A novel hierarchically porous, hyper-cross-linked siloxane-organic hybrid (PSN-5) has been synthesized by Friedel-Crafts self-condensation of benzyl chloride-terminated double-four-ring cubic siloxane cages as a singular molecular precursor. Simultaneous polymerization of the organic functional groups and destruction of the siloxane cages during synthesis yielded PSN-5, which has an ultrahigh BET surface area (∼2500 m(2) g(-1)) and large pore volume (∼3.3 cm(3) g(-1)) that to our knowledge are the highest values reported for siloxane-based materials. PSN-5 also shows a high H(2) uptake of 1.25 wt % at 77 K and 760 Torr.
We have constructed a novel class of "doublehydrophobic" block polypeptides based on the hydrophobic domains found in native elastin, an extracellular matrix protein responsible for the elasticity and resilience of tissues. The block polypeptides comprise proline-rich poly(VPGXG) and glycinerich poly(VGGVG), both of which dehydrate at higher temperature but form distinct secondary structures, β-turn and β-sheet respectively. In water at 45 °C, the block polypeptides initially assemble into nanoparticles rich in βturn structures, which further connect into long (>10 μm), beaded nanofibers along with the increase in the β-sheet content. The nanofibers obtained are well-dispersed in water, and show thermoresponsive properties. Polypeptides comprising each block component assemble into different morphologies, showing that the conjugation of poly(VPGXG) and poly(VGGVG) plays a role for beaded fiber formation. These results may provide innovative ideas for designing peptide-based materials but also opportunities for developing novel materials useful for tissue engineering and drug delivery systems.
A significant progress has recently been made in the synthesis of monodisperse silica nanoparticles less than 30 nm in diameter by using basic amino acids (e.g., lysine) as a base catalyst for hydrolysis of silicon alkoxide. Alternatively, a more versatile and economical amino acid-free method has been developed to synthesize uniform silica nanospheres (SNSs) with low polydispersity (<12%) in liquid-liquid biphasic systems containing tetraethoxysilane (TEOS), water, and primary amine (or ammonia) under precisely controlled pH conditions (pH 10.8-11.4). The diameter of the SNSs determined from scanning electron microscopy (SEM) can be tuned from ∼12 to ∼36 nm by simply changing the initial pH of the aqueous phase in the reaction mixtures. Furthermore, the as-synthesized sol was taken as the starting material for studying the influences of the type of base catalysts on the solvent evaporation-induced three-dimensional (3D) self-assembly of SNSs. X-ray diffraction (XRD) and nitrogen adsorption-desorption are used to characterize the degree of packing of the resulting 3D arrays. The assembled SNSs with large interparticle mesopores with the diameter of ca. 8.1 nm and low packing fraction of ca. 66.1% are observed upon solvent evaporation of as-synthesized sol in the presence of primary amine. This indicates that SNSs are loosely packed, compared with the packing fraction of 74% for a face-centered cubic array of ideal hard spheres. In contrast, with the aid of an organic buffer or lysine as additives, the assembly of SNSs having smaller mesopores (ca. 3.9 nm) and higher packing fraction of 70.5-71.5% are achieved. It is suggested that the chemical additives with the ability to maintain relatively strong repulsive interaction until the final stage of evaporation play a vital role in the fabrication of well-ordered SNSs arrays.
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