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61.
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addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts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. 相似文献
62.
Zhai X. Garate E. Prohaska R. Benford G. Fisher A. 《IEEE transactions on plasma science. IEEE Nuclear and Plasma Sciences Society》1993,21(1):142-150
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 相似文献
63.
The standard model on non-commutative space-time 总被引:1,自引:0,他引:1
X. Calmet B. Jurčo P. Schupp J. Wess M. Wohlgenannt 《The European Physical Journal C - Particles and Fields》2002,23(2):363-376
We consider the standard model on a non-commutative space and expand the action in the non-commutativity parameter . No new particles are introduced; the structure group is . We derive the leading order action. At zeroth order the action coincides with the ordinary standard model. At leading order
in we find new vertices which are absent in the standard model on commutative space-time. The most striking features are couplings
between quarks, gluons and electroweak bosons and many new vertices in the charged and neutral currents. We find that parity
is violated in non-commutative QCD. The Higgs mechanism can be applied. QED is not deformed in the minimal version of the
NCSM to the order considered.
Received: 29 November 2001 / Published online: 25 January 2002 相似文献
64.
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. 相似文献
65.
Observation of spontaneous pattern with six-fold symmetry in disk-shaped ZnO complex microstructures
L.W. Yang Y.J. Gao X.L. Wu Y.M. Yang G.S. Huang Z.Y. Zhang P.K. Chu 《Applied Physics A: Materials Science & Processing》2007,89(1):173-176
Using a simple vapor phase transport technique, we have fabricated unique complex disk-shaped ZnO microstructures comprising
a small disk coaxially grown on a large one and observed spatially perfect six-fold symmetric patterns. The observed results
can be explained based on the spontaneous nanoindentation (NI) effect under the geometric constraints and the explanation
can be extended to fathom the growth mechanism of other highly symmetrical ZnO nanostructures. Our results indicate that NI
not only can elucidate the mechanical properties of surfaces and thin films but also is an effective approach to fabricate
ordered nanostructures with high precision on the location of the building blocks.
PACS 81.16.Rf; 81.07.-b; 81.05.Dz 相似文献
66.
J. Xu J. Mei X.H. Huang X. Li Z. Li W. Li K. Chen 《Applied Physics A: Materials Science & Processing》2005,80(1):123-126
The effect of nitrogen surface doping on the electron field emission characteristics of hydrogenated amorphous carbon films was studied. It was found that the emission threshold electric field decreased after nitrogen surface doping which indicated the reduction of the emission barrier at the film surface. It was demonstrated that this improvement arose from the decrease of the effective work function due to the formation of a dipole layer induced by chemical termination and chemical structural change on the film surface. PACS 52.75.Xx; 73.30 +y; 73.61.Jc 相似文献
67.
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. 相似文献
68.
Rodrigo París José Luis de la Fuente 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3538-3549
Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), 1H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007 相似文献
69.
We present a new verified optimization method to find regions for Hénon systems where the conditions of chaotic behaviour
hold. The present paper provides a methodology to verify chaos for certain mappings and regions. We discuss first how to check
the set theoretical conditions of a respective theorem in a reliable way by computer programs. Then we introduce optimization
problems that provide a model to locate chaotic regions. We prove the correctness of the underlying checking algorithms and
the optimization model. We have verified an earlier published chaotic region, and we also give new chaotic places located
by the new technique. 相似文献
70.
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. 相似文献