Improvements for ground-based remote sensing of atmospheric aerosol properties by additional polarimetric measurements

We discuss the improvements in the aerosol properties characterization resulting from the additional multi-wavelength polarization measurements measured by a new CIMEL polarized sun/sky-photometer, CE318-DP. In order to process direct-sun, sky and polarization measurements in a wide spectral range (340–1640 nm), we developed new calibration methods and strategies, e.g. using the Langley plot method to calibrate both direct-sun irradiance and sky radiance, as well as combining laboratory facilities with a vicarious method to calibrate the polarized sky measurements. For studying the impact of new polarimetric measurements on the retrievals of aerosol properties, we have processed an extensive record of field measurements using an updated Dubovik and King retrieval algorithm [Dubovik O, Sinyuk A, Lapyonok T, Holben BN, Mishchenko MI, et al. Application of spheroid models to account for aerosol particle nonsphericity in remote sensing of desert dust. J Geophys Res 2006;111:D11208.]. A preliminary analysis shows that adding polarization in the inversion can reduce possible errors (notably for about 30% of our field cases) in the fine mode size distribution, real part of refractive index and particle shape parameter retrievals, especially for small particles.     

Organo-iron mediated synthesis of functional dendrimers with 1 → 3 connectivity

The organo-iron mediated activation of arene in the sandwich complexes [FeCp(η⁶-arene)][PF₆] is shown to produce 1 → 3 connectivity at benzylic positions that was utilized for dendrimer syntheses. This mini-review of the work carried out in the authors’ laboratory summarizes this principle and its applications with emphasis on recent significant improvements in the CpFe⁺-mediated reactions, recyclability of the CpFe⁺ group, mechanistic features and examples of efficient and useful functionalization reactions.     

Ring-rearrangement metathesis of substituted dihydropyrans and dihydrofurans

The rearrangement of dihydropyrans and dihydrofurans featuring appending olefins has been studied. The rearranged products bear resemblance with polyunsaturated di- and trisaccharides. Examples of functionalization prior to, or following, rearrangement are provided suggesting that the method should be useful for the synthesis of nonclassical saccharides. This work also illustrates the power of cascade methatetic processes for increasing molecular complexity starting from relatively simple heterocycles.     

Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules

We studied the electronic and conductance properties of two thiophene–curcuminoid molecules, 2‐thphCCM ( 1 ) and 3‐thphCCM ( 2 ), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO–LUMO band gap energies, showing that molecule 1 has lower values than 2 . Theoretical calculations show the same trend. Self‐assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO–LUMO gap in both molecules to almost the same value. Single‐molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.     

Dynamic light scattering study of the ultrasonication of P(VDF-TrFE): A new model

The purpose of this paper is to understand the mechanisms occurring during the ultrasonication of the copolymer poly(vinylidenedifluoride-trifluoroethylene). In these experimental conditions, the polymer adopts a core–shell structure and its hydrodynamic diameter is measured by dynamic light scattering. The results show that, without covalent bonds breakage, the hydrodynamic diameter decreases with ultrasonication time and a smaller size population appears. This evolution is reversible in a matter of days. A new two-step mechanism is proposed to describe this phenomenon: first the erosion of a core–shell structure and second the contraction of the core. Beyond shedding a new light on the phenomena occurring during the sonication of polymers used in nanocomposites elaboration, this work also strongly questions the traditional techniques used to study the degradation of polymers, which use the hydrodynamic diameter measurement to determine the molecular weight.     

Homoclinic Solutions for Swift-Hohenberg and Suspension Bridge Type Equations

We establish the existence of homoclinic solutions for a class of fourth-order equations which includes the Swift-Hohenberg model and the suspension bridge equation. In the first case, the nonlinearity has three zeros, corresponding to a double-well potential, while in the second case the nonlinearity is asymptotically constant on one side. The Swift-Hohenberg model is a higher-order extension of the classical Fisher-Kolmogorov model. Its more complicated dynamics give rise to further possibilities of pattern formation. The suspension bridge equation was studied by Chen and McKenna (J. Differential Equations136 (1997), 325-355); we give a positive answer to an open question raised by the authors.     

Development and application of a novel immunoassay for measuring oxidative DNA damage in the environment

We developed a facile, cost-effective competitive binding assay for the analysis of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) in DNA, using a polyclonal rabbit antiserum raised against an 8-oxodGuo hapten coupled to bovine serum albumin and radiolabeled synthetic ligand containing multiple 8-oxodGuo residues. This radioimmunoassay (RIA) displays a high affinity for 8-oxodGuo in DNA, with a detection limit of approximately 1 adduct in 10(5) bases of DNA. 8-oxodGuo standards for RIA were quantified by high-performance liquid chromatography and electrochemical detection in DNA diluted in methylene blue and exposed to visible light. As an initial application we quantified 8-oxodGuo in dosimeters deployed at increasing depths in the Southern Ocean during the austral spring of the 1998 field season or at the surface at Palmer Station, Antarctica, throughout the 1999 field season. Cyclobutane pyrimidine dimers (CPD) were quantified using an established RIA. We found that the frequency of both photoproducts decreased with depth. However, CPD induction was attenuated at a faster rate than 8-oxodGuo, correlating with the differential attenuation of solar ultraviolet wavelengths in the water column. CPD induction was closely related with ultraviolet-B radiation (UVB) attenuation, whereas the lower attenuation of 8-oxodGuo suggests that oxidative damage is more closely related to ultraviolet-A radiation (UVA) irradiance. The ratio of 8-oxodGuo: CPD was also found to covary with changes in stratospheric ozone concentrations at Palmer Station. These data demonstrate the usefulness of these assays for environmental photobiology and the potential for their use in studying the relative impacts of UVB versus UVA, including ozone depletion events.