Identification of a stereoblock poly(methyl methacrylate) sample with a stereocomplex

Acid hydrolysis of a stereoblock poly(methyl methacrylate) sample leads to a mixture of isotactic and syndiotactic poly(methacrylic acid) which can be separated by electrophoresis. The experiment confirms the stereochemical identity between the so-called “stereoblock” poly(methyl methacrylate) and the stereocomplex which syndiotactic and isotactic poly(methyl methacrylate) form in the ratio 2:1. A possible mechanism of replica polymerization is suggested to account for this effect.     

Crystalline phase effects on esca valence bands of Zr(IV) and Ti(IV) acid phosphates

The valence bands (V.B.) of ESCA spectra of Zr(IV) and Ti(IV) acid phosphates in different crystalline phases are reported. The various bands are assigned by comparison with Li₃PO₄. Variations on changing the crystalline phase for compounds having the same M(IV) ion are found. Two types of molecular orbitals are mainly involved. One related to PO bonds is affected by the crystalline phase. The other, related to M(IV)O bonds and confined into the layers of the compounds, are less sensitive to crystalline environment. Variation in the symmetry of the tetrahedral type PO^3?₄ anion are proposed to be mainly responsible of the observed effects.     

Structural homologies in benzylamino-N,N-bis methylphosphonic acid and its layered zirconium derivative

A new layered zirconium diphosphonate fluoride, ZrF(O₃PCH₂)₂NHCH₂C₆H₅ has been prepared and its structure determined ab initio by X-ray powder data and refined with the Rietveld method (orthorhombic, , , , space group Pbca, , Z=8, R_wp=0.080). Both phosphonic groups of each diphosphonate building block are bonded to zirconium atoms on the same side of each layer. Benzyl groups from adjacent layers are interdigitated in the interlayer region, with probable π-π stacking interactions. The structure of the free benzylamino-N,N-bis methylphosphonic acid has been determined by single crystal X-ray data (monoclinic, space group P2₁, , , , β=92.930(3)°, , Z=2, R₁=0.072, wR₂=0.150). As in the zirconium derivative, benzyl groups from adjacent layers are interdigitated and create a regular alternation of polar and non-polar regions.     

Diffusion in polyacrylate aqueous systems at 25°C. Role of reference frame choice in interpreting diffusion coefficient data

Diffusion coefficients have been measured for the binary systems sodium polyacrylate-water and polyacrylic acid-water at 25°C as a function of concentration. Diffusion coefficients have been also measured for the ternary system sodium chloride-sodium polyacrylate-water at constant NaCl concentration and varying polyacrylate concentration. The experimental results have been compared with some limit expressions, available in literature, for the four D _ik diffusion coefficients of systems containing two electrolytes with a common ion. The ternary system shows strong interaction between flows: as the polyelectrolyte concentration, C₂, approaches zero, the main diffusion coefficient D₂₂ and the cross coefficient D₂₁ approach zero, while the cross coefficient D₁₂ reach quite high values. The water motion during the diffusion process is also discussed.     

THz Generation via Optical Rectification in Nanomaterials: Universal Modeling Approach and Effective χ¯¯(2) Description

Optical rectification (OR) at the nanoscale has attracted an increasing interest in the prospect of providing efficient ultracompact terahertz (THz) sources. Here, a universal modeling approach capable of addressing both isotropic and anisotropic all-dielectric nonlinear nanomaterials on an ultra-broad spectral range, covering the highly dispersive phonon-polariton window, and different orientations of the crystallographic axes with respect to the geometry of the structure is reported. This analysis is exemplified by considering two study cases, that is, nanopillars of AlGaAs and of LiNbO₃. A close comparison between the two cases is established in terms of THz generation efficiency from 4 to 14 THz. Phonon-polariton contributions to the OR process are disentangled from the electronic one, and a model order reduction based on the reciprocity theorem is applied and validated on both the considered configurations. These results, combined with the inspection of the THz near-field features, pave the way to the design and optimization of nonlinear metasurfaces for THz generation and detection at the nanoscale.     

Water‐Mediated Proton Conduction in a Robust Triazolyl Phosphonate Metal–Organic Framework with Hydrophilic Nanochannels

The development of water‐mediated proton‐conducting materials operating above 100 °C remains challenging because the extended structures of existing materials usually deteriorate at high temperatures. A new triazolyl phosphonate metal–organic framework (MOF) [La₃ L ₄(H₂O)₆]Cl ? x H₂O ( 1 , L ^2?=4‐(4H‐1,2,4‐triazol‐4‐yl)phenyl phosphonate) with highly hydrophilic 1D channels was synthesized hydrothermally. Compound 1 is an example of a phosphonate MOF with large regular pores with 1.9 nm in diameter. It forms a water‐stable, porous structure that can be reversibly hydrated and dehydrated. The proton‐conducting properties of 1 were investigated by impedance spectroscopy. Magic‐angle spinning (MAS) and pulse field gradient (PFG) NMR spectroscopies confirm the dynamic nature of the incorporated water molecules. The diffusivities, determined by PFG NMR and IR microscopy, were found to be close to that of liquid water. This porous framework accomplishes the challenges of water stability and proton conduction even at 110 °C. The conductivity in 1 is proposed to occur by the vehicle mechanism.     

Velocity Measurements of a Free-Surface Turbulent Flow Penetrating a Porous Medium Composed of Uniform-Size Spheres

We present a laboratory experimental investigation of the interaction between the turbulent flow in an open channel and the turbulent flow within its very permeable bed. The bed was composed of uniform-size spheres packed in a cubic pattern. Fluid velocities were measured by Particle Image Velocimetry (PIV), which allowed us to investigate the spatial distribution of the time-averaged flow properties in the zone where they are strongly affected by the geometry of the rough bed. We investigate the effect of bed porosity on these flow properties by comparing the results of two experimental configurations: one with an impermeable bed composed of a single layer of spheres and another with a permeable bed composed of five layers. For the latter case, PIV measurements of velocities were also carried out inside two pores adjacent to the bed surface. This data provides an insight into the mechanisms of momentum transfer between the turbulent open channel flow and the turbulent flow within its very permeable bed.     

Complete nondegenerate locally standard CR manifolds

Abstract. Let M be a complete nondegenerate locally standard CR manifold. We show that a necessary and sufficient condition for M to be compact is that the Lie algebra of its infinitesimal CR automorphisms is semisimple. In general we realize M as a Mostow fibration over a compact CR manifoldB whose universal covering is a Cartesian product of Hermitian symmetric spaces and compact nondegenerate standard CR manifolds. Received: 22 July 1998 / Published online: 8 May 2000     

In Situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated CeIV-Based Metal–Organic Frameworks with UiO-66 and MIL-140 Architectures**

We report on the results of an in situ synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce^IV-based metal–organic frameworks (MOFs), analogues of the already well investigated Zr^IV-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as reagents, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds, varying parameters such as temperature, amount of the protonation modulator nitric acid and amount of the coordination modulator acetic acid. When only HNO₃ is present in the reaction environment, only F4_MIL-140A(Ce) is obtained. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C. Upon addition of AcOH to the system, alongside HNO₃, mixed-phased products are obtained. F4_UiO-66(Ce) is always formed faster, and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate-determining step. A higher amount of HNO₃ favours the formation of F4_MIL-140A(Ce), whereas increasing the amount of AcOH favours the formation of F4_UiO-66(Ce). Based on the in situ results, a new optimised route to achieving a pure, high-quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.     

The Structures,Morphologies, and Photophysical Properties of Multiluminescent Layered Lanthanide–Phosphono–Carboxylate Nanoparticles

A new family of layered metal(III)–phosphono–carboxylate nanostructures (M=Y, Eu, Tb, Er, and Yb) was hydrothermally synthesized and their structures and morphologies were characterized by X‐ray powder diffraction and TEM. 4‐[Bis(phosphonomethyl)amino]caproic acid and 4‐ [bis(phosphonomethyl)amino]undecan‐ oic acid, with general formula (H₂O₃PCH₂)₂NR (R=C₅H₁₀COOH (P2CAPR) and C₁₀H₂₂COOH (P2UND), respectively) were used as building blocks for the preparation of novel layered hybrid materials in which the inorganic layers were composed of MO₇ or MO₈ polyhedra and PO₃C tetrahedra. The interlayer region was occupied by carboxyalkyl chains. These layered compounds were easily dispersed as stable solutions in alkylamine/water upon ultrasonication. These dispersions were constituted of rectangular elongated nanoparticles (NPs), which showed a distribution of sizes ranging from 20–500 nm. These new materials had interesting photophysical properties because they were multiluminescent compounds. These properties gave rise to several emission bands, which were spread over the broad spectroscopic region, from the near‐UV up to the near‐IR regions. Each emission band had a specific lifetime, which ranged from the sub‐ps to the ms scale.