The TEPSICO-II apparatus at UVSOR and threshold electron spectra of some molecules over the wavelength range 35–120 nm

An apparatus designed for studies of state selected unimolecular and ion-molecule reactions using synchrotron radiation is described. It is installed in the UVSOR storage ring in Okazaki. Threshold electron spectra of some rare gas atoms and diatomic and polyatomic molecules taken with this apparatus are presented and discussed.     

Dependency of ligand free energy landscapes on charge parameters and solvent models

We performed replica-exchange molecular dynamics (REMD) simulations of six ligands to examine the dependency of their free energy landscapes on charge parameters and solvent models. Six different charge parameter sets for each ligand were first generated by RESP and AM1-BCC methods using three different conformations independently. RESP charges showed some conformational dependency. On the other hand, AM1-BCC charges did not show conformational dependency and well reproduced the overall trend of RESP charges. The free energy landscapes obtained from the REMD simulations of ligands in vacuum, Generalized-Born (GB), and TIP3P solutions were then analyzed. We found that even small charge differences can produce qualitatively different landscapes in vacuum condition, but the differences tend to be much smaller under GB and TIP3P conditions. The simulations in the GB model well reproduced the landscapes in the TIP3P model using only a fraction of the computational cost. The protein-bound ligand conformations were rarely the global minimum states, but similar conformations were found to exist in aqueous solution without proteins in regions close to the global minimum, local minimum or intermediate states.     

Non-extractable photoinitiators based on thiol-functionalized benzophenones and thioxanthones

Non-extractable photoinitiators could be advantageous for use in biological, electronic, and food packaging applications. Therefore, thioxanthone and benzophenone derivatives were synthesized from 1,6-hexane dithiol and chlorinated benzophenone or thioxanthone. The efficiency of thiol-functionalized photoinitiators in combination with amine co-initiators was compared to benzophenone and isopropylthioxanthone with amine co-initiators, and the cleavage of photoinitiator 2,2-dimethoxy-1,2-diphenylethan-1-one in acrylic resins. The reaction kinetics were analyzed using photo-differential scanning calorimetry and real-time FTIR. Coating physical properties were evaluated by pendulum and pencil hardness, steel-wool scratch and mandrel bend tests. The non-extractable photoinitiators had higher absorbance than their benzophenone or isopropylthioxanthone counterparts due to the sulfide substitution on the phenyl ring, and the free thiol groups reacted with the acrylate by either an amine catalyzed Michael addition or a free-radical chain process. The combination of thiol-functionalized photoinitiators with secondary amines provides an efficient photoinitiator system that is locked into the photopolymerized network and cannot be extracted with typical solvents.     

Small-span bending test for determination of elastic-plastic properties of ultrathin Pt wires

A mechanical testing methodology for determination of elastic-plastic properties of very thin metallic wires using small-span bending under lateral load is described. Sufficient strain is locally developed in the tested section of wire by unsymmetrical bending with two opposite probes where one end of the wire is fixed on a substrate with rigid joint by Joule heat welding. From the load-displacement relationships obtained experimentally, Young’s modulus is determined by analytical formulation. Moreover, yield stress and hardening modulus of the wire are identified using an optimization strategy with finite-element analyses. The thin Pt wires with a nominal diameter of about 625 nm are examined by the testing scheme and the wires are found to have higher yield stress compared to bulk Pt.     

Public policy structuring incorporating reciprocal expectation analysis

This paper proposes a method of structuring public policy by incorporating reciprocal expectation analysis. The proposed method is characterized by three components: identification of the problem structure perceived by stakeholders using cognitive maps, policy structuring analysis with a value–driver matrix and a reciprocal expectation matrix, and feasibility analysis of agreements among the stakeholders. The three types of relationship among stakeholders are derived from the feasibility analysis, which are “Dosho-imu”, “Isho-imu”, and “Domu”. Three tests of feasibility to reach the agreement are then proposed: “information-sharing test”, “bargaining test”, and “reframing test”. A case study is presented, applying the method to strategic transportation planning in the Kanto region of Japan. Finally, the potential functions of the proposed method in practice are discussed.     

Proton response of high sensitivity CR-39 copolymer

We studied the track response for the copolymer of CR-39 monomer with N-isopropylacrylamide (NIPAAm) as well as etching properties. It was found that copoly (CR-39/NIPAAm/Naugard 445) composed in wieght ratio of 99/1/0.01 is highly sensitive to low LET particles in the region below 10 keV/μm of LET and able to record normally incident particles of LET down to 1.5 keV/μm, recording protons up to the energy of 27 MeV. These results were compared with the responses for two types of CR-39 detectors containing a small quantity of antioxidant. The threshold energy proton registration is discussed.     

Total synthesis of (±)-erythravine based on ring closing dienyne metathesis

The first total synthesis of (±)-erythravine was achieved in thirteen steps from 3,4-dimethoxyphenethylamine using ring closing dienyne metathesis as the key step.     

The effect of UV irradiation on the reduction of Au(III) ions adsorbed on manganese dioxide.

The effect of UV (ultraviolet) irradiation on the adsorption of Au(III) ions on manganese dioxide and their reduction to Au(0) (gold with 0 valence state) was investigated using XPS (X-ray photoelectron spectroscopy) and 197Au M?ssbauer spectroscopy. The UV irradiation accelerated the adsorption and the reduction. From the fact that the proportion of Au(0) estimated from Au 4f XPS spectra for surface analysis was significantly smaller than that from 197Au M?ssbauer spectra for bulk analysis, we deduced that Au(0) was interpenetrated to the inside of manganese dioxide (into deeper places than about 30 A) where XPS is impossible to detect. The content of surface hydroxyl groups on manganese dioxide also increased due to the UV irradiation. The relationship between the charge in the content of hydroxyl groups and the interpenetration of Au(0) is discussed.