Vapor-particle partitioning of hydrocarbons in Western Mediterranean urban and marine atmospheres

An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon.     

Substituted m-phenylene bridges as strong ferromagnetic couplers for Cu(II)-bridge-Cu(II) magnetic interactions: new perspectives

Based on a combined theoretical-experimental study, we propose that substituted m-phenylene ligands (m-N-Phi-N) can act as tuneable strong ferromagnetic couplers connecting Cu(II) ions; a new complex presenting that bridge with J close to +15 cm(-1) has been suggested and synthesized.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.     

Chips and Qi: microcomponent-based analysis in traditional Chinese medicine

Over the last 50 years or so Traditional Chinese medicine (TCM) has been subject to intensive basic and clinical research. Although the effectiveness and remarkable safety of TCM have been documented after controlled clinical studies, there are several herbal and animal parts that are toxic or difficult to identify. DNA polymorphism-based assays have recently been developed for the identification of herbal medicines. In this approach, small amounts of DNA are amplified by the polymerase chain reaction and the reactions products are analyzed by gel electrophoresis, sequencing, or hybridization with species-specific probes. With the DNA based identification of TCM materials as an example, chip-based analytical micro devices were developed with the goal of fabricating an integrated device that will enable sample preparation, amplification, and analysis on a single microchip-based device ("lab-on-a-chip"). The application of a silicon-based polymerase chain reaction microreactor and a DNA microarray for the DNA sequence-based identification of toxic medicinal plants is reported here.     

Photoacclimation in spathiphyllum

We studied photoacclimation in Spathiphyllum grown at an irradiance of 40 or 420 micromol/m2 s (LL or HL, respectively). All parameters studied responded to acclimation. Leaves at LL, in contrast to HL, were thinner and oriented perpendicular to the incident light, had more chlorophyll per g f w, fewer stomata on the upper leaf surface and a reduced layer of mesophyll cells. Their chloroplasts at HL had wider grana with less thylakoids per granum, and better organized photosystems than at LL. PSI and PSII activities per mg chlorophyll ( Vmax ), and PSI and PSII content (total activity per g f w), were lower at LL than at HL and so was the light requirement for saturation of the PSI or PSII partial photoreactions, suggesting that fewer photosystems with larger antenna size prevail at LL, but many more with smaller antenna size at HL. Analysis of chlorophyll distribution among the thylakoid pigment-protein complexes showed less antenna chlorophyll serving PSII (CPa+LHCP1+LHCP3) than that serving PSI (CPIa+CPI+LHCP2) at LL as compared to HL, and thus a lower PSII/PSI ratio at LL, in agreement with the general finding that LL plants, with larger PSII antenna size, have lower PSII/PSI ratio. The increase in PSI antenna size at LL was correlated with the increase in the distribution of chlorophyll in pigment-protein complexes serving PSI, and a very large chlorophyll/protein molar ratio in the isolated CPI complex. On the other hand, the PSII antenna chlorophyll (CPa+LHCP1+LHCP3) on a g f w basis, and the chlorophyll a/b ratio remained more or less constant at LL or HL. This may reflect our finding that Spathiphyllum contains mainly the 27 kDa inner LHCII antenna protein, the size of which remains unaffected by photoacclimation. The increase in the distribution of chlorophyll in pigment-protein complexes serving PSII at HL, therefore, reflects the higher population of PSII at HL. Very high PSI activity was found at HL, which we attribute to the highly organized small in size PSI.     

IN VITRO STUDIES ON THE PHOTOSENSITIZED OXIDATION OF LENS PROTEINS BY PORPHYRINS

Abstract Porphyrins, which may be introduced into the eye as a result of abnormal porphyrin metabolism (uroporphyrin–Uro) or when used in the diagnosis or photodynamic therapy of certain tumors, including intraocular tumors (hematoporphyrin–Hp and'hematoporphyrin derivative'–Hpd and mesotetra( P -sulfonatophenyl)porphyrin–TPPS) are efficient photosensitizers in biological systems. We have been studying the potential phototoxic side effects of these drugs in the lens of the eye. Encapsulated in the human lens is a mixture of soluble protein crystallins. With little turnover of protein in the lens, any photosensitized modifications will accumulate and may result in an opacification of the lens. To evaluate the potential of different porphyrins to induce such damage, a series of porphyrins were photolyzed (transmission above 295 nm) in the presence of calf lens protein (2 mg m⁻¹). Marked photopolymerization and histidine destruction were observed for the lens protein photolyzed in the presence of all of the drugs. We have found that the relative effectiveness of the following porphyrins to induce that damage is: Uro = TPPS Hpd = Hp. Both the singlet oxygen quencher, azide, and the free radical scavenger, penicillamine, decrease this photosensitized oxidative damage to lens protein. TPPS binds significantly to lens protein and this binding leads to conformational changes in that protein.     

Studies on the synthesis of pentacyclic strychnos indole alkaloids. photocyclization of n-chloroacetyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino[4,3-b]indole derivatives

Photocyclization of 2-chloroacetyl-1,2,3,4,5,6-hexahydro-1, 5-methanoazocino[4,3-b]indole ($\text{5}$) takes place at the indole 4-position to give a 1 ,2 ,3 ,4 , 5 ,6-hexahydro-2 ,11-ethano-1 ,5-methanoazocino [4 , 3-6] indole system. Consequently, the method appears to be unsuitable for constructing the pyrrolidine ring of pentacyclic Strychnos indole alkaloids.     

Standardization of multi-nuclide mixtures by a new spectrum unfolding method

A new spectrum unfolding method has been applied to double-labeled mixtures with excellent results, while the CIEMAT/NIST method has been used for gels. The convenience of applying both methods has been demonstrated with mixtures containing more than three components.⁹⁰Sr+⁹⁰Y,⁸⁹Sr,²⁰⁴TI,⁴⁵Ca and³⁵S nuclides were combined as three, four and five components, and the different quench values and activity ratios were assayed. The discrepancies between computed and experimental activities were also obtained. Mixtures with some of their components below background have been prepared in order to test low-level activities.