Electronic structures of the highest occupied molecular orbital bands of a pentacene ultrathin film

We report the energy dispersions of the highest occupied molecular orbitals (HOMO)-derived bands of a pentacene (Pn) thin film, whose in-plane structure resembles closely that of the ab plane of a low-density bulk Pn phase. Our present photoemission result indicates that the overlap of the pi-orbitals of adjacent Pn molecules is larger than what was expected from theoretical calculations. Further, of the two HOMO-derived bands, the large dispersion width of the band with higher binding energy suggests that this one mainly contributes to the bandlike charge transport in a Pn crystal.     

Acid-induced conformational alteration of cis-preferential aromatic amides bearing N-methyl-N-(2-pyridyl) moiety

A series of cis-preferential aromatic N-methyl amides was designed and synthesized, and acid-induced conformational alteration of these compounds was investigated by means of NMR measurements in solution and X-ray crystal structure analysis. Compounds with a terminal N-methyl-N-(2-pyridyl) amide unit showed acid-induced conformational change from cis to trans, while those with a terminal N-methyl-2-pyridinecarboxamide unit showed a change of the carbonyl orientation from anti to syn with retention of cis conformation.     

Synthesis of the proposed structure of phaeosphaeride A

The first total synthesis of the proposed structure of phaeosphaeride A has been achieved via six-membered-ring formation by means of an intramolecular vinyl-anion aldol reaction as the key step. This synthesis suggests a revised configurational assignment for phaeosphaeride A.     

Stabilization mechanism of clarithromycin tablets under gastric pH conditions

It has been reported that tablets of clarithromycin (CAM), a 14-membered macrolide antibiotic, are especially stable under low pH conditions such as in gastric fluid, and showed excellent antibacterial efficiency even though CAM molecules themselves are rapidly decomposed. Therefore, we aimed to clarify the stabilization mechanism of CAM tablets under low pH conditions. From the results of stability and dissolution tests, the optimal decomposition rate constant (K(dec)) and dissolution rate constant (K(dis)) at various pH values were calculated by curve-fitting to consecutive reactions. Consequently, log(K(dec)) increased as pH decreased. On the other hand, log(K(dis)) increased as pH decreased from 3.0 to 1.5, but decreased as pH decreased from 1.5 to 1.0. In addition, the disintegration time of commercially available tablets at pH 1.0 and 1.2 was found to be delayed, resulting in a decrease of K(dis). Furthermore, from powder X-ray diffraction, HPLC and elemental analysis, the delay in disintegration time might be attributable to the formation of a transparent gel, formed by the reaction between CAM molecule and hydrochloric acid under low pH conditions, on the surface of CAM tablet. On the basis of these results, this report can be considered the first case where a transparent gel prevents gastric fluid from penetrating the tablet, resulting in reduced decomposition of CAM following oral administrating.     

Electric field dependent photocurrent generation in a thin-film organic photovoltaic device with a [70]fullerene-benzodifuranone dyad

A [70]fullerene-benzodifuranone acceptor dyad synthesized by a Ag?-mediated coupling reaction was used to construct a thin-film organic solar cell. The fullerene and the benzodifuranone dye in the dyad have close-lying LUMO levels in the range of 3.7-3.9 eV, so that energy transfer from the dye to the fullerene can take place. A p-n heterojunction photovoltaic device consisting of a tetrabenzoporphyrin and a [70]fullerene-benzodifuranone dyad showed a weak but discernible contribution from light absorption of the dyad to the photocurrent under both a positive and a negative effective bias. These results indicate that the benzodifuranone moiety attached to the acceptor contributes to light-harvesting by energy transfer.     

Electronic structures and charge-transfer spectra of tris[2.2.2]paraxylylene and related compounds

Electronic spectra of tris[2.2.2]paraxylylene (3°-PX) and some related compounds were measured in order to investigate the electronic interaction (pπ-pπ and pσ-pσ type) between “normal” (undistorted) benzene rings. 3°-PX showed a large hypochromic effect, i.e., its oscillator strength was observed to be 0·61 times of that of the corresponding linear polyparaxylylene. Charge-transfer (CT) spectra between these compounds and some electron acceptors were also studied. MO calculations (the VI/1, CNDO/2 and CI methods) were carried out in order to elucidate the electronic structure of 3°-PX and also the CT interactions between tetracyanoethylene and 3°-PX, benzene, toluene or p-xylene.     

Dansyl-Modified γ-Cyclodextrin as a fluorescent sensor for molecular recognition

The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usualF conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C₁₂H₁₇N₄OS⁺·I^– · 1.5 H₂O, monoclinic,P2₁/c, a=12.585(2), b=25.303(5), c=12.030(2) Å, =115.15(1)°,V=3468(1) ų,Z=8,D _c=1.606 g cm^–3,R=0.045 for 3328 observed reflections. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP. 82156 (13 pages).     

Study on the surface density of surface-active substances through total-reflection X-ray absorption fine structure measurement

The total-reflection X-ray absorption fine structure (XAFS) method previously employed for the adsorption of dodecyltrimethylammonium bromide (DTAB) at the air/water interface was applied to that in the presence of NaBr. The surface concentration of the bromide ions Gamma(X)(B) of DTAB and NaBr was evaluated by using the Br K-edge absorption jump values of the total-reflection XAFS spectra and was compared to the corresponding value Gamma(H)(B) estimated from the dependence of surface tension on the bulk concentrations of DTAB m(1) and NaBr m(2). The Gamma(X)(B) values trace almost perfectly the Gamma(X)(B) versus m(1) curve up to a concentration near the critical micelle concentration (cmc) and deviate gradually above the concentration. This behavior is basically similar to that of the single DTAB system and ensures that the XAFS method is also applicable to the DTAB system, even in the presence of NaBr. In addition, this method was extended to the single nonionic amphiphile with covalently bonded bromine, and the surface concentrations of 6-bromo-1-hexanol (BrC6OH), Gamma(X)(1) and Gamma(H)(B), were evaluated and compared with each other. It was found that the Gamma(X)(1) value almost perfectly traces the Gamma(H)(1) versus m(1) curve, even at high surface concentrations. The excellent coincidence confirmed that the total-reflection XAFS method can be applied to the nonionic amphiphile system as well as a cationic surfactant with or without an added salt system. Finally, the difference between the Gamma(X)(B) and Gamma(H)(B) values observed in the DTAB with and without an added salt system is briefly described.     

Time-resolved total internal reflection fluorescence spectroscopy of polymer films

Using total internal reflection, the possibility of a subnanosecond fluorescence spectroscopy for elucidating photophysical and photochemical processes of polymer surface is demonstrated. The thickness which can be studied under the present experimental conditions is of the order of 0.01 μm.     

On class numbers of quadratic extensions¶over function fields

We consider class numbers of quadratic extensions over a fixed function field. We will show that there exist infinitely many quadratic extensions which have class numbers not being divisible by 3 and satisfy prescribed ramification conditions. Received: 24 October 1997 / Revised version: 26 February 1998