Mechanical properties of hexylene- and phenylene-bridged polysilsesquioxane aerogels and xerogels

Bridged polysilsesquioxanes are increasingly used to prepare protective coatings, particulate chromatographic materials, and adsorbents. However, little is known about the mechanical properties of the materials and how they are influenced by the nature of the bridging group. In this paper, we have prepared monolithic xerogels and aerogels of hexylene- and phenylene-bridged polysilsesquioxanes and have measured their flexural strength and modulus. Consistent with their compact structure, the porous, glassy phenylene- and hexylene-bridged xerogels were hundreds of stronger than the analogous aerogels. The nature of the bridging group did not appear to affect the mechanical properties of the xerogels, in contrast, it presented a profound effect on the mechanical properties of the aerogels. Phenylene-bridged aerogels were brittle and 30% stronger than silica aerogels of the same density. However, the opaque hexylene-bridged aerogels were found to be elastic and appreciably weaker than the phenylene-bridged or silica aerogels.     

Partition functions for quantum gravity, black holes, elliptic genera and Lie algebra homologies

There is a remarkable connection between quantum generating functions of field theory and formal power series associated with dimensions of chains and homologies of suitable Lie algebras. We discuss the homological aspects of this connection with its applications to partition functions of the minimal three-dimensional gravities in the space-time asymptotic to AdS₃, which also describe the three-dimensional Euclidean black holes, the pure N=1 supergravity, and a sigma model on N-fold generalized symmetric products. We also consider in the same context elliptic genera of some supersymmetric sigma models. These examples can be considered as a straightforward application of the machinery of modular forms and spectral functions (with values in the congruence subgroup of SL(2,Z)) to partition functions represented by means of formal power series that encode Lie algebra properties.     

Turning the Light on Phenols: New Opportunities in Organic Synthesis

Phenols ( I ) are extremely relevant chemical functionalities in natural, synthetic and industrial chemistry. Their corresponding electron-rich anions, namely phenolates ( I ), are characterized by interesting physicochemical properties that can be drastically altered upon light excitation. Specifically, phenolates ( I ) become strong reducing agents in the excited state and are able to generate reactive radicals from suitable precursors via single-electron transfer processes. Thus, these species can photochemically trigger strategic bond-forming reactions, including their direct aromatic C−H functionalization. Moreover, substituted phenolate anions can act as photocatalysts to enable synthetically useful organic transformations. An alternative mechanistic manifold is represented by the ability of phenolate derivatives I to form ground state electron donor-acceptor (EDA) complexes with electron-poor radical sources. These complementary scenarios have paved the way for the development of a wide range of relevant organic reactions. In this Minireview, we present the main examples of this research field, and give insight on emerging trends in phenols photocatalysis towards richer organic synthesis.     

Surfactant-mediated desorption of polymer from the nanoparticle interface

The surfactant-mediated desorption of adsorbed poly(vinylpyrrolidone), PVP, from anionic silica surfaces by sodium dodecyl sulfate, SDS, was observed. While photon correlation spectroscopy shows that the size of the polymer-surfactant-particle ensemble grows with added SDS, a reduction in the near-surface polymer concentration is measured by solvent relaxation NMR. Volume fraction profiles of the polymer layer extracted from small-angle neutron scattering experiments illustrate that the adsorbed polymer layer has become more diffuse and the polymer chains more elongated as a result of the addition of SDS. The total adsorbed amount is shown to decrease due to Coulombic repulsion between the surfactant-polymer complexes and between the complexes and the anionic silica surface.     

Strong convergence of the discontinuous Galerkin scheme for the low regularity miscible displacement equations

Strong convergence of the numerical solution to a weak solution is proved for a nonlinear coupled flow and transport problem arising in porous media. The method combines a mixed finite element method for the pressure and velocity with an interior penalty discontinuous Galerkin method in space for the concentration. Using functional tools specific to broken Sobolev spaces, the convergence of the broken gradient of the numerical concentration to the weak solution is obtained in the L² norm. © 2016 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 489–513, 2017     

Poly(amido‐amine)s Carrying Primary Amino Groups as Side Substituents

Poly(amido‐amine)s carrying primary amino groups as side substituents have been obtained by polyaddition of N‐triphenylmethyl‐monosubstituted 1,2‐diaminoethane (TPHMAE) to 2,2‐bisacrylamido acetic acid or 1,4‐bisacryloylpiperazine and subsequent removal of the protecting triphenylmethyl group by treating the resultant polymers with aqueous hydrochloric acid. Soluble polymers can be also obtained directly by the polyaddition of monoprotonated 1,2‐diaminoethane to 2,2‐bisacrylamido acetic acid in the presence of a limited amount of added acetic or hydrochloric acid. The resultant polymers are of a higher molecular weight than the corresponding ones prepared from TPHMAE. By adding a limited amount of N‐triphenylmethyl‐monosubstituted 1,2‐diaminoethane to the monomer mixtures leading to poly(amido‐amine)s with a recognised potential as nonviral vectors, such as ISA 23 and ISA 1, a controlled number of pendant primary amino groups have been introduced. By this procedure, ISA 23 and ISA 1 become suitable as polymer carriers for carboxylated drugs as well as amenable to the labelling techniques by fluorescent probes commonly employed for proteins.

Formation of monoprotected primary diamines.     

Preparation and characterization of a europium(II) bromide-chloride phase EuBr1.5Cl0.5

A divalent europium chloride-bromide phase, EuBr_1.56(7)Cl_0.46(2) has been prepared and identified on the basis of analytical, X-ray powder diffraction and single-crystal data. Although the phase is considered isostructural with EuCl₂ (PbCl₂ structure type, a = 0.9230 (5), b = 0.7890 (4), c = 0.4613 (3) nm, space group Pbnm), the single-crystal data indicate long-range order in the form of a superstructure which doubles the b parameter. In the pseudocell the square pyramidal anion sites are occupied principally by bromide ions, the tetrahedral sites almost equally by bromide and chlorine ions. Structural details and the long-range order are discussed. Evidence is presented for the existence of another europium(II) mixed halide phase, EuBr_1.8(2)Cl_0.16(2).     

S?F and S?C Activation of SF6 and SF5 Derivatives at Rhodium: Conversion of SF6 into H2S

The degradation of SF₆ and SF₅ organyls by S F and S C bond‐activation reactions at [{Rh(μ‐H)(dippp)}₂] under mild conditions is reported. Fluorido and thiolato species were identified as products or intermediates, and were characterized by X‐ray diffraction analysis and multinuclear NMR spectroscopy. An unprecedented cyclic process for the conversion of the potent greenhouse gas SF₆ into H₂S was developed.     

Exploring the Association of Electron-Donating Corroles with Phthalocyanines as Electron Acceptors

Electron-donating corroles (Cor) were integrated with electron-accepting phthalocyanines (Pc) to afford two different non-covalent Cor ⋅ Pc systems. At the forefront was the coordination between a 10-meso-pyridine Cor and a ZnPc. The complexation was corroborated in a combination of NMR, absorption, and fluorescence assays, and revealed association with binding constants as high as 10⁶ m ⁻¹. Steady-state and time-resolved spectroscopies evidenced that regardless of exciting Cor or Pc, the charge-separated state evolved efficiently in both cases, followed by a slow charge-recombination to reinstate the ground state. The introduction of non-covalent linkages between Cor and Pc induces sizeable differences in the context of light harvesting and transfer of charges when compared with covalently linked Cor-Pc conjugates.