Thermally induced crystallization, hole-transport, NLO and photovoltaic activity of a bis-diarylamine-based push-pull molecule

The synthesis of a molecule constituted of two diarylamine-based push-pull chromophores covalently linked via their nitrogen atom is described. Comparison of the electronic properties with the parent monomer shows that dimerization has negligible influence on the electronic properties of the molecule but exerts a dramatic impact on the capacity of the material to self-reorganize. Application of thermal annealing to thin films induces the crystallization under original morphologies, a process accompanied by a partial bleaching of the absorption in the visible range and by a huge increase of hole-mobility. X-ray diffraction data on single crystals reveal the presence of π-stacked organization with a non-centrosymmetric co-facial arrangement of the dipoles which leads to intrinsic 2nd order bulk NLO properties of thin films as evidenced by second harmonic generation under 800 nm laser light. The implications of this thermally induced crystallization on the photovoltaic properties of the material are discussed on the basis of preliminary results obtained on simple bilayer organic solar cells

A Mechanofluorochromic push-pull small molecule with aggregation-controlled linear and nonlinear optical properties

A small push-pull molecule involving a diphenylamine substituted by an oligo-oxyethylene chain is described. The compound exhibits aggregation-induced emission with solvent-dependent emission wavelength. Spun-cast deep-red amorphous films rapidly self-reorganize into colorless crystalline films which exhibit mechanofluorochromism and aggregation-induced second harmonic generation

Opportunities of deoxyribonucleic acid complexes composites for nonlinear optical applications

In this paper, we illustrate new functionalities for nonlinear optical applications of bio-molecular systems. This study presents DNA complex with new ionic surfactants. These surfactants enabled DNA solubility in solvents other than alcohols, like aromatic and chlorinated ones. Composites with two nonlinear optical (NLO) active dyes are subjects of the second and third harmonic generation experiments. The found effective nonlinear susceptibilities values are much higher than that for standard fused silica. We also demonstrate any influence of the surfactant on NLO properties. (C) 2011 American Institute of Physics. [doi:10.1063/1.3655985

Hydration and protein folding in water and in reverse micelles: compressibility and volume changes

ABSTRACT The partial specific volume and adiabatic compressibility of proteins reflect the hydration properties of the solvent-exposed protein surface, as well as changes in conformational states. Reverse micelles, or water-in-oil microemulsions, are protein-sized, optically-clear microassemblies in which hydration can be experimentally controlled. We explore, by densimetry and ultrasound velocimetry, three basic proteins: cytochrome c, lysozyme, and myelin basic protein in reverse micelles made of sodium bis (2-ethylhexyl) sulfosuccinate, water, and isooctane and in aqueous solvents. For comparison, we use ␤-lactoglobulin (pI ϭ 5.1) as a reference protein. We examine the partial specific volume and adiabatic compressibility of the proteins at increasing levels of micellar hydration. For the lowest water content compatible with complete solubilization, all proteins display their highest compressibility values, independent of their amino acid sequence and charge. These values lie within the range of empirical intrinsic protein compressibility estimates. In addition, we obtain volumetric data for the transition of myelin basic protein from its initially unfolded state in water free of denaturants, to a folded, compact conformation within the water-controlled microenvironment of reverse micelles. These results disclose yet another aspect of the protein structural properties observed in membrane-mimetic molecular assemblies

Ultrasonic studies of alcohol-induced transconformation in beta-lactoglobulin: the intermediate state

ABSTRACT In mixed alcohol-water solvents, bovine b-lactoglobulin undergoes a cooperative transition from b-sheet to a high a-helix content conformer. We report here the characterization of b-lactoglobulin by compressibility and spectroscopy measurements during this transconformation. Both the volume and compressibility increase as a function of alcohol concentration, up to maximal values which depend on the chemical nature of the three alcohols used: hexafluoroisopropanol, trifluoroethanol, and isopropanol. The order of effectiveness of alcohols in inducing the compressibility transition is identical to that previously reported for circular dichroism and thus independent of the observation technique. The highly cooperative sigmoidal curves found by compressibility determination match closely those obtained by circular dichroism at 222 nm, indicating a correlation between the two phenomena measured by the two different techniques. The presence of an equilibrium intermediate form was shown by the interaction of b-lactoglobulin with 8-anilino-1-naphthalene sulfonic acid, a probe widely used to detect molten-globule states of proteins. It was correlated with the plateau region of the volume curves and with the inflexion points of the sigmoidal compressibility curves. Ultrasound characterization of proteins can be carried out in optically transparent or nontransparent media

Crystalline Arrays of Pairs of Molecular Rotors: Correlated Motion, Rotational Barriers, and Space-Inversion Symmetry Breaking Due to Conformational Mutations

The rod-like molecule bis 4-(4-pyridyl)ethynyl)bicyclo[2.2.2]oct-1-yl)buta-1,3-diyne, 1, contains two 1,4-bis(ethynyl)bicyclo[2.2.2]octane (ethynyl) chiral rotators linked by a diyne fragment and self assembles in a one-dimensional, monoclinic C2/c centrosymmetric structure where two equilibrium positions with large occupancy imbalance (88% versus 12%) are identified on a single rotor site Combining variable temperature (70-300 K) proton spin-lattice relaxation, H-1 T-1(-1), at two different H-1 Larmor frequencies (55 and 210 MHz) and DFT calculations of rotational barriers, we were able to assign two types of Brownian rotators with different activation energies, 1.85 and 6.1 kcal mol(-1), to the two H-1 spin-lattice relaxation processes on the single rotor site. On the basis of DFT calculations, the low-energy process has been assigned to adjacent rotors in a well-correlated synchronous motion, whereas the high-energy process is the manifestation of an abrupt change in their kinematics once two blades of adjacent rotors are seen to rub together. Although crystals of 1 should be second harmonic inactive, a large second-order optical response is recorded when the electric field oscillates in a direction parallel to the unique rotor axle director. We conclude that conformational mutations by torsional interconversion of the three blades of the BCO units break space-inversion symmetry in sequences of mutamers in dynamic equilibrium in the crystal in domains at a rnesoscopic scale comparable with the wavelength of light used A control experiment was performed with a crystalline film of a similar tetrayne molecule, 1,4-bis(3-((trimethylsilyl)ethynyl)bicyclo-[1.1.1]pent-1-yObuta-1,3-diyne, whose bic-ydopentane units can rotate but are achiral and produce no second-order optical response

Complete lung agenesis caused by complex genomic rearrangements with neo-TAD formation at the SHH locus

During human organogenesis, lung development is a timely and tightly regulated developmental process under the control of a large number of signaling molecules. Understanding how genetic variants can disturb normal lung development causing different lung malformations is a major goal for dissecting molecular mechanisms during embryogenesis. Here, through exome sequencing (ES), array CGH, genome sequencing (GS) and Hi-C, we aimed at elucidating the molecular basis of bilateral isolated lung agenesis in three fetuses born to a non-consanguineous family. We detected a complex genomic rearrangement containing duplicated, triplicated and deleted fragments involving the SHH locus in fetuses presenting complete agenesis of both lungs and near-complete agenesis of the trachea, diagnosed by ultrasound screening and confirmed at autopsy following termination. The rearrangement did not include SHH itself, but several regulatory elements for lung development, such as MACS1, a major SHH lung enhancer, and the neighboring genes MNX1 and NOM1. The rearrangement incorporated parts of two topologically associating domains (TADs) including their boundaries. Hi-C of cells from one of the affected fetuses showed the formation of two novel TADs each containing SHH enhancers and the MNX1 and NOM1 genes. Hi-C together with GS indicate that the new 3D conformation is likely causative for this condition by an inappropriate activation of MNX1 included in the neo-TADs by MACS1 enhancer, further highlighting the importance of the 3D chromatin conformation in human disease

The role of tenascin-C in tissue injury and tumorigenesis

The extracellular matrix molecule tenascin-C is highly expressed during embryonic development, tissue repair and in pathological situations such as chronic inflammation and cancer. Tenascin-C interacts with several other extracellular matrix molecules and cell-surface receptors, thus affecting tissue architecture, tissue resilience and cell responses. Tenascin-C modulates cell migration, proliferation and cellular signaling through induction of pro-inflammatory cytokines and oncogenic signaling molecules amongst other mechanisms. Given the causal role of inflammation in cancer progression, common mechanisms might be controlled by tenascin-C during both events. Drugs targeting the expression or function of tenascin-C or the tenascin-C protein itself are currently being developed and some drugs have already reached advanced clinical trials. This generates hope that increased knowledge about tenascin-C will further improve management of diseases with high tenascin-C expression such as chronic inflammation, heart failure, artheriosclerosis and cancer

L'Atlas de la région Centre : financement et diffusion

Gindre P., Bord J.-P. L'Atlas de la région Centre : financement et diffusion. In: Norois, n°139, Juillet-Septembre 1988. pp. 323-330

Echographie par corrélation : caractéristiques et performances

Ultrasonic imaging using the correlation technique overcomes the problems of conventional pulse echo systems by tsansmitting a continuous coded signal. The target location is determined by cross-correlation of the emitted and the received signal. The band compression allows, by increasing SNR, the retrieval of echo signals buried in the receiver noise. Thus in medical-type echography, where the signal attenuation at fixed depth is proportional to the frequency, the SNR improvement allows the use of higher frequency signals and leads to improved resolution. We report here the results of comparative experimental studies of echo B type images as obtained by the classical pulse echo and correlation techniques. Because the optimisation of the coded signal plays a crucial role in the performance of the correlation technique we will also present a comparative study of the performances of the most common codes. In particular we shall emphasise the relative importance of the central lobe as compared to the side lobes of the correlation function, which is directly connected to the dynamic of the imaging system The respective advantages of the echo images obtained with the most promising coded signals will be discussed