Evaluation of molecular spin-orbit integrals by a gaussian expansion method

A method is presented for the evaluation of molecular multi-centre spin-orbit integrals of Coulomb, hybrid and exchange types using cartesian gaussian functions. It is shown that if gaussian bases are employed the spin-same-orbit integrals reduce to one-electron field integrals and the spin-other-orbit integrals to two-electron field integrals. The final formulae for these integrals are found to be convenient for computer programming. Some relationships among the nuclear attraction, the field and the field-gradient integrals as well as among the electronic repulsion, the two-electron field, and the zero-field splitting integrals are discussed in connection with the spin-orbit integrals. Some calculations are carried out for the radicals CH₂ and NH.     

Dynamic transitions through scattors in dissipative systems

Scattering of particle-like patterns in dissipative systems is studied, especially we focus on the issue how the input-output relation is controlled at a head-on collision where traveling pulses or spots interact strongly. It remains an open problem due to the large deformation of patterns at a colliding point. We found that a special type of unstable steady or time-periodic solutions called scattors and their stable and unstable manifolds direct the traffic flow of orbits. Such scattors are in general highly unstable even in the one-dimensional case which causes a variety of input-output relations through the scattering process. We illustrate the ubiquity of scattors by using the complex Ginzburg-Landau equation, the Gray-Scott model, and a three-component reaction diffusion model arising in gas-discharge phenomena.     

Data Analysis Environment for X-ray Free-Electron Laser Experiments at SACLA

X-ray free-electron lasers (XFELs) with full spatial coherence, extreme brilliance, and ultra-fast pulse duration [1 P. Emma et al., Nat. Photon. 4, 641–647 (2010).[Crossref], [Web of Science ®] , [Google Scholar], 2 T. Ishikawa et al., Nat. Photon. 6, 540–544 (2012).[Crossref], [Web of Science ®] , [Google Scholar]] allow the investigation of complex phenomena in physics, chemistry, and biology with angstrom and femtosecond resolutions. In particular, a concept of “diffraction before destruction” [3 R. Neutze et al., Nature 406, 752–757 (2000).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] has been demonstrated for serial femtosecond crystallography (SFX) [4 H. N. Chapman et al., Nature 470, 73–77 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 5 S. Boutet et al., Science 337, 362–364 (2012).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] and coherent diffractive imaging (CDI) [6 M. M. Seibert et al., Nature 470, 78–81 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. Using femto-second XFEL pulses, diffraction data are collected before radiation damage to samples has time to occur. Since samples are exchanged for each XFEL pulse, shot-to-shot data acquisition (DAQ) is mandatory to correlate the recorded data with the sample characteristics. The shot-to-shot DAQ must be synchronized with the repetition rate of the XFEL source, typically several tens to one hundred Hz for the machine based on normal-conducting accelerators. Shot-to-shot recording of XFEL pulse characteristics is also essential because they fluctuate due to the stochastic nature of a self-amplified spontaneous emission (SASE). We must carefully analyze a huge data set taking the fluctuation into account.     

Determination of cadmium and bismuth in high-purity zinc metal by inductively coupled plasma mass spectrometry with on-line matrix separation

Traces of cadmium and bismuth in high-purity zinc metal were determined by inductively coupled plasma mass spectrometry (ICP-MS) in combination with flow injection (FI) on-line matrix separation (FI-ICP-MS). The anion-exchange separation method of the potassium iodide (KI) system was applied to the separation of the analytes from the matrix zinc. The analytes, cadmium and bismuth, were adsorbed on the anion-exchange (BIO. RAD AG1-X8) mini-column (1.0 mm i.d.x 100 mm bed length), while the matrix zinc can be completely removed from the anion-exchange resin. The analytes were eluted by 2 mol/l HNO(3) and directly introduced into the ICP-MS. The detection limits (D.L.) obtained by using a single injection (350 microl) were 0.81 and 0.075 ng g(-1) for cadmium and bismuth, respectively. In the case of multi-injection concentration onto the anion-exchange mini-column (five injections 350 microl each), the detection limits could be improved to 0.16 and 0.014 ng g(-1) for cadmium and bismuth, respectively. The reproducibilities of the single injection and the multi-injection method were satisfactory with a relative standard deviation of less than 5% (at the 10 and 1 ng ml(-1) level for the single injection and the multi-injection method, respectively). The method was successfully applied to the determination of trace impurities in four samples of high-purity zinc metal (7 nines grade) and three standard reference materials of high-purity unalloyed zinc samples (from NIST).     

Fluorescence detection of ATP based on the ATP-mediated aggregation of pyrene-appended boronic acid on a polycation

A novel fluorescent sensing system for ATP has been created utilizing the ATP-mediated aggregation process of pyrene-appended boronic acid on a polycation.     

A new approach for the investigation of isoprenoid biosynthesis featuring pathway switching,deuterium hyperlabeling,and 1H NMR spectroscopy. The reaction mechanism of a novel streptomyces diterpene cyclase

Recent methodology for the investigation of isoprenoid biosynthesis featuring pathway switching and hyperdeuteration has shown significant advantages in elucidating the reaction mechanism of a novel Streptomyces diterpene cyclase with use of precise atom-level analysis. Insight into the cyclization mechanism involved in the conversion of geranylgeranyl diphosphate (GGPP) into a clerodane hydrocarbon terpentetriene was obtained by heterologous expression in doubly engineered Streptomyces lividans of a diterpene cyclase gene derived from Streptomyces griseolosporeus, a producer of an unique diterpenoid cytotoxic antibiotic terpentecin, and by in vivo labeling with mevalonate-d(9). The cyclization involved electrophilic protonation, cationic ring closure, Wagner-Meerwein-type rearrangements, and deprotonation. A key feature was that the labeled metabolite as a mixture of predominantly deuterated mosaic molecules provided sufficient information that close analysis of the labeling pattern for each individual isoprene unit was achieved primarily by (1)H NMR spectroscopy. The cyclization of GGPP into the clerodane skeleton catalyzed by the cyclase appears to involve Si-face specific protonation, intermediates with A/B chair-boat conformation, and specific methyl and hydride migrations to give an intermediary C-4 carbocation. Subsequent collapse of the cation through specific removal of the initiating proton and final elimination of diphosphate gives rise to the terpentetriene hydrocarbon.     

Three-variable reversible Gray-Scott model

Even though the field of nonequilibrium thermodynamics has been popular and its importance has been suggested by Demirel and Sandler [J. Phys. Chem. B 108, 31 (2004)], there are only a few investigations of reaction-diffusion systems from the aspect of thermodynamics. A possible reason is that model equations are complicated and difficult to analyze because the corresponding chemical reactions need to be reversible for thermodynamical calculations. Here, we introduce a simple model for calculation of entropy production rate: a three-variable reversible Gray-Scott model. The rate of entropy production in self-replicating pattern formation is calculated, and the results are compared with those reported based on the Brusselator model in the context of biological cell division.     

Clavulones,new type of prostanoids from the stolonifer clavulariaviridis quoy and gaimard

Three new prostanoids, clavulone I($\text{1}$), II($\text{2}$) and III($\text{3}$), were isolated from the Japanese Stolonifer $\text{Claularia}$$\text{viridis}$ Quoy and Gaimard. The structures of these prostanoids were determined on the basis of spectral data and chemical reactions.     

Solution viscosity behavior of polystyrene-based cationic ionomers: Effects of quaternary-group structure and counter ion

The dilute solution viscosity was investigated for several polystyrene-based cationic io-nomers. It was found that intramolecular aggregation among the ionic groups was strongly dependent on the sizes of quaternary onium groups and counter anions. The extent of the aggregation was controled by the solvent polarity and the solvation to the ionic groups. When there was a strong selective soivation to small counter ions, the structure of onium groups shows a minor effect on the viscosity behavior, indicating little aggregation among the ionic groups. A strong solvation to small quaternary cations also eliminates the intra-molecular aggregation and the influence of counter ions was barely observable. When the selective solvation to counter ions was disabled by the enlarged size of the counter ions, however, the viscosity depended on onium group structure or spacer chain length. If the solvent solvates neither counter ions nor quaternary groups, the smaller the sizes of onium cation and counter anion, the lower the reduced viscosity due to an enhancement of the ionic aggregate formation. © 1995 John Wiley & Sons, Inc.