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 In other solvents, the radical chain addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts to norbornene.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

The spectrum of normal oscillations of an elastoplastic medium with dissipation

Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, No. 4, pp. 108–112, July–August, 1993.     

Synthesis of ω-amino- and ω-carboxyalkylamides of N-acetylmuramoyl-L-alanyl-D-isoglutamine

The synthesis has been effected of derivatives of MDP having a spacer with an amino or carboxy group. The final stage of the synthesis was the condensation of Boc-L-Ala-D-iGln with 6-aminohexanol (followed by the two-stage replacement of the hydroxy by an azido group) or with benzyl 6-aminohexanoate.Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 122–125, January–February, 1993.     

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.     

Synthesis of furaxanenitrolic acids

Previously unreported furoxanenitrolic acids have been synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1117–1119, August, 1993.     

About non-linear realization of quantumSL q(2, R) group

Published in Teoreticheskaya i Matematicheskaya Fizika, Vol. 95, No. 2, pp. 183–186, May, 1993.     

Vibrational control of crystal growth from liquid phase

Modeling and numerical simulations of the convective flows induced by the vibration of the monocrystal during crystal growth have been performed for two configurations simulating the Cz and FZ methods. This permitted to emphasize the role of different vibrational mechanisms in the formation of the average flows. It is shown that an appropriate combination of these mechanisms can be used to counteract the usual convective flows (buoyancy- and/or thermocapillary-driven) inherent to crystal growth processes from the liquid phase. While vibrational convection is rather complex due to these identified mechanisms, the new modeling used in the present paper opens up very promising perspectives to efficiently control heat and mass transfer during real industrial applications of crystal growth from the liquid phase.     

Crystal structures of two ancylite modifications

The crystal structures of two ancylite specimens from Khibiny massif (the Kola Peninsula, Russia)—ancylite-(Ce) from alkali hydrothermalites (Sr_1.01Ca_0.02Ba_0.01)_Σ1.04(Ce_0.52La_0.28Nd_0.11Pr_0.04 Sm_0.01)_Σ0.96(CO₃)₂(OH_0.83F_0.13)_Σ0.96 · 0.9H₂O and ancylite-(Ce) from carbonatites—have (Sr_0.80Ca_0.05Ba_0.01)_Σ0.86(Ce_0.62La_0.40Nd_0.09Pr_0.03) _Σ1.14(CO₃)₂(OH_0.99F_0.15)_Σ1.14 · 1.0H₂O been refined by the Rietveld method. A focusing STOE-STADIP diffractometer with a bent Ge(111) primary monochromator was used (λ MoK _{α 1} radiation, 2.16° < 2θ < 54.98°; reflection number 237–437). All the computations for ancylite from alkali hydrothermalites were performed within the sp. gr. Pmc2₁, a = 5.0634(1) Å, b = 8.5898(1) Å, c = 7.2781(1) Å, V = 316.55(1) ų, R _wp = 1.90; the computations for ancylite from carbonatites were performed within the sp. gr. Pmcn, a = 5.0577(1) Å, b = 8.5665(2) Å, c = 7.3151(2) Å, V = 316.94(1) ų, R _wp = 2.38 in the anisotropic approximation of thermal vibrations of cations and oxygen atoms.     

Monte Carlo determinations of the beta dose rate to tooth enamel

The results of Monte Carlo simulations of the beta dose rate to enamel are presented. The dose rates are the most comprehensive to date, incorporating the beta spectrum from 21 different radionuclides, all internal conversion and Auger electrons, the majority of the bremsstrahlung radiation, effects due to radon loss in the uranium series, and variations in the moisture content of the sediment. Applications to a new dating technique in archaeology using electron spin resonance and beta-gradient isochrons are discussed.