The reaction pattern of norbornene with excited state carbonyl compounds: Photochemical preparations of norbornene derivatives

We established that acetylacetone and acetone photolytically sensitize norbornene to undergo an efficient radical addition of solvent (ranging from hexane, cyclic ethers, haloalkanes, acetone, alcohols and acetonitrile) across the double bond. In view of its synthetic applicability, sensitized photoreactions of norbornene were reviewed and their mechanisms were compared. Photolysis of acetylacetone in the presence of norbornene in hexane induced i) acetylacetone to cycloadd to norbornene giving the expected 1,5-diketone, and ii) sensitization by triplet excited acetylacetone to generate reactive norbornene, which underwent dimerization as well as the addition of a solvent molecule by radical chain processes. In other solvents, the radical chain addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts to norbornene. While the excited species of acetylacetone for the sensitization was deduced to be its spectroscopic triplet excited state, that for the cycloaddition should involve a different one which may be a twisted triplet acetylacetone; sensitization experiments showed that the cycloaddition did not occur from the spectroscopic triplet state. Triplet excited acetone sensitized norbornene to undergo the same solvent addition more efficiently and cleanly than acetylacetone did. In view of various conflicts existing in the proposed energy transfer mechanism, the sensitized norbornene reactions were rationalized with electron transfer and a cation radical chain mechanism.     

Experimental study of a plasma-filled backward wave oscillator

Experimental studies of a plasma-filled X-band backward-wave oscillator (BWO) are presented. Depending on the background gas pressure, microwave frequency upshifts of up to 1 GHz appeared along with an enhancement by a factor of 7 in the total microwave power emission. The bandwidth of the microwave emission increased from ⩽0.5 GHz to 2 GHz when the BWO was working at the RF power enhancement pressure region. The RF power enhancement appeared over a much wider pressure range in a high beam current case (10-100 mT for 3 kA) than in a lower beam case (80-115 mT for 1.6 kA). The plasma-filled BWO has higher power output than the vacuum BWO over a broader region of magnetic guide field strength. Trivelpiece-Gould modes (T-G modes) are observed with frequencies up to the background plasma frequency in a plasma-filled BWO. Mode competition between the T-G modes and the X-band Tm₀₁ mode prevailed when the background plasma density was below 6×10¹¹ cm^-3 . At a critical background plasma density of ≃8×10¹¹ cm^-3 power enhancement appeared in both X-band and the T-G modes. Power enhancement of the S-band in this mode collaboration region reached up to 8 dB. Electric fields measured by the Stark-effect method were as high as 34 kV/cm while the BWO power level was 80 MW. These electric fields lasted throughout the high-power microwave pulse     

Structure of astacin and implications for activation of astacins and zinc-ligation of collagenases.

Astacin, a digestive zinc-endopeptidase from the crayfish Astacus astacus L., is the prototype for the 'astacin family', which includes mammalian metallo-endopeptidases and developmentally regulated proteins of man, fruitfly, frog and sea urchin. Here we report the X-ray crystal structure of astacin, which reveals a deep active-site cleft, with the zinc at its bottom ligated by three histidines, a water molecule and a more remote tyrosine. The third histidine (His 102) forms part of a consensus sequence, shared not only by the members of the astacin family, but also by otherwise sequentially unrelated proteinases, such as vertebrate collagenases. It may therefore represent the elusive 'third' zinc ligand in these enzymes. The amino terminus of astacin is buried forming an internal salt-bridge with Glu 103, adjacent to His 102. Astacin pro-forms extended at the N terminus, as observed for some 'latent' mammalian astacin homologues, did not exhibit this 'active' conformation, indicating an activation mechanism reminiscent of trypsin-like serine proteinases.     

Determination of the portfolio selection for a property-liability insurance company

This paper presents an analysis of a portfolio model which can be used to assist a property-liability insurance company in determining the optimal composition of the insurance and investment portfolios. By introducing insurer's threshold risk and relaxing some non-realistic assumptions made in traditional chance constraint insurance and investment portfolio models, we propose a method for an insurer to maximize his return threshold for a given threshold risk level. This proposed model can be used to optimize the composition of underwriting and investment portfolios regarding the insurer's threshold risk level, as well as to generate the efficient frontier by adjusting insurer's threshold risk levels. A numerical example is given based on the industry's aggregated data for a sixteen year period.     

Microstructural evolution of decagonal quasicrystal in the undercooled Al72Ni12Co16 alloy melts

The microstructure evolution of decagonal quasicrystals in Al₇₂Ni₁₂Co₁₆ alloy was investigated by the electromagnetic melting and cyclic superheating method. Single-phase decagonal quasicrystals have been obtained when the undercoolings were larger than 60 K. The decagonal quasicrystals formed at various undercoolings show different microstructural morphologies. Furthermore, grain refinement was found near the undercooling of 120 K. Based on current thermodynamic and dendrite growth theories, a dimensionless superheating parameter was adopted to explain the effect of processing conditions on the microstructure of Al₇₂Ni₁₂Co₁₆ alloy. The result indicate that the fine equiaxied microstructure of decagonal quasicrystal (D-phase) formed near on undercooling of 120 K originates from the break-up of dendrites.     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

Sensitivity of depolarized lidar signals to cloud and aerosol particle properties

Measurements from depolarized lidars provide a promising method to retrieve both cloud and aerosol properties and a versatile complement to passive satellite-based sensors. For lidar observations of clouds and aerosols, multiple scattering plays an important role in the scattering process. Monte Carlo simulations are carried out to investigate the sensitivity of lidar backscattering depolarization to cloud and aerosol properties. Lidar parameters are chosen to be similar to those of the upcoming space-based CALIPSO lidar. Cases are considered that consist of a single cloud or aerosol layer, as well as a case in which cirrus clouds overlay different types of aerosols. It is demonstrated that besides thermodynamic cloud phase, the depolarized lidar signal may provide additional information on ice or aerosol particle shapes. However, our results show little sensitivity to ice or aerosol particle sizes. Additionally, for the case of multiple but overlapping layers involving both clouds and aerosols, the depolarized lidar contains information that can help identify the particle properties of each layer.     

On Characterizations of Proper Efficiency for Nonconvex Multiobjective Optimization

In this paper, nonconvex multiobjective optimization problems are studied. New characterizations of a properly efficient solution in the sense of Geoffrion's are established in terms of the stability of one scalar optimization problem and the existence of an exact penalty function of a scalar constrained program, respectively. One of the characterizations is applied to derive necessary conditions for a properly efficient control-parameter pair of a nonconvex multiobjective discrete optimal control problem with linear constraints.     

146Ce核的八级形变带和准γ带

通过测量²⁵²Cf自发裂变所产生的瞬发γ射线, 对¹⁴⁶Ce核的高自旋结构进行了重新研究, 结果更新了以前报道的能级纲图, 把八级形变集体带扩展到更高的自旋, 并且重新构建了可能的准γ带结构. 此外, 用反射不对称壳模型(RASM)对¹⁴⁶Ce核的八级形变带进行了计算, 低自旋处的计算结果与实验数据符合得很好.