Yoshihisa Inoue

The aim of the present study was to examine the reactions in the interface between tissues and pure titanium. The adsorption behaviors of the extracellular matrix proteins HFG and HFN on titanium and gold were compared. The amount of adsorbed proteins on the metallic surfaces was measured after adsorption and desorption tests, using atomic force microscopy. The conformation changes of the proteins adsorbed were examined with a Fourier transform infrared spectrophotometer. The results showed that the adsorption of the two proteins were greater on the titanium plates than on the gold plates. It is reasonable to assume that proteins adsorb to surfaces through several steps, and that both HFG and HFN attach mainly to gold by physical adsorption, but to titanium by chemical adsorption. Furthermore, the conformation changes for both test proteins were greater on the titanium plates than on the gold plates. The initial adsorption of extracellular matrix proteins to metal is an important factor in determining the biocompatibility of a dental material in the oral cavity. This testing method might be effective when developing new active dental implants.

Catalytic enantiodifferentiating photoisomerization of cyclooctene (1Z) included and sensitized by regioisomeric 6-O-(o-, m-, and p-methoxybenzoyl)-β-cyclodextrins (CDs) was performed under a variety of solvent conditions for higher enantioselectivities. The enantiomeric excess (ee) of chiral (E)-isomer (1E) produced was a critical function of all the internal and external factors examined, in particular, the sensitizer structure and the solvent conditions, to afford (R)-1E in record-high ee’s of up to 67% upon sensitization with the meta-substituted β-CD host in water and salt solutions but neither in 50% aqueous ethanol nor with the ortho- and para-substituted hosts. The mechanistic origin of the sudden ee enhancement achieved under the specific conditions is discussed on the basis of the circular dichroism spectral behaviors upon substrate inclusion and the compensatory enthalpy–entropy relationship of the activation parameters for the enantiodifferentiating photoisomerization.

Planar chiral cyclophanopillar[5]arenes with a fused oligo(oxyethylene) or polymethylene subring (MUJs), existing as an equilibrium mixture of subring-included (in) and -excluded (out) conformers, respond to hydrostatic pressure to exhibit dynamic chiroptical property changes, leading to an unprecedented pressure-driven chirality inversion and the largest ever-reported leap of anisotropy (g) factor for the MUJ with a dodecamethylene subring. The pressure susceptivity of MUJs, assessed by the change in g per unit pressure, is a critical function of the size and nature of the subring incorporated and the solvent employed. Mechanistic elucidations reveal that the in–out equilibrium, as the origin of the MUJ's chiroptical property changes, is on a delicate balance of the competitive inclusion of subrings versus solvent molecules as well as the solvation of the excluded subring. The present results further encourage our use of pressure as a unique tool for dynamically manipulating various supramolecular devices/machines.

Possessing an extra anionic handle for chiral supramolecular interactions, 2,6-anthracenedicarboxylate exhibited greater photochirogenic performance than 2-anthracenecarboxylate to afford the anti-cyclodimer in up to 94% yield and −72% enantiomeric excess upon photoirradiation with dicationic γ-cyclodextrins.

The famous solvatochromic Reichardt’s dye was applied to quantify hydrostatic pressure in media. The UV/vis spectra of the dye in various organic solvents are shifted bathochromically or hypsochromically at the shorter- or longer-wavelength band, respectively, upon hydrostatic pressurization. The E_T value, determined by an absorption maximum, in ethyl acetate increases from 38.5 kcal mol^–1 at 0.1 MPa to 39.2 kcal mol^–1 at 300 MPa, which is mostly equal to the one in chloroform at 0.1 MPa. These spectroscopic origins were supported by the time-dependent density functional theory (TD-DFT) calculations. The concept and approach proposed in this paper, i.e., a dual indicator, should attract the attention of a broad spectrum in multidisciplinary science.

Stereoisomeric β-cyclodextrin (CD) dimers linked with a sulfur atom or an arene spacer were designed to create a tethered dual CD capsule for precisely manipulating the regio- and enantio-selectivities of the photocyclodimerization of 2-anthracenecarboxylate (AC) to four classical stereoisomeric 9,10:9’,10’-cyclodimers and two nonclassical 5,8:9’,10’-cyclodimers. Among the dimeric CD hosts prepared, exo-3-thia-β-CD dimer formed 1:1 and 1:2 host-guest complexes with AC in aqueous solutions, the former of which hindered but the latter facilitated the AC photocyclodimerization with regio- and enantioselectivities much higher than those obtained with native β-CD or the other β-CD dimers. The stereochemical outcomes turned out to be highly sensitive to and hence critically manipulatble by the linking position and configuration of the connected saccharide units and the linker length, as well as the external variants, such as temperature, pH, and added salt. Eventually, the photocyclodimerization of AC mediated by the dimeric β-CD host gave enantiopure syn-head-to-tail-9,10:9’,10’-cyclodimer in 97-98% yield in a pH 5.1 buffer solution at 0.5 °C and also in an aqueous CsCl solution at -20 °C.