Molecule-Based Artificial Photosynthesis

Guidelines for the design of molecules with a long lifetime of the charge-separated state and for the formation of a self-assembled monolayer were studied by preparing various model compounds linking donor and acceptor with chemical bonds. Based on the obtained results we designed and prepared the SAMs of C₆₀-(porphyrin)-(ferrocene)-(CH₂)₁₁SH on a gold surface and observed a photocurrent with high efficiency (25% quantum yield). In addition, a well-defined, rigid-sheet-structured oligoporphyrin with 21 porphyrin chromophores was prepared as a model for antenna chlorophylls.     

Localization and completion of nilpotent groups of automorphisms

We study nilpotent subgroups of automorphism groups in the category of groups and the homotopy category of spaces. We establish localization and completion theorems for nilpotent groups of automorphisms of nilpotent groups. We then apply these algebraic theorems to prove analogous results for certain groups of self-homotopy equivalences of spaces.     

Influence of the Grain Boundaries on the Heat Transfer in Laser Ceramics

Grain boundaries play a key role in determining several key properties of polycrystalline laser ceramics. Heat transfer measurements at low temperature constitute a good tool to probe grain boundaries. We review the results of heat transfer measurements in polycrystalline Y₃Al₅O₁₂ garnets as well as Y₂O₃ and Lu₂O₃ sesquioxide materials obtained by self-energy-driven sintering of nano-particles. The average phonon mean free path in Y₃Al₅O₁₂ was found to be significantly larger than the average grain size and to scale with temperature as T ⁻² at low temperature. Existing models describing the interaction between phonons and grain boundaries are reviewed. Correct temperature dependence of the mean free path and order of magnitude of scattering rates were found by assuming the existence of a grain boundary layer having acoustic properties different from those of the bulk. A different temperature dependence of phonon mean free path was found for the sesquioxides and was ascribed to the stronger elastic anisotropy of these materials. The thermal resistance associated to the grain boundaries of laser ceramics was found to be lower than in other dense polycrystalline ceramic materials reported in the literature.     

Labeling of Polymer Nanostructures for Medical Imaging: Importance of crosslinking extent, spacer length, and charge density

Radiolabeling studies were employed to investigate the influence of structure on the efficiency of surface functionalization for poly(acrylic acid)-coated shell crosslinked nanoparticles (SCKs) with two types of amine-terminated DOTA chelators. An intricate interplay between the chemical and physical properties of both the DOTA derivative and the SCK nanostructures was revealed, demonstrating the importance of structural control.     

Class number parity for cyclotomic fields

We give a simple criterion for the parity of the class number of the cyclotomic field.

     

Thermal decomposition of poly(sec-amyl methacrylate)

The thermal decomposition of poly(sec-amyl methacrylate) is studied by simultaneous thermogravimetry–gas chromatography–mass spectrometry and by pyrolysis–gas chromatography. The TG curve has four distinct breaks and a plateau. Results of the identification of the evolved gas at the individual breaks by GC–MS techniques lead to the conclusion that these breaks correspond to the individual processes in the decomposition mechanism like that of poly(tert-butyl methacrylate): the first break, the depolymerization initiated at the unsaturated chain ends; the second break, the depolymerization initiated at the saturated chain ends; the third break, the ester decomposition; the plateau, the inhibition of decomposition by the formation of poly(methacrylic anhydride); the fourth break, the decomposition of poly(methacrylic anhydride). The extent of ester decomposition is related to the substituent constants based on Hammett equation. The ester decomposition product is separated into three pentene isomers by pyrolysis–gas chromatography: trans-2-pentene, cis-2-pentene, and 1-pentene. As raising decomposition temperature, the composition ratio of trans-2-pentene decreases and becomes constant above 620 K, and the composition ratios of cis-2-pentene and 1-pentene increase and also become constant above 620 K. These results are accounted for by mobility of atoms included in the substituent at forming a ring transition state.     

Photoconductivity of poly(N-acryloylcarbazole)

The photoconductivity of poly(N-acryloylcarbazole) (PACz), with the pendant carbazolyl group only a short distance from the skeletal chain of the polymer but separated from it by a carbonyl group, is investigated and compared with that of poly(N-vinylcarbazole) (PVCz). There is no significant difference between PACz and PVCz in the temperature, light intensity, and spectral dependences of the photocurrent. The photoconductivity of PACz, however, is much inferior to that of PVCz and even to that of poly(N-carbazolylethylvinylether), a representative vinyl polymer with pendant carbazolyl groups far from the skeletal chain. The poor photoconductivity of PACz is discussed in relation to the intensity of the electronic interaction between neighboring carbazolyl groups in the polymer chain and to singlet exciton migration. It is attributed mainly to an extremely low efficiency of extrinsic carrier generation via a singlet exciton, which is due to the poor electron-donating character and the extremely short lifetime of a singlet exciton in the presence of the carbonyl group.     

Specificity and biomineralization activities of Ti-binding peptide-1 (TBP-1)

Numerous peptide aptamers that recognize inorganic materials have been isolated using in vitro peptide evolution systems. However, it remains unknown how peptides interact with inorganic materials or how specific those interactions are. We, therefore, assessed the target specificities of the peptide aptamer TBP-1 (RKLPDAPGMHTW) by monitoring its ability to bind 10 different metals. We found that phages displaying TBP-1 bound to Ti, Si, and Ag surfaces but not to Au, Cr, Pt, Sn, Zn, Cu, or Fe. As previously seen with Ti, binding to Si and Ag was diminished by R1A, P4A, or D5A mutation, suggesting that the same molecular mechanism underlies TBP-1 binding to all three materials. We also observed that a synthetic TBP-1 peptide mediated mineralization of both silica and Ag. It, thus, appears that although the overall chemical characteristics of Ti, Si, and Ag surfaces are dissimilar, they share a common subnanometric structure that is recognized by TBP-1.