse irradiation using a soft picosecond x-ray laser beam

To study the interactions between picosecond soft x-ray laser (SXRL) beams and material surfaces, gold (Au), copper (Cu), and silicon (Si) surfaces were irradiated with SXRL pulses having a wavelength of 13.9 nm and a duration of ～7 ps. Following irradiation, the surfaces of the substrates were observed using a scanning electron microscope and an atomic force microscope. With single pulse irradiation, ripple-like structures were formed on the Au and Cu surfaces. These structures were different from previously investigated conical structures formed on an Al surface. In addition, it was confirmed that the development of modified structures, i.e., growth of hillocks on the Au and Cu surfaces, was observed after multiple SXRL pulse exposures. However, on the Si surface, deep holes that seemed to be melted structures induced by the accumulation of multiple pulses of irradiations were found. Therefore, it was concluded that SXRL beam irradiation of various material surfaces causes different types of surface modifications, and the changes in the surface behaviors are attributed to the differences in the elemental properties, such as the attenuation length of x-ray photons.     

Second harmonic generation in inclusion complexes

Second harmonic generation (S.H.G.) in inclusion complexes between dimethyl -cyclodextrin (dimethyl -CD) and nitroaniline derivatives occurs. This is due to the destruction of the centrosymmtric crystal structure in nitroaniline derivatives caused by forming inclusion complexes. S.H.G. intensity of dimethyl -CD complex with N-methyl-nitroaniline is 5.5 times as large as that of urea.     

A racemization test in peptide synthesis using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM)

Racemization of the C-terminal amino acid (Ala) has been studied in various solvents during coupling between 4-methoxybenzyloxycarbonyl (Z(OMe))-Gly-L-Ala-OH and phenylalanine benzyl ester (H-Phe-OBzl) with 4-(4,6-dimethoxy-1,3,5-thiazin-2-yl)-4-methylmorpholinium chloride (DMT-MM). The reaction occurred without substantial racemization in AcOEt, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), CH3CN, and 2-PrOH, while a slight racemization was observed in dimethyl sulfoxide (DMSO), EtOH, and MeOH. The extent of racemization may correlate with the polarity of the solvents.