Influence of connectivity and porosity on ligand-based luminescence in zinc metal-organic frameworks

Applications of metal-organic frameworks (MOFs) require close correlation between their structure and function. We describe the preparation and characterization of two zinc MOFs based on a flexible and emissive linker molecule, stilbene, which retains its luminescence within these solid materials. Reaction of trans-4,4'-stilbene dicarboxylic acid and zinc nitrate in N,N-dimethylformamide (DMF) yielded a dense 2-D network, 1, featuring zinc in both octahedral and tetrahedral coordination environments connected by trans-stilbene links. Similar reaction in N,N-diethylformamide (DEF) at higher temperatures resulted in a porous, 3-D framework structure, 2. This framework consists of two interpenetrating cubic lattices, each featuring basic zinc carboxylate vertices joined by trans-stilbene, analogous to the isoreticular MOF (IRMOF) series. We demonstrate that the optical properties of both 1 and 2 correlate with the local ligand environments observed in the crystal structures. Steady-state and time-resolved spectroscopic measurements reveal that the stilbene linkers in the dense structure 1 exhibit a small degree of interchromophore coupling. In contrast, the stilbenoid units in 2 display very little interaction in this low-density 3-D framework, with excitation and emission spectra characteristic of monomeric stilbenes, similar to the dicarboxylic acid in dilute solution. In both cases, the rigidity of the stilbene linker increases upon coordination to the inorganic units through inhibition of torsion about the central ethylene bond, resulting in luminescent crystals with increased emission lifetimes compared to solutions of trans-stilbene. The emission spectrum of 2 is found to depend on the nature of the incorporated solvent molecules, suggesting use of this or related materials in sensor applications.     

Expedient BINOL derivative arylations

A dramatic improvement of our previous methodology based on a Suzuki–Miyaura cross-coupling to access 3,3′-disubstituted H₈-BINOLs using microwave heating is reported herein. These new conditions represent a large gain in term of atom-economy, reaction time, catalyst loading, and excess of reagents employed.     

Monitoring and Quantifying the Passive Transport of Molecules Through Patch–Clamp Suspended Real and Model Cell Membranes

Transport of active molecules across biological membranes is a central issue for the success of many pharmaceutical strategies. Herein, we combine the patch–clamp principle with amperometric detection for monitoring fluxes of redox‐tagged molecular species across a suspended membrane patched from a macrophage. Solvent‐ and protein‐free lipid bilayers (DPhPC, DOPC, DOPG) patched from single‐wall GUV have been thoroughly investigated and the corresponding fluxes measurements quantified. The quality of the patches and their proper sealing were successfully characterized by electrochemical impedance spectroscopy. This procedure appears versatile and perfectly adequate to allow the investigation of transport and quantification of the transport properties through direct measurement of the coefficients of partition and diffusion of the compound in the membrane, thus offering insight on such important biological and pharmacological issues.     

Ultrasonic wave propagation in heterogeneous solid media: theoretical analysis and experimental validation

This research deals with the ultrasonic characterization of thermal damage in concrete. This damage leads to the appearance of microcracks which then evolve in terms of volume rate and size in the material. The scattering of ultrasonic waves from the inclusions is present in this type of medium. The propagation of the longitudinal wave in the heterogeneous media is studied via a homogenization model that integrates the multiple scattering of waves. The model allows us to determine the phase velocity and the attenuation according to the elements which make the medium. Simulations adapted to the concrete are developed in order to test the responses of the model. These behaviors are validated by an experimental study: the measurements of phase velocity and attenuation are performed in immersion, with a comparison method, on a frequency domain which ranges from 160 kHz to 1.3 MHz. The analysis of different theoretical and experimental results obtained on cement-based media leads to the model validation, on the phase velocity behavior, in the case of a damage simulated by expanded polystyrene spheres in granular media. The application to the case of a thermally damaged concrete shows a good qualitative agreement for the changes in velocity and attenuation.     

Reflection and transmission at normal incidence onto air-saturated porous materials and direct measurements based on parametric demodulated ultrasonic waves

The present work is related to the characterization of air-saturated porous media by using parametric demodulated ultrasonic waves. One uses two different powerful ultrasonic emitters working either at 47 kHz or at 162 kHz which are electronically amplitude modulated over the 200 Hz-4 kHz or 2 kHz-40 kHz bandwidths respectively. The demodulation process takes place in air, due to its nonlinearity enabling to generate audio range acoustical waves or alternatively low frequency ultrasonic waves which can be used to characterize porous materials in the reflection configuration at normal incidence. Some appropriate theoretical calculations are introduced for three configurations of interest, i.e. a porous slab, a porous layer mounted onto a rigid plate, and a porous half space, in the case of the equivalent-fluid model. Comparisons between theoretical modeling and experimental data are provided and prospective industrial applications are discussed.     

An improved multimodal method for sound propagation in nonuniform lined ducts

An efficient method is proposed for modeling time harmonic acoustic propagation in a nonuniform lined duct without flow. The lining impedance is axially segmented uniform, but varies circumferentially. The sound pressure is expanded in term of rigid duct modes and an additional function that carries the information about the impedance boundary. The rigid duct modes and the additional function are known a priori so that calculations of the true liner modes, which are difficult, are avoided. By matching the pressure and axial velocity at the interface between different uniform segments, scattering matrices are obtained for each individual segment; these are then combined to construct a global scattering matrix for multiple segments. The present method is an improvement of the multimodal propagation method, developed in a previous paper [Bi et al., J. Sound Vib. 289, 1091-1111 (2006)]. The radial rate of convergence is improved from O(n(-2)), where n is the radial mode indices, to O(n(-4)). It is numerically shown that using the present method, acoustic propagation in the nonuniform lined intake of an aeroengine can be calculated by a personal computer for dimensionless frequency K up to 80, approaching the third blade passing frequency of turbofan noise.     

A characterization of the scattered acoustic intensity field in the resonance region for simple spheres

The properties of the scattered acoustic vector fields generated by simple spheres illuminated by monotonic continuous wave (CW) plane waves are investigated. Analytical solutions are derived from general acoustic pressure scattering models and analyzed for wave numbers in the resonance region. Of particular interest is the understanding of the characteristics of the scattered acoustic vector field in the near-to-far-field transition region. The separable active and reactive components of the acoustic intensity are used to investigate the structural features of the scattered field components. Numerical results are presented for the near and transition regions for a rigid sphere. A method of mapping nulls in the scattered intensity field components is described. The analysis is then extended to include a simple fluid-filled boundary and finally the evacuated thin-walled shell. Near field acoustic intensity field structures are compared against mechanical material properties of vacuous shells. The ability to extract scattered field features is illustrated with measurements obtained from a recent in-air experiment using an anechoic chamber and acoustic vector sensor probes to measure the scattered acoustic vector field from rigid spheres.     

Construction and Borel summability of planar 4-dimensional euclidean field theory

We use the methods of [1] to show that the planar part of the renormalized perturbation theory for ₄ ⁴ -euclidean field theory is Borel-summable on the asymptotically free side of the theory. The Borel sum can therefore be taken as a rigorous definition of theN limit of a massiveN×N matrix model with a +trg ⁴ interaction, hence with wrong sign ofg. Our construction is relevant for a solution of the ultra-violet problem for planar QCD. We also propose a program for studying the structure of the renormalons singularities within the planar world.     

Plumes and waves in two-dimensional turbulent thermal convection

We have conducted a high-resolution, two-dimensional direct numerical simulation of Rayleigh-Bénard convection with stress-free and periodic boundary conditions at a Rayleigh (Ra) number of 10(8) and Prandtl (Pr) number of unity. An aspect-ratio three box has been considered. A single cell has been used as the initial condition. First, the flow develops into time-dependent convection with a strong asymmetry and highly convoluted thermal plumes delineating a large-scale circulation. Smaller thermal plumes detach from the boundary layer and extend over the entire cell, creating a local inversion of the temperature gradient adjacent to the boundary layers. Then the conditions leading to the formation of internal waves are fulfilled, as the local Richardson number decreases sufficiently small to cross the linear threshold of Ri=0.25. Together with the strong shear, convective rolls with a Kelvin-Helmholtz wavelike character are produced. The secondary boundary layer itself becomes unstable and produces smaller plumes. At later times, the large-scale circulation is destroyed and the internal waves disappear. A Reynolds number, based on the global scale, of Re=500, is attained at this stage. Only isolated thermal plumes and vortices are present. Thus, internal waves can be generated at finite Prandtl number fluids for sufficiently high Ra in the presence of a large-scale circulation. Spectral analysis reveals that the kinetic energy decays with a logarithmic slope of -3, while the logarithmic slope of the thermal variance has a value of around -5 / 3.     

On the Second Cohomology of K?hler Groups

Carlson and Toledo conjectured that if an infinite group Γ is the fundamental group of a compact K?hler manifold, then virtually H²(G, \mathbb R) 1 0{H^{2}(\Gamma, {\mathbb R}) \ne 0} . We assume that Γ admits an unbounded reductive rigid linear representation. This representation necessarily comes from a complex variation of Hodge structure ( \mathbbC{\mathbb{C}} -VHS) on the K?hler manifold. We prove the conjecture under some assumption on the \mathbbC{\mathbb{C}} -VHS. We also study some related geometric/topological properties of period domains associated to such a \mathbbC{\mathbb{C}} -VHS.