Pulsed EPR Analysis of the Photo-Induced Triplet Radical Pair in the BLUF Protein SyPixD: Determination of the Protein–Protein Distance and Orientation in the Oligomeric Protein

A photo-induced radical pair of FADH^· and Y8^· and in BLUF protein SyPixD was studied by pulsed electron paramagnetic resonance (EPR) spectroscopy. Blue light illumination at 150 K for 30 min followed by cooling to 50 K during illumination induced the stable radical pair. The EPR signal has been characterized by a Pake doublet signal with complete S = 1 spin state. The radical pair was utilized as a probe to analyze the oligomer of SyPixD. The relative arrangement of PixD proteins in the complex was investigated by pulsed electron–electron double resonance (PELDOR) with the orientation selection. Based on the decameric structure in the crystal, the possible structure for the PELDOR results was discussed.     

Initial oxidation of Ni(1 1 1) observed by electron emission microscopy: PEEM and MEEM

The initial oxidation of Ni(1 1 1) in the temperature range of 550-700 K has been monitored by photoelectron emission microscopy (PEEM) and metastable-atom electron emission microscopy (MEEM). The PEEM and MEEM images show uniform patterns for the chemisorbed overlayer, reflecting the electronic homogeneity as seen at the μm scale. During the nucleation and lateral growth of oxide, however, the μm-scale pattern due to the formation of oxide domains appears and its evolution depends strongly on the substrate temperature and dose pressure of gaseous O₂. Our data indicate that the high-temperature oxidation is regarded as a successive multi-nucleation process in a reaction-diffusion field.     

Application of a green function to a metal containing a vacancy and an impurity atom

A double time Green function is used to obtain the interaction energy between a vacancy and a transition-metal impurity atom in noble metals. The main part of the interaction energy has the RKKY type expression.     

Hydrogen chemisorption on Ni(110) by high-resolution electron energy loss spectroscopy

High-resolution electron energy loss spectra of hydrogen-covered Ni(110) surfaces both at 100 and 300 K are presented. The adsorbed sites of hydrogen atoms are discussed.High-resolution electron energy loss spectra of hydrogen covered Ni(110) surfaces have been studied. Tentative models for the adsorbed sites of hydrogen atoms are as follows: (1) For the (2 × 1)-H surface, hydrogen is adsorbed in the three-coordinated sites of the rudimentary (111) face of the unreconstructed Ni(110) substrate. (2) For the low-temperature (1 × 2)-H surface, hydrogen is adsorbed in the three-coordinated sites and, probably, in the two-fold hollow sites of the distorted Ni(110) substrate. (3) For the room-temperature (1 × 2)-H surface, hydrogen is disorderedly adsorbed in the three-coordinated, two-fold hollow and short-bridge sites and, possibly, in the octahedral sites of the distorted Ni(110) substrate. Some of the unresolved problems in the above assignments are summarized: (1) Strictly, the three-coordinated sites above are somewhat different from those discussed in the molecular-beam diffraction study [5]. (2) For the low-temperature (1 × 2)-H surface, the loss associated with hydrogen in the two-fold hollow sites is apparently not observed. (3) Intensity changes of the three losses for the room-temperature (1 × 2)-H surface with increasing hydrogen pressure (Fig. 2) are not well understood.     

Novel lactonization of ethenetricarboxylate derivatives: intermolecular trapping of alkenes

A novel cyclization of 1,1-diethyl 2-tert-butyl ethenetricarboxylate (1a) in the presence of a Lewis acid afforded a 5,5-dimethyl-gamma-lactone derivative 2a. The reaction process has been shown to arise from formation by trapping of isobutylene generated in situ. Lewis acid-promoted intermolecular reactions of 1,1-diethyl 2-hydrogen ethenetricarboxylate (5) and various alkenes to afford highly functionalized gamma-lactones were also developed. [reaction: see text]     

Nickel-catalyzed intermolecular [3 + 2 + 2] cocyclization of ethyl cyclopropylideneacetate and alkynes

The [3 + 2 + 2] cocyclization of ethyl cyclopropylideneacetate (1a) and terminal alkynes (2) proceeded smoothly in the presence of 10 mol % "Ni(PPh3)2", which was prepared in situ from Ni(cod)2 and PPh3. The high reactivity of 1a, which was induced by the introduction of an electron-withdrawing group, is very important for the progress of this reaction. The cycloheptadiene derivatives were synthesized in highly selective manner in good yields.     

Electron spin resonance in the spin-1/2 quasi-one-dimensional antiferromagnet with Dzyaloshinskii-Moriya interaction BaCu2Ge2O7

We have investigated the electron spin resonance (ESR) on single crystals of BaCu2Ge2O7 at temperatures between 300 and 2 K and in a large frequency band, 9.6-134 GHz, in order to test the predictions of a recent theory, proposed by Oshikawa and Affleck (OA) [Phys. Rev. Lett. 82, 5136 (1999)]], which describes the ESR in a spin-1/2 Heisenberg chain with the Dzyaloshinskii-Moriya interaction. We find, in particular, that the ESR linewidth, Delta H, displays a rich temperature behavior. As the temperature decreases from T(max)/2 approximately 170 to 50 K, Delta H shows a rapid and linear decrease, Delta H approximately T. At low temperatures, below 50 K, Delta H acquires a strong dependence on the magnetic field orientation and for H axially c it shows a (h/T)(2) behavior which is due to an induced staggered field h, according to OA's prediction.