Excited state property of hardly photodissociable heme-CO adduct studied by time-dependent density functional theory

While most of CO-bound hemes are easily photodissociated with a quantum yield of nearly unity, we occasionally encounter a CO-heme which appears hardly photodissociable under the ordinary measurement conditions of resonance Raman spectra using CW laser excitation and a spinning cell. This study aims to understand such hemes theoretically, that is, the excited-state properties of the five-coordinate heme-CO adduct (5cH) as well as the 6c heme-CO adduct (6cH) with a weak axial ligand. Using a hybrid density functional theory, we scrutinized the properties of the ground and excited spin states of the computational models of a 5cH and a water-ligated 6cH (6cH-H(2)O) and compared these properties with those of a photodissociable imidazole-ligated 6cH (6cH-Im). Jahn-Teller softening for the Fe-C-O bending potential in the a(1)-e excited state was suggested. The excited-state properties of 6cH-Im and 5cH were further studied with time-dependent DFT theory. The reaction products of 6cH-Im and 5cH were assumed to be quintet and triplet states, respectively. According to the time-dependent DFT calculations, the Q excited state of 6cH-Im, which is initially a pure pi-pi state, crosses the Fe-CO dissociative state (2A') without large elongation of the Fe-CO bond. In contrast, the Q state of the 5cH does not cross the Fe-CO dissociative state but results in the formation of the excited spin state with a bent Fe-C-O. Consequently, photoisomerization from linear to bent Fe-C-O in the 5cH is a likely mechanism for apparent nonphotodissociation.     

Intrinsic vacancy-induced nanoscale wire structure in heteroepitaxial Ga2Se3/Si(001)

A highly anisotropic growth morphology is found for heteroepitaxial gallium sesquiselenide (Ga2Se3) on the lattice matched substrate, arsenic-terminated Si(001). Scanning tunneling microscopy of Ga2Se3 films reveals nanoscale, wirelike structures covering the surface in parallel lines, less than 1 nm wide and up to 30 nm long. Core-level photoemission spectroscopy and diffraction reveals the local structure of buried Ga and Se atoms to reflect the bulk, defected zinc-blende structure of beta-Ga2Se3, which contains ordered 110 arrays of Ga vacancies. These ordered vacancy lines are proposed to be responsible for the observed growth anisotropy in heteroepitaxial Ga2Se3.     

Microwave EPR spectroscopy of cobalt-doped germanium cuprate

Resonance magnetoabsorption spectra of CuGeO₃ single crystals containing 2% Co impurity have been studied in the frequency range 60–360 GHz in magnetic fields of up to 16 T and in the temperature interval 2–60 K with the magnetic field B aligned parallel to the a crystallographic axis. In addition to the Cu²⁺ chain resonance, a new absorption line (unobserved previously in doped CuGeO₃ and deriving apparently from the Co²⁺ ions) was detected in EPR spectra. Quantitative analysis of the spectra suggests that the spin-Peierls transition occurs in about 10% Cu²⁺ chains, while the spin-Peierls state in the remaining 90% chains is completely destroyed by cobalt doping. The results obtained reveal considerable deviations from the universally accepted scenario of CuGeO₃ doping and are discussed within alternative theoretical models, namely, the quantum critical behavior (based on the EPR theory for quasi-one-dimensional systems) and a three-dimensional antiferromagnet with the Néel temperature lowered by disorder.     

Building a Simple Model of a Pulse-Frequency-Modulation Photosensor and Demonstration of a 128 x 128-pixel Pulse-Frequency-Modulation Image Sensor Fabricated in a Standard 0.35-$mUm Complementary Metal-Oxide Semiconductor Technology

We present a simple model of the pulse-frequency-modulation (PFM) photosensor that provides explicit relationships between circuit parameters and output characteristics. The model treats the PFM photosensor with a feedback loop as an open loop circuit. Several characteristics such as output pulse frequency for light intensity and photosensitivity are expressed by device parameters of a photodiode, reset transistor, and chain of inverters. The relationships derived from the proposed model help us to comprehend the results by simulation program with integrated circuit emphasis (SPICE) or experiments. We design and fabricate a 128 x 128-pixel PFM image sensor with photosensitivity of 0.15 Hz/lux. As a demonstration, a figure of a dinosaur is captured using the fabricated image sensor to discuss its operation. Characteristics of a normal pixel and white and black defect pixels are measured and discussed based on the results of formulations.     

Ruthenium catalyzed addition reaction of carboxylic acid across olefins without beta-hydride elimination

The cationic ruthenium catalyst (Cp*RuCl2)2/AgOTf/Ligand promotes the addition reaction of carboxylic acids across olefins without beta-hydride elimination.     

Adsorption of thiolates to singly coordinated sites on Au111 evidenced by photoelectron diffraction

The adsorption structure of methylthiolate (CH3S) adsorbed on Au(111), a long-standing controversial issue, has been unambiguously determined by scanned-energy and scanned-angle S 2p photoelectron diffraction. The methylthiolate molecules are found to occupy atop sites with a S-Au distance of 2.42 +/- 0.03 A. The angular distribution of the S 2p photoelectrons due to forward scattering reveals that the S-C bond is inclined by approximately 50 degrees from the surface normal towards both the [211] and [121] (nearest-neighbor thiolate) directions.     

An idea for predicting the evaporation residue cross section in superheavy mass region

A trial to clarify the main contributors to the evaporation residue cross section in the superheavy mass region is presented. The precise analysis of these factors enables us to understand more clearly the trend of experimental data decreasing exponentially when the atomic number of the residue nucleus increases. It is found that almost all of the experimental data producing nuclei with Z=104 to 114 are fitted with a common parameter set within a reasonable allowance, i.e., ±0.7 order. In this sense, this model has a reliable predictability for the synthesis of new elements.     

Preparation of organic-inorganic composites containing rod-like phthalocyanine polymers

Sol-gel polymerization of tetraethoxysilane in the presence of amphiphilic phthalocyanine polymer 2 produced organic-inorganic composites with the rod-like phthalocaynine polymers incorporated within ordered hexagonal channels.     

Selective ligation to sterically isolated metallophthalocyanines

A new class of sterically hindered phthalocyanine has been synthesized and characterized. Pentaphenylbenzene units were introduced at the periphery of each phthalocyanine to yield a sterically protected metal center. The attachment of the bulky oligophenylbenzene units resulted in the complete isolation of individual MPc molecules. The pockets around a cobalt center affect selectivity in the ligation of pyridines that have different sizes and shapes.