The effect of reduction on rhenium(I) complexes with binaphthyridine and biquinoline ligands: a spectroscopic and computational study

A number of rhenium complexes with binaphthyridine and biquinoline ligands have been synthesized and studied. These are [Re(L)(CO)3Cl] where L = 3,3'-dimethylene-2,2'-bi-1,8-naphthyridine (dbn), 2,2'-bi-1,8-naphthyridine (bn), 3,3'-dimethylene-2,2'-biquinoline (dbq), and 3,3'-dimethyl-2,2'-biquinoline (diq). This series represents ligands in which the electronic properties and steric preferences are tuned. These complexes are modeled using density functional theory (DFT). An analysis of the resonance Raman spectra for these complexes, in concert with the vibrational assignments, reveals that the accepting molecular orbital (MO) in the metal-to-ligand charge transfer (MLCT) transition is the LUMO and causes bonding changes at the inter-ring section of the ligand. The electronic absorption spectroelectrochemistry for the reduced complexes of [Re(dbn)(CO)3Cl], [Re(dbq)(CO)3Cl], and [Re(diq)(CO)3Cl] suggest that the singly occupied MO is delocalized over the entire ligand structure despite the nonplanar nature of the diq ligand in [Re(diq)(CO)3Cl]. The IR spectroelectrochemistry for [Re(dbn)(CO)3Cl], [Re(dbq)(CO)3Cl], and [Re(bn)(CO)3Cl] reveal that reduction lowers the CO ligand vibrational frequencies to a similar extent in all three complexes. The substitution of naphthyridine for quinoline has little effect on the nature of the singly occupied MO. These data are supported by DFT calculations on the reduced complexes, which reveal that the ligands are flattened out by reduction: This may explain the similarity in the properties of the reduced complexes.     

Slow-light fourier transform interferometer

We describe a new type of Fourier transform (FT) interferometer in which the tunable optical delay between the two arms is realized by using a continuously variable slow-light medium instead of a moving arm as in a conventional setup. The spectral resolution of such a FT interferometer exceeds that of a conventional setup of comparable size by a factor equal to the maximum group index of the slow-light medium. The scheme is experimentally demonstrated by using a rubidium atomic vapor cell as the tunable slow-light medium, and the spectral resolution is enhanced by a factor of approximately 100.     

Thermal degradation of trimethylolpropane/adipic acid hyperbranched poly(ester)s

Hyperbranched poly(ester)s offer attractive features for applications in a number of areas, particularly as platforms for the support of controlled release actives in the agricultural and biomedical fields. Such materials have been generated from trimethylolpropane and adipic acid, and fully characterized using chromatographic, spectroscopic, and thermal methods. The thermal stability of these polymers has been assessed using thermogravimetry and infrared spectroscopy. The degradation characteristics of these materials have been compared to those of two linear adipic acid polymers. The prominent feature of the thermal degradation of the hyperbranched poly(ester)s is ether formation while that for the comparable linear poly(ester)s is ester pyrolysis resulting in chain scission.     

锂离子电池硅基负极材料的研究进展

硅基材料是新一代高容量锂离子蓄电池负极材料的典型代表,近年来已成为理论研究和应用研究的热点.本文介绍了锂离子电池硅基负极材料的制备方法、电化学性能及其研究现状,分析了硅材料作为锂离子电池负极材料存在的问题;讨论了硅材料作为锂离子电池负极材料的研究前景.并指出若能克服目前存在问题,将有望成为新一代锂离子电池负极材料.     

Calibration of a Bonner sphere extension (BSE) for high-energy neutron spectrometry

In a recent work, we constructed modular multisphere system which expands upon the design of an existing, commercially available Bonner sphere system by adding concentric shells of copper, tungsten, or lead. Our modular multisphere system is referred to as the Bonner Sphere Extension (BSE). The BSE was tested in a high energy neutron beam (thermal to 800 MeV) at Los Alamos Neutron Science Center and provided improvement in the measurement of the neutron spectrum in the energy regions above 20 MeV when compared to the standard BSS (Burgett, 2008 and Howell et al., 2009).However, when the initial test of the system was carried-out at LANSCE, the BSE had not yet been calibrated. Therefore the objective of the present study was to perform calibration measurements. These calibration measurements were carried out using monoenergetic neutron ISO 8529-1 reference beams at the Physikalisch-Technische Bundesanstalt (PTB), Braunschweig, Germany. The following monoenergetic reference beams were used for these experiments: 14.8 MeV, 1.2 MeV, 565 keV, and 144 keV. Response functions for the BSE were calculated using the Monte Carlo N-Particle Code, eXtended (MCNPX). The percent difference between the measured and calculated responses was calculated for each sphere and energy. The difference between measured and calculated responses for individual spheres ranged between 7.9 % and 16.7 % and the arithmetic mean for all spheres was (10.9 ± 1.8) %. These sphere specific correction factors will be applied for all future measurements carried-out with the BSE.     

使用色散可调啁啾光纤光栅在常规单模光纤中实现超过100km,10Gb/s的转输 *

报道了用简单的应力方法使均匀光栅成为线性啁啾光纤光栅的技术 ,并推导出了相应理论 ,发现最大色散补偿带宽与色散的乘积近似为常数 .在常规单模光纤G652,10Gb/s系统中实现超过100km的色散补偿 .     

Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles

β-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β-ketonitriles. The products could be further derivatized to valuable chiral α,α-disubstituted-β-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.     

First observation of the point spread function of optical transition radiation

We represent the first experimental observation of the point spread function (PSF) of optical transition radiation (OTR) performed at KEK-Accelerator Test Facility extraction line. We have demonstrated that the PSF vertical polarization component has a central minimum with a two lobe distribution. However, the distribution width varied significantly with wavelength. We assume that we observed a severe effect from spherical or chromatic aberrations which are not taken into account in any existing theoretical model. We believe that the result of this work will encourage theoreticians to continue developing the theory as it is important for various transition radiation applications. Nonuniform distribution of the OTR PSF creates an opportunity for developing a submicrometer transverse beam size monitor.