Hidehiro Uekusa

Cation-Dependent Formation of Superstructures by One-Pot Self-Organization of Hydrogen-Bonded Nickel Complexes

Four different types of molecular arrangements can be formed by one-pot synthesis, depending on the type of counter cation used, when a new anionic tris(biimidazolato)nickel(II) complex is used to form a network held together by hydrogen bonds. The connections occur through biimidazolate ligands, which can act as hydrogen bond donor as well as acceptor (see scheme).

Observation of Field-Induced Transverse Neel Ordering in the Spin Gap System TlCuCl3.

Neutron elastic scattering experiments have been performed on the spin gap system TlCuCl 3 in magnetic fields parallel to the b -axis. The magnetic Bragg peaks which indicate the field-induced Neel ordering were observed for the magnetic field higher than the gap field H g ≈5.5 T at Q =( h , 0, l ) with odd l in the a * - c * plane. The spin structure in the ordered phase was determined. The temperature and field dependence of the Bragg peak intensities and the phase boundary obtained were discussed in connection with a recent theory which describes the field-induced Neel ordering as a Bose-Einstein condensation of magnons.

Magnetization plateaus in NH4CuCl3

The magnetic susceptibility and high-field magnetization process of NH 4 CuCl 3 with double chains of CuCl 3 have been measured using single crystals. No anomaly indicative of the three-dimensional ordering is observed in susceptibility data above 1.7 K. It is found, by magnetization measurement down to 0.5 K, that in contrast to KCuCl 3 and TlCuCl 3 , NH 4 CuCl 3 has a gapless magnetic ground state at zero field. It is observed that the magnetization curve has two plateaus at one-quarter and three-quarters of the saturation magnetization, irrespective of the external field direction. The origin of the plateaus is attributed not to the magnetic anisotropy, but to the quantum effect. The relation between the plateaus and the period of the spin state is discussed in terms of a recent theory presented by Oshikawa et al . [Phys. Rev. Lett. 78 (1997) 1984].

Cocrystallization and amorphization induced by drug–excipient interaction improves the physical properties of acyclovir

Although acyclovir is one of the most important antiviral drugs used today, there are several problems with its physical properties. The aim of this study is to prepare cocrystals or amorphous complex of acyclovir using drug-excipient interactions to improve the physical properties of the drug, especially its dissolution rate and transdermal absorption. Screening for formation of cocrystals and the presence of amorphous acyclovir was conducted with various pharmaceutical excipinents, with the use of the solution-crystallization method and liquid-assisted cogrinding. The potential cocrystalline phase and the amorphized complex were characterized by PXRD, TG/DTA, IR, DSC and HPLC techniques. The screening indicated that acyclovir formed novel cocrystals with tartaric acid and was amorphized with citric acid. The acyclovir-tartaric acid cocrystal (ACV-TA cocrystal) structure was determined from synchrotron X-ray powder diffraction data. T(g) of the amorphous acyclovir-citric acid compound (ACV-CA amorphous) was determined by DSC. The initial dissolution rate of the ACV-TA cocrystals was considerably faster than that of anhydrous acyclovir. In vitro skin permeation of ACV-CA amorphous from polyethylene glycol (PEG) ointment was remarkably higher than that of the crystalline acyclovir. We successfully improved the physical properties of acyclovir by the cocrystallization and amorphization techniques, using pharmaceutical excipients.

Determination of the Structural Features of a Long-Lived Electron-Transfer State of 9-Mesityl-10-methylacridinium Ion

Extensive efforts have been devoted to developing electron donor-acceptor systems that mimic the utilization of solar energy that occurs in photosynthesis. X-ray crystallographic analysis shows how absorbed photon energy is stabilized in those compounds by structural changes upon photoinduced electron transfer (ET). In this study, structural changes of a simple electron donor-acceptor dyad, 9-mesityl-10-methylacridinium cation (Acr(+)-Mes), upon photoinduced ET were directly observed by laser pump and X-ray probe crystallographic analysis. The N-methyl group in Acr(+) was bent, and a weak electrostatic interaction between Mes and a counteranion in the crystal (ClO(4)) was generated by photoinduced ET. These structural changes correspond to reduction and oxidation due to photoinduced ET and directly elucidate the mechanism in Acr(+)-Mes for mimicking photosynthesis efficiently.

Novel terpenes generated by heterologous expression of bacterial terpene synthase genes in an engineered Streptomyces host

Mining of bacterial genome data has revealed numerous presumptive terpene synthases. Heterologous expression of several putative terpene synthase genes in an engineered Streptomyces host has revealed 13 newly discovered terpenes whose GC-MS and NMR data did not match with any known compounds in spectroscopic databases. Each of the genes encoding the corresponding terpene synthases were silent in their parent microorganisms. Heterologous expression and detailed NMR spectroscopic analysis allowed assignment of the structures of 13 new cyclic terpenes. Among these newly identified compounds, two were found to be linear triquinane sesquiterpenes that have never previously been isolated from bacteria or any other source. The remaining 11 new compounds were shown to be diterpene hydrocarbons and alcohol, including hydropyrene (1), hydropyrenol (2), tsukubadiene (11) and odyverdienes A (12) and B (13) each displaying a novel diterpene skeleton that had not previously been reported.

Boron-Selective Biaryl Coupling Approach to Versatile Dibenzoxaborins and Application to Concise Synthesis of Defucogilvocarcin M

An efficient synthetic method for versatile dibenzoxaborins based on boron-selective Suzuki-Miyaura cross-coupling between o-borylphenols and aryl halides or triflates bearing a 1,8-diaminonaphthalene-protected o-boryl group is reported. A short synthesis of defucogilvocarcin M was achieved using the proposed method in combination with several other boron-mediated transformations.

Enhanced clickability of doubly sterically-hindered aryl azides

Steric character is one of the most fundamental factors to determine the reactivity of the substrate in organic synthesis. In bimolecular reaction, the sterically-bulky group situated close to the reactive center generally prevents the approach of the reaction partner retarding the bond formation. This report describes, to the contrary, significantly enhanced reactivity of 2,6-disubstituted phenyl azides observed in catalyst-free 1,3-dipolar cycloaddition with alkynes, unexpectedly reacting faster than unsubstituted phenyl azide and even more faster than unhindered alkyl azide, despite the steric hindrance adjacent to the reactive azido group. Experimental and computational studies have indicated that the steric hindrance eliciting the inhibition of resonance between azido group and the aromatic ring is the primary cause of this apparently-paradoxical phenomenon. This is the first type of steric acceleration, indicating a possibility of designing a highly reactive functional group by strategically locating it in the sterically-congested environment.

Self-Assembly of Nanometer-Sized Boroxine Cages from Diboronic Acids

By use of the reversible trimerization of boronic acids, the series of boroxine cages 3-mer, 6-mer, and 12-mer were constructed from rationally designed diboronic acids whose bond angles between two C-B bonds are 60°, 84°, and 117°, respectively. Boroxine cages 6-mer and 12-mer have 1.5 and 2.5 nm sized cavities, respectively.

Oxidative Annulation of Arenecarboxylic and Acrylic Acids with Alkynes Under Ambient Conditions Catalyzed by an Electron-Deficient Rhodium(III) Complex

It has been established that an electron-deficient Cp(E) rhodium(III) complex catalyzes the oxidative [4+2] annulation of substituted arenecarboxylic and acrylic acids with alkynes under ambient conditions (at RT-40 °C, under air) without using excess amounts of substrates to produce the corresponding substituted isocoumarins and α-pyrones in high yields. Minor modification of reaction conditions depending on the coordination ability of alkynes realized the high efficiency.