Solution Adsorption of Fluorinated Zinc Phthalocyanines on Titania: Combined XPS, UV-Vis, and Contact Angle Study.

The equilibrium solution adsorption of perfluorinated metal phthalocyanines FPcZn ( = 16, 64) on titania was investigated. This method was explored as an alternative to the frequently used vapor deposition technique for the preparation of solid-supported phthalocyanines for applications such as sensitizers, catalysts, and sensors. According to X-ray photoelectron spectroscopy (XPS), UV-vis, and water contact angles, the adsorption of phthalocyanines from acetone solution occurred readily at room temperature resulting in the formation of hydrophobic surfaces of the solid-supported phthalocyanines.

"Raincoat for explosives": Surface chemistry approach to control wetting of nitrocellulose with nitroglycerin.

Hypothesis: Wicking and percolation of a liquid in porous media is, among other factors, strongly affected by wettability of the pores. Nitrocellulose (NC) fibrous matrix impregnated with nitroglycerin (NG) is a main component of propellant formulations. Over time, NG, being a wetting liquid, leaks out from the matrix causing fires and explosions resulting from the storage.

Covalent functionalization of silica surface using "inert" poly(dimethylsiloxanes).

Methyl-terminated poly(dimethylsiloxanes) (PDMSs) are typically considered to be inert and not suitable for surface functionalization reactions because of the absence of readily hydrolyzable groups. Nevertheless, these siloxanes do react with silica and other oxides, producing chemically grafted organic surfaces. Known since the 1970s and then forgotten and recently rediscovered, this reaction provides a versatile yet simple method for the covalent functionalization of inorganic surfaces.

Capture and imaging of a prehairpin fusion intermediate of the paramyxovirus PIV5.

During cell entry, enveloped viruses fuse their viral membrane with a cellular membrane in a process driven by energetically favorable, large-scale conformational rearrangements of their fusion proteins. Structures of the pre- and postfusion states of the fusion proteins including paramyxovirus PIV5 F and influenza virus hemagglutinin suggest that this occurs via two intermediates. Following formation of an initial complex, the proteins structurally elongate, driving a hydrophobic N-terminal "fusion peptide" away from the protein surface into the target membrane.

Synthesis of chiral mesoporous silicas with oligo(saccharide) surfaces and their use in separation of stereoisomers.

Novel chiral mesoporous silicas (SBA-15 motif) with chemically bonded oligo(saccharides) (1, 3, and 7 glucose units) were obtained through the cocondensation of organosilicon derivatives of the oligo(saccharides) and silica precursors in the presence of polymer surfactant template under mild acidic conditions. The pore order and structure of the materials prepared were characterized by transmission electron microscopy and nitrogen adsorption. The direct application of the oligo(saccharide)-grafted SBA-15 stationary phases in the HPLC separations of stereoisomers was demonstrated for the first time.

Adsorption and wetting characterization of hydrophobic SBA-15 silicas.

This work describes adsorption and wetting characterization of hydrophobic ordered mesoporous silicas (OMSs) with the SBA-15 motif. Three synthetic approaches to prepare hydrophobic SBA-15 silicas were explored: grafting with (1) covalently-attached monolayers (CAMs) of C(n)H(2)(n+1)Si(CH(3))(2)N(CH(3))(2), (2) self-assembled monolayers (SAMs) of C(n)H(2)(n+1)Si(OEt)(3), and (3) direct ("one-pot") co-condensation of TEOS with C(n)H(2)(n+1)Si(OEt)(3) in presence of P123 (n=1-18). The materials prepared were characterized by nitrogen adsorption, TEM, and chemical analysis.

Lipid membranes supported on optically transparent nanosilicas: synthesis and application in characterization of protein-membrane interactions.

We describe methods of preparation of lipid membranes supported on optically transparent nanosilicas (20 and 30 nm diameter) and an initial application of these materials to characterize membrane-protein binding using conventional circular dichroism and fluorescence spectroscopy.

Wetting study of imidazolium ionic liquids.

In this work, we present a systematic contact angles study of a series of 1-alkyl, 3-methyl-imidazolium ionic liquids (ILs) on well-defined polar and nonpolar monolayer surfaces supported on Si wafers. The advancing and receding contact angles of ILs were used to determine the surface energy of the monolayer surfaces using Neumann's equation-of-state and Zisman's critical surface tension approaches. In parallel, the contact angles of conventional probe fluids (molecular liquids) including water, formamide, methylene iodide, ethylene glycol, and hexadecane were determined on the same surfaces.

Displacement reactions of covalently attached organosilicon monolayers on Si.

The covalently attached monolayers of alkylsilanes (R(CH(3))(2)SiX) on Si undergo complete displacement by the solutions of different organosilanes (R'(CH(3))(2)SiX). By varying the reaction time, the degree of displacement can be controlled offering a convenient method for the preparation of surfaces with mixed functionalities (R and R').

Wettability changes induced by biochemical surface reactions.

We report the use of proteins, lipids, and enzymes for the preparation of surfaces with reversible wettability changes, in particular, surfaces capable of switching from hydrophobic to hydrophilic and back. We demonstrate that these reactions can be used for engineering capillary systems with gating properties.

Highly-ordered layered organo-mineral materials prepared via reactions of n-alkylphosphonic acids with apatite.

This work describes a novel class of layered organo-mineral materials manufactured via a single-step solution-phase reaction of n-alkylphosphonic acids (CnH(2n+1)P(O)(OH)2) with calcium hydroxyapatite mineral (CaHAP). TEM, SAXS, WAXS, FTIR, and Vapor Phase Adsorption data suggest that these alkyl-CaHAP materials present a surface-modified CaHAP matrix coated with ordered layers of calcium alkylphosphonates that are strongly adhered to the surface. Interlayer spacing increases from 1.

Wetting in hydrophobic nanochannels: a challenge of classical capillarity.

We report an investigation of the water-hydrophobic interface in well-defined nanochannels (R approximately 2-4 nm). Wetting in these systems cannot be described by classical (macroscopic) capillary theory: (1) water occupies only a fraction ( approximately 60%) of the pore volume, and (2) the capillary pressures are approximately 60-90% greater than predicted by the Laplace equation. The results suggest the presence of approximately 0.

Calorimetric study of the reactions of n-alkylphosphonic acids with metal oxide surfaces.

The reaction enthalpies for the solution-phase self-assembly of n-alkylphosphonic acids on the surfaces of TiO2 and ZrO2 have been determined using isothermal titration calorimetry at 298 K. The reaction enthalpies were negative (exothermic) for methyl- and n-octylphosphonic acids and positive (endothermic) for n-octadecylphosphonic acid with both metal oxides. The enthalpy/energy analysis showed that the net enthalpy of the formation of self-assembled monolayers (SAMs) at solid-liquid interface can be presented as follows: DeltaHr=-D-(DeltaHsol+DeltaHdil)-(ES-ESAM), where D is the binding energy of the SAM molecules with the solid; DeltaHsol and DeltaHdil are the enthalpies of dissolution and dilution; ES and ESAM are the surface energies of bare solid and SAM, respectively.

Thermal stability of organic monolayers chemically grafted to minerals.

The thermal degradation of monolayers of alkylsilicon hydrides (RSiH(3)), alkylphosphonic acids (RP(O)(OH)(2)), and alkyldimethylchlorosilanes (R(CH(3))(2)SiCl) supported on silica, alumina, titania, zirconia, and calcium hydroxyapatite particles was investigated using thermal gravimetric analysis (TGA). The common feature in the TGA was a dramatic weight loss between approximately 200 and approximately 600 degrees C (N(2) atmosphere), which was not present for bare minerals, and, thus, was assigned to the degradation of the surface grafted organic species. The onset of weight loss and the temperature of maximal weight loss rate (T(MAX)) showed no dependence on the mineral and were determined by the nature of the chemical group directly attached to the surface.

Hydrolytic stability of organic monolayers supported on TiO2 and ZrO2.

The hydrolytic stability of C18 monolayers supported on TiO2 and ZrO2 was studied. Three types of monolayers were prepared from the following octadecyl modifiers: (1) octadecyldimethylchlorosilane (C18H37Si(CH3)2Cl); (2) octadecylsilane (C18H37SiH3); and (3) octadecylphosphonic acid (C18H37P(O)(OH)2). The hydrolysis of the surfaces prepared was studied under static conditions at 25 and 65 degrees C at pH 1-10.

Reaction of organosilicon hydrides with solid surfaces: an example of surface-catalyzed self-assembly.

The solution-phase reactions of octadecylsilane (C(18)H(37)SiH(3)) with 10 high surface area metal oxides (groups II-VIII) were investigated. C(18)H(37)SiH(3) reacted with most metal oxides at room temperature and produced supported monolayers (self-assembled monolayers, SAMs) with a high grafting density of C(18), approximately 4.5-5 groups/nm(2).