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 In other solvents, the radical chain addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts to norbornene.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

A common motif in G-protein-coupled seven transmembrane helix receptors

Summary G-protein-coupled receptors all share the seven transmembrane helix motif similar to bacteriorhodopsin. This similarity was exploited to build models for these receptors. From an analysis of a multi-sequence alignment of 225 G-protein-coupled receptors belonging to the rhodopsin-like superfamily, conclusions could be drawn about functional residues. Seven residues in the transmembrane regions are conserved throughout all aligned receptors. These residues cluster at the cytosolic side of the transmembrane helices and are for all rhodopsin-like G-protein-coupled receptors implied in signal transduction. An analysis of correlated mutations reveals a number of residues, both in the helices and in the cytosolic loops, that might be important in the signal transduction pathway in subfamilies of this receptor family.     

High performance liquid chromatographic separation of polar and non-polar chlorophyll pigments from algae using a wide pore polymeric octadecylsilica column

A method employing a wide pore polymeric reversed phase column has been developed for the separation of most of the chlorophylls and related compounds previously described as occurring in marine microalgae. The high selectivity toward molecular shape of this kind of stationary phase has enabled compounds of very similar structure, such as chlorophylls c₁, c₂ and Mg-divinylpheoporphyrin a₅ monomethyl ester, and chlorophyll a and the phytol-substituted chlorophyll c-like pigments, which commonly coelute on monomeric bonded phases, to be resolved in a single run. Some of these pigments, formerly thought to be a single compound, have, in fact, been demonstrated to be groups of two or more. The method has been successfully applied to both algal cultures and natural sea water samples. When visible light absorbance detection was used, the method proved suitable for separation of various carotenoids.     

Observation of ionic thermocurrents in zirconia-based solid electrolytes

In ionic conductors, long range-migrating charges are a main cause of polarization processes. This has complicated, up to date, the study of ionic thermocurrents (ITC) in solid electrolytes. However, the method is appealing, as it probes directly charge-formation phenomena that are important both from a scientific point of view and for applications. This work reports on the observation of ITC in solid electrolytes. Under appropriate experimental conditions, the ITC response of a zirconia sample electroded with platinum is a reproducible one, thus opening the way to a new characterization method that may complement other well established methods, such as Impedance Spectroscopy and a number of electrochemical techniques. The general trends of the response, which is composed of two well resolved ITC peaks, is discussed. One of them, taking place at higher temperatures, conforms to the standard shape of a first order kinetics depolarization process. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Inclusive production of neutral vector mesons in hadronic Z decays

A data sample of about 3.0 million hadronicZ decays collected by the ALEPH experiment at LEP in the years 1991 through 1994 is used to make an inclusive selection of B hadron events. In this event sample 4227±140±252B* mesons in the decayB*→Bγ and 1944±108±161B** _u,d mesons decaying into a B meson and a charged pion are reconstructed. Here and in the followingB** _u,d denotes the eightL=1(bū) and (bd) states and their charge conjugate. For the well establishedB* meson the following quantities are obtained:ΔM=M _B*−M_B=(45.30±0.35±0.87) MeV/c² andN _B*/(N _B+N _B*)=(77.1±2.6±7.0)%. The angular distribution of the photons in theB* rest frame is used to measure the relative contribution of longitudinalB* polarization states to beσ _L/(σ _L+σ _T)=(33±6±5)%.     

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.