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 In other solvents, the radical chain addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts to norbornene.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.     

A PULSED LASER AND PULSE RADIOLYSIS STUDY OF AMPHIPHILIC CHLOROPHYLL DERIVATIVES WITH PDT ACTIVITY TOWARD MALIGNANT MELANOMA

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(^lΔ₈), with essentially unit efficiency as evidenced by time-resolved IR luminescence measurements.     

Magnetic resonance imaging of rigid polymers at elevated temperatures with SPRITE

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.     

Development of high-speed video cameras for Dynamic PIV

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.     

The 2D Rancieite-type manganic acid and its alkali-exchanged derivatives: Part I — Chemical characterization and thermal behavior

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.     

Application of stochastic optimal control to the suboptimal design of thrust-mass profiles

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.     

Decomposability of matrix polynomials with coefficients possessing quasi-simple structure

The decomposability of matrix polynomials with commuting coefficients of quasi-simple structure into regular factors and the solvability of the corresponding matrix polynomial one-sided equations are investigated.Translated from Ukrainskii Matematicheskie Zhurnal, Vol. 44, No. 12, pp. 1716–1718, December, 1992.     

Selective saturation and inversion of multiple resonances in high-resolution solid-state 13C experiments using slow spinning CP/MAS and tailored DANTE pulse sequences.

Taking advantage of the long 13C T1 values generally encountered in solids, selective saturation and inversion of more than one resonance in 13C CP/MAS experiments can be achieved by sequentially applying several DANTE pulse sequences centered at different transmitter frequency offsets. A new selective saturation pulse sequence is introduced composed of a series of 90 degrees DANTE sequences separated by interrupted decoupling periods during which the selected resonance is destroyed. Applications of this method, including the simplification of the measurement of the principal values of the 13C chemical shift tensor under slow MAS conditions, are described. The determination of the aromaticity of coal using a relatively slow MAS rate is also described.     

The epitaxial growth of gaas using alkylarsine: Part 2. molecular orbital calculation

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.