Herein, we report on the ability to create complex 2-D and 3-D silica networks in vitro via polycationic peptide-mediated biosilicification under experimentally altered chemical and physical influences. These structures differ from the sphere-like silica network of particles obtained in vitro under static conditions. Under chemical influences, overall morphologies were observed to shift from a characteristic network of sphere-like silica particles to a sheetlike structure in the presence of -OH groups from additives and to sharp-edged, platelike structures in the presence of larger polycationic peptide matrixes. Under physical influences, using externally applied force fields, overall silica morphologies were observed to transition from sphere-like to fiberlike and dendrite-like structures. These findings could lead to the future development of bio-inspired complex 2-D and 3-D silica micro- and nano-devices.

The specific density and molar liquid volume of 40 imidazolium-based ionic liquids were predicted using the COSMO-RS method, a thermodynamic model based on quantum chemistry calculations. A molecular model of ion pairs was proposed to simulate the pure ionic liquid compounds. These ion-paired structures were generated at the B3LYP/6-31++G** computational level by combining the cations 1-methyl- (Mmim+), 1-ethyl- (Emim+), 1-butyl- (Bmim+), 1-hexyl- (Hxmim+), and 1-octyl-3-methylimidazolium (Omim+) with the anions chloride (Cl-), tetrafluoroborate (BF4 -), tetrachloroferrate (FeCl4 -), hexafluorophosphate (PF6 -), bis(trifluoromethanesulfonyl)imide (Tf2N-), methylsulfate (MeSO4 -), ethylsulfate (EtSO4 -), and trifluoromethanesulfonate (CF3SO3 -). Satisfactory agreement with the available experimental measurements was obtained, showing the capability of the current computational approach to describe the effect of the anion nature and cation substituent on the volumetric properties of this family of ionic liquids. Thus, calculated and experimental density values of ionic liquids (and also other common solvents) were fitted by linear regressions with correlation coefficients R > 0.99 and standard deviations SD < 20 kg/m3. Consequently, molar liquid volumes were also predicted very accurately by COSMO-RS, indicating the suitability of the ion-pair model to describe intermolecular interactions of pure ionic liquids. In this sense, the σ-profiles of the ion-paired molecules were used to qualitatively analyze the influence of cation and anion natures of ionic liquids on their volumetric properties. As a result of the analysis, we propose the charge distribution area below the σ-profile (S σ -profile) as a simple a priori parameter to characterize the contributions of cation and anion to the ionic liquid behavior as tool to design solvents.

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