Melting Temperatures of Monazite and Xenotime

The melting temperatures of natural and synthetic monazite and xenotime (rare-earth ortnophosphates) were measured, using a heliostat-type solar furnace. The results obtained are as follows: natural monazite from Japan (2057°40°C), synthetic monazite RPO₄ (R=La, 2072°20°C; R=Ce, 2045°20°C; R=Pr, 1938°20°C; R=Nd, 1975°20°C; R=Sm, 1916°20°C), and synthetic xenotime RPO₄(R=Y, 1995°20°C; R=Er, 1896°20°C).     

Conformational properties of the guanine-binding site of ribonuclease T1 inferred from the X-ray structure and protein engineering

Recognition by ribonuclease T₁ of guanine bases via multidentatehydrogen bonding and stacking interactions appears to be mediatedmainly by a short peptide segment formed by one stretch of aheptapeptide, Tyr⁴²-Asn⁴³-Asn⁴⁴-Tyr⁴⁵-Gly⁴⁶-Gly⁴⁷-Phe⁴⁸. Thesegment displays a unique folding of the polypeptide chain—consistingof a reverse turn, Asn⁴⁴-Tyr⁴⁵-Glu⁴⁶-Gly⁴⁷, stabilized by ahydrogen-bond network involving the side chain of Asn⁴⁴, themain-chain atoms of Asn⁴⁴, Gly⁴⁷ and Phe⁴⁸ and one water molecule.The segment is connected to the C terminus of a ß-strandand expands into a loop region between Asn⁴³ and Ser⁵⁴. Lowvalues for the crystallographic thermal parameters of the segmentindicate that the structure has a rigidity comparable to thatof a ß-pleated sheet. Replacement of Asn⁴⁴ with alanineleads to a far lower enzymatic activity and demonstrates thatthe side chain of Asn⁴⁴ plays a key role in polypeptide foldingin addition to a role in maintaining the segment structure.Substitution of Asn⁴³ by alanine to remove a weak hydrogen bondto the guanine base destabilized the transition state of thecomplex by 6.3 kJ/mol at 37°C. In contrast, mutation ofGlu⁴⁶ to alanine to remove a strong hydrogen bond to the guaninebase caused a destabilization of the complex by 14.0 kJ/mol.A double-mutant enzyme with substitutions of Asn⁴³ by a histidineand Asn⁴⁴ by an aspartic acid, to reproduce the natural substitutionsfound in ribonuclease M_s, showed an activity and base specificitysimilar to that of the wild-type ribonuclease M_s. The segmenttherefore appears to be well conserved in several fungal ribonucleases.     

Rapid erasing of wettability patterns based on TiO2-PDMS composite films

TiO₂-polydimethylsiloxane (TiO₂-PDMS) composite films are prepared using the sol–gel method from a Ti(OBu)₄–benzoylacetone solution containing PDMS. The prepared films are cured by irradiation with ultraviolet (UV) light. Structural changes in the films after UV irradiation are confirmed by UV–vis absorption experiments, which show that an absorption band characteristic of the benzoylacetonate chelate rings disappears. This finding is ascribed to structural changes associated with the dissociation of the chelate rings. The IR spectra of the thin films exhibit a broad absorption band after UV irradiation, indicating that a Ti–O–Ti network forms in the thin film. Contact angles are measured for the TiO₂-PDMS thin films, showing wettability conversion from hydrophobic to superhydrophilic states by irradiation with oxygen plasma for 1 s. This phenomenon is explained by XPS experiments which reveal that the number of carbon atoms decreases, whereas the number of oxygen atoms increases on the surface of the TiO₂-PDMS composite films. Finally, hydrophobic–superhydrophilic patterns are fabricated based on a patterned TiO₂-PDMS composite film. The film displays a rapid change to superhydrophilicity over the whole film surface upon plasma irradiation for 1 s, which means that the wettability patterns are rapidly erasable.     

High-performance antireflective coatings with a porous nanoparticle layer for visible wavelengths

Ghosts and flares are well-known problems that are caused by reflections from lens surfaces when we take photographs. It is more difficult to prevent such stray light in a digital camera than in a film camera because of high reflectance from the low-pass filter and diffraction from the image sensor. To prevent such stray light, we introduce an ultralow refractive index layer into the antireflective (AR) coatings. We used the solgel method to form porous fluoride layers with ultralow refractive indices, and we succeeded in developing a unique process to form AR coatings with superior performance.     

Network copolyesters from benzenepolycarboxylic acids and 1,6-hexanediol

Network copolyesters were prepared from trimesic (Y), pyromellitic (X) or mellitic (Y_H) acids and 1,6-hexanediol (6G). Prepolymers prepared by meltpolycondensation were cast from dimethylformamide solution and postpolymerized at 260°C for 6h to form a network. The resultant films were transparent, flexible and insoluble in any organic solvents. Degree of reaction estimated from the infrared absorbance of ester and methylene groups was almost the same for all films, 94–96%. X-ray diffraction intensity curves and densities showed that the ordering of networks was decreased by the copolymerization, which was remarkable for 6G–X/Y_H copolymer films and was consistent with the higher decreases of heat-distortion temperature for these copolymer films. The copolymerization also caused decrease of thermal stability, tensile properties and alkali resistance and increase of dye absorption.