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71.
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addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts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
72.
A PULSED LASER AND PULSE RADIOLYSIS STUDY OF AMPHIPHILIC CHLOROPHYLL DERIVATIVES WITH PDT ACTIVITY TOWARD MALIGNANT MELANOMA 总被引:1,自引:0,他引:1
L. Fiedor A. A. Gorman I. Hamblett V. Rosenbach-Belkin Y. Salomon A. Scherz I. Tregub 《Photochemistry and photobiology》1993,58(4):506-511
Two amphiphilic derivatives of chlorophyll, which have high potential as photodynamic therapy sensitizers for malignant melanoma have been investigated by a combination of laser flash photolysis and pulse radiolysis. It is shown that direct excitation of monomeric forms of these molecules in both hydrophilic and hydrophobic environments produces significant yields of the corresponding triplet states, which have been characterized in terms of spectral and kinetic parameters. In both environments, scavenging of the triplets by oxygen produces singlet oxygen, O2 (l Δ8 ), with essentially unit efficiency as evidenced by time-resolved IR luminescence measurements. 相似文献
73.
Jürg Kramer 《Elemente der Mathematik》2002,57(3):115-120
74.
B. MacMillan M. Halse M. Schneider L. Fardy Y. H. Chui B. J. Balcom 《Applied magnetic resonance》2002,22(2):247-256
Magnetic resonance imaging has rarely been applied to rigid polymeric materials, due primarily to the strong dipolar coupling and short signal lifetimes inherent in these materials. SPRITE (single point ramped imaging withT 1 enhancement) (B. J. Balcom, R. P. MacGregor, S. D. Beyea, D. P. Green, R. L. Armstrong, T. W. Bremner: J. Magn. Reson. A123, 131–134, 1996) is particularly well suited to imaging solid materials. With SPRITE, the only requirement is thatT 2* be long enough so that the signal can be phase-encoded. The minimum phase encoding time is limited by the maximum gradient strength available and by the instrument deadtime. At present this is usually tens of microseconds and will only improve with refinements in technology. We have used the SPRITE sequence in conjunction with raising the sample temperature to obtain images of rigid polymers that have largely frustrated conventional imaging methods. This approach provides a straightforward and reliable method for imaging a class of samples that, up until now, have been very difficult to image. 相似文献
75.
The most promising next generation Image Velocimtry (IV) is the high-speed Dynamic PIV. It requires the development of innovative
high-speed video camera sensors. We started by specifying the required performance of these new sensors, for measurements
in air and water flows. These criteria founded on the most recent developments in PIV algorithms and incorporate results from
a large questionnaire survey of users of high-speed video cameras in Japan. The results suggest that the followings are required:
(1) frame rate of 1,000,000 fps, (2) pixel count of 1,000,000 pixels, (3) frame storage capacity of 100–200 frames for tracing
a single event and 10,000 frames for turbulent measurements, (4) gray levels of 4–8 bits for PTV; 12 bits for observation.
Finally, we reviewed the state of the art of high-speed video-image sensors. Currently the standard parallel-readout sensors
can operate at 1 Kfps with a pixel count of approximately 1 Kpixels. The In-situ Storage Image Sensor (ISIS) developed by
the authors has recently achieved frame rates of 1 Mfps. 相似文献
76.
The 2D Rancieite type manganic acid was prepared by reduction of KMnO4 in acidic medium. Its ion exchange behavior allows to prepare alkali derivatives. All compounds were characterized with use of a combination of X-ray diffraction, chemical analyses, TGA, magnetic measurements and spectroscopic techniques. The evolution of their chemical composition versus temperature was studied between 180 and 400 °C. It shows that the dehydration process is partly reversible in these compounds whereas the weak reduction is irreversible. The 2D Rancieite-type manganic acid is readily different from a Birnessite-type phyllomanganate, as shown by several features: the interlayer distance, the ion exchange capacity, the thermal behavior, the interlayer cation content, the manganese average oxidation state, the magnetic behavior and the IR spectrum. 相似文献
77.
Y. Yavin 《Journal of Optimization Theory and Applications》1993,78(1):77-91
Stochastic optimal control techniques are applied to compare the performance of identical medium-range air-to-air missiles which have different thrust-mass profiles. The measure of the performance is the probability of reaching a lock-on-point with a favorable range of guidance and flight parameters, during a fixed time interval [0,t
f
], given that, during the flight, the trajectories of the missile are subjected to a variety of constraints including dynamic pressure constraints. 相似文献
78.
The contributions to the coefficient functions of the quark and the mixed quark-gluon condensate to mesonic correlators are calculated for the first time to all orders in the quark masses, and to lowest order in the strong coupling constant. Existing results on the coefficient functions of the unit operator and the gluon condensate are reviewed. The proper factorization of short- and long-distance contributions in the operator product expansion is discussed in detail. It is found that to accomplish this task rigorously the operator product expansion has to be performed in terms ofnon-normal-ordered condensates. The resulting coefficient functions are improved with the help of the renormalization group. The scale invariant combination of dimension 5 operators, including mixing with the mass operator, which is needed for the renormalization group improvement, is calculated in the leading order.Supported by the German Bundesministerium für Forschung und Technologie, under the contract 06 TM 761 相似文献
79.
Semi-empirical molecular orbital calculations were carried out for the compounds (C2H5)3As, (C2H5)3Ga and RAsH2 (R = C2H5, i-C3H7, i-C4H9, and t-C4H9) by using the CNDO/2-U program, and their capability of β-elimination reaction is compared on the basis of the torsion energy to the transition state, electrostatic interactions and orbital overlapping between the central atom and the β-hydrogen, and bond order of the metal-carbon, and carbon-hydrogen bond. In the comparison of (C2H5)3As with (C2H5)3Ga, we found that the β-elimination of (C2H5)3As could hardly be expected to take place in the thermal decomposition. The capability of β-elimination would be smaller in C2H5AsH2 than that in (C2H5)3As. Moreover when the ethyl group is replaced by a t-butyl group in RAsH2, the β-elimination reaction appears to become more difficult and a large possibility for a radical process is suggested. 相似文献
80.
Correspondence is established between sigma models, minimal surfaces and the Monge–Ampére equation. The Lax pairs of the minimality condition of the minimal surfaces and the Monge–Ampére equations are given. Existence of infinitely many nonlocal conservation laws is shown and some Bäcklund transformations are also given. 相似文献