Biomedical subjects

Gerhard H Findenegg

Publications and source records attributed to Gerhard H Findenegg.

10 recordsLinked to original sources

PubMed2006

Adsorption of dodecyltrimethylammonium bromide and sodium bromide on gold studied by liquid chromatography and flow adsorption microcalorimetry.

Here, we report on a new aspect of the adsorption of Br- on the surface of gold. The adsorption of dodecyltrimethylammonium bromide (C12TABr) from aqueous solutions onto macroporous gold particles was studied by continuous flow frontal analysis solid/liquid chromatography and flow adsorption microcalorimetry. The material balance and enthalpy balance of adsorption and the change in the solution pH were measured simultaneously. Initially, Br- is irreversibly bound to high-affinity surface sites counterbalanced by the adsorption of H+ from the aqueous phase. The surface speciation is accompanied by the formation of C12TAOH, which in turn results in a significant pH increase in the bulk solution. The net process was found to be strongly exothermic (-280 kJ.mol(-1)), which is indicative of the occurrence of chemisorption. The specific adsorption of Br- is followed by the reversible adsorption of C12TABr to produce a firmly bound monolayer in a head-to-surface arrangement (-53 kJ.mol(-1)). In a relatively narrow range of the surface coverage, various composite structures may develop on the top layer and eventually transform to full-cylindrical surface aggregates. The surface aggregation was found to be reversible, with an enthalpy change of -11 kJ.mol(-1). The importance of the specific binding of Br- to the surface of gold was confirmed by measurement of the initial adsorption of NaBr on the microparticles. The initial adsorption was found to be irreversible, with an enthalpy change of approximately -240 kJ.mol(-1). This process involved the formation of an AuBr-/H+ electric double layer at the gold/water interface, accompanied by a dramatic increase in the solution pH due to the release of a copious amount of OH- in the bulk liquid phase.

Journal Article↗

PubMed2005

Self-assembly of a metallosupramolecular coordination polyelectrolyte in the pores of SBA-15 and MCM-41 silica.

It is shown that intrinsically stiff chain aggregates of a metallosupramolecular coordination polyelectrolyte (MEPE) can form in the cylindrical nanopores of MCM-41 and SBA-15 silica by self-assembly of its constituents (metal ions and organic ligand). The UV/vis spectra of the resulting MEPE-silica composites exhibit the characteristic metal-to-ligand charge transfer band of the MEPE complex in solution. For the MEPE-silica composite in SBA-15 an iron content of 1.2 wt % was found, corresponding to ca. 10 MEPE chains disposed side by side in the 8 nm wide pores of the SBA-15 matrix. In the case of MCM-41 (pore width < 3 nm), where only one MEPE chain per pore can be accommodated, an iron content of 0.3 wt % was obtained, corresponding to half-filling of the pores. It was also found that MEPE chains spontaneously enter the pores of SBA-15, when a solution of MEPE is exposed to the silica matrix.

Journal Article↗

PubMed2005

Local structure of a phase-separating binary mixture in a mesoporous glass matrix studied by small-angle neutron scattering.

The mesoscopic structure of the binary system isobutyric acid + heavy water (D(2)O) confined in a porous glass (controlled-pore silica glass, mean pore width ca. 10 nm) was studied by small-angle neutron scattering at off-critical compositions in a temperature range above and below the upper critical solution point. The scattering data were analyzed in terms of a structure factor model similar to that proposed by Formisano and Teixeira [Eur. Phys. J. E 1, 1 (2000)], but allowing for both Ornstein-Zernike-type composition fluctuations and domainlike structures in the microphase-separated state of the pore liquid. The results indicate that the phase separation in the pores is shifted by ca. 10 K and spread out in temperature. Microphase separation is pictured as a transition from partial segregation at high temperature, due to the strong preferential adsorption of water at the pore wall, to a tube or capsule configuration of the two phases at low temperatures, depending on the overall composition of the pore liquid. Results for samples in which the composition of the pore liquid can vary with temperature due to equilibration with extra-pore liquid are consistent with this picture.

Journal Article↗

PubMed2005

Pulsed-flow microcalorimetric study of the template-monolayer region of nonionic surfactants adsorbed at the graphite/water interface.

The formation of half-cylindrical surfactant aggregates at the graphite/aqueous solution interface is templated by an ordered monolayer of molecules disposed parallel to the graphite basal plane. Beyond a critical alkyl chain length, monolayer formation is effectively irreversible. Since enthalpic interactions in this template-monolayer region cannot be resolved with adequate accuracy by the traditional adsorption calorimetric methods, we applied a novel method, pulsed-flow calorimetry, for simultaneous measurement of the material balance and the enthalpy balance in this high-affinity region. For the three nonionic surfactants studied, n-octyl beta-D-glucoside (C(8)G(1)), dimethyl-n-decylamine oxide (C(10)DAO), and n-octyl tetraethylene glycol monoether (C(8)E(4)), the adsorption was found to be strongly exothermic and effectively irreversible at low adsorbate densities, and the differential heat of adsorption markedly decreased with increasing surface coverage in this region. This deviation from the ideal adsorption behavior was attributed to intermolecular interactions within the adsorption layer rather than to surface heterogeneity of the graphite basal planes. A thermodynamic consistency test clearly demonstrated that pulsed-flow calorimetry is a unique experimental method for the study of nonreversible adsorption phenomena at solid/solution interfaces, representing an excellent tool to complement traditional methods, e.g., frontal-flow and titration adsorption calorimetry. Studies by the frontal-flow method revealed that aggregation on top of the surfactant monolayer was endothermic and reversible.

Journal Article↗

PubMed2005

Evidence of surface charge at the air/water interface from thin-film studies on polyelectrolyte-coated substrates.

The stability of thin water films on silicon substrates coated with cationic and anionic polyelectrolytes was investigated by the thin film pressure balance technique. Depending on the surface charge of the substrate, the water films are either stable (on negatively charged wafers) or rupture rapidly (on positively charged wafers). It is supposed that this behavior is due to a negative surface charge of the free water surface. The underlying assumption that the films' stability is due to electrostatic interactions is supported by measurements of the disjoining pressure on silicon wafers with a native oxide layer, which indicates a decrease of the film thickness, and thus decreasing repulsive interaction between the two film interfaces, with increasing ionic strength.

Journal Article↗

PubMed2005

Phase behavior and local structure of a binary mixture in pores: mean-field lattice model calculations for analyzing neutron scattering data.

We investigate the phase behavior of an asymmetric binary liquid A-W mixture confined between two planar homogenous substrates (slit pore). Molecules of species W interact preferentially with the solid walls via a long-range potential. Assuming nearest-neighbor attractions between the liquid molecules, we employ a lattice-gas model and a mean-field approximation for the grand potential. Minimization of this potential yields the density profiles of thermodynamically stable phases for fixed temperature, chemical potentials of both species, pore width and strengths of attraction. This model is used to analyze experimental small-angle neutron-scattering (SANS) data on the microscopic structure of the binary system isobutyric acid (iBA)+heavy water (D2O) inside a mesoscopic porous matrix (controlled-pore glass of about 10 nm mean pore width). Confinement-independent model parameters are adjusted so that the theoretical liquid-liquid coexistence curve in the bulk matches its experimental counterpart. By choosing appropriate values of the pore width and the attraction strength between substrates and water we analyze the effect of confinement on the phase diagram. In addition to a depression of the liquid-liquid critical point we observe surface induced phase transitions as well as water-film adsorption near the walls. The temperature dependence of the structure of water-rich and iBA-rich phases of constant composition are discussed in detail. The theoretical predictions are consistent with results of the SANS study and assist their interpretation.

Journal Article↗

PubMed2004

Hydrogen bonding of water confined in mesoporous silica MCM-41 and SBA-15 studied by 1H solid-state NMR.

The adsorption of water in two mesoporous silica materials with cylindrical pores of uniform diameter, MCM-41 and SBA-15, was studied by 1H MAS (MAS=magic angle spinning) and static solid-state NMR spectroscopy. All observed hydrogen atoms are either surface -SiOH groups or hydrogen-bonded water molecules. Unlike MCM-41, some strongly bound water molecules exist at the inner surfaces of SBA-15 that are assigned to surface defects. At higher filling levels, a further difference between MCM-41 and SBA-15 is observed. Water molecules in MCM-41 exhibit a bimodal line distribution of chemical shifts, with one peak at the position of inner-bulk water, and the second peak at the position of water molecules in fast exchange with surface -SiOH groups. In SBA-15, a single line is observed that shifts continuously as the pore filling is increased. This result is attributed to a different pore-filling mechanism for the two silica materials. In MCM-41, due to its small pore diameter (3.3 nm), pore filling by pore condensation (axial-pore-filling mode) occurs at a low relative pressure, corresponding roughly to a single adsorbed monolayer. For SBA-15, owing to its larger pore diameter (8 nm), a gradual increase in the thickness of the adsorbed layer (radial-pore-filling mode) prevails until pore condensation takes place at a higher level of pore filling.

Hydrogen Bonding↗

PubMed2004

Characterization of polybutadiene-poly(ethyleneoxide) aggregates in aqueous solution: a light-scattering and small-angle neutron-scattering study.

For diblockcopolymers of polybutadiene-poly(ethyleneoxide) (PB-PEO) type, water is a selective solvent. In dependence of the length of both blocks and the block length ratio, these polymers form a multitude of self-assembled structures in solution. In the present work scattering methods are used to investigate the water-soluble polymer PB125-PEO155 . It is found to form long rodlike micelles, which are characterized with respect to the aggregate length L , the cross sectional radius RCS , the radial scattering length density profile sigma r, and the radial aggregation number Nrad. Model-independent as well as model-based approaches are used for the scattering data analysis. From dynamic light scattering (DLS) and static light scattering (SLS) experiments the weight averaged length Lw of these stiff elongated aggregates is determined to Lw=350 nm . Small angle neutron scattering (SANS) reveals a cross sectional radius of RCS=17 nm and in combination with results from the SLS the radial aggregation number is found to be Nrad=70 .

Journal Article↗

PubMed2004

Confinement effect on the adsorption from a binary liquid system near liquid/liquid phase separation.

The preferential adsorption of one component of a binary system at the inner surfaces of mesoporous silica glasses was studied in a wide composition range at temperatures close to liquid/liquid phase separation. Confinement effects on the adsorption were investigated by using three controlled-pore glass (CPG-10) materials of different mean pore size (10 to 50 nm). For the experimental system (2-butoxyethanol+water), which exhibits an upper miscibility gap, strong preferential adsorption of water occurs, as the coexistence curve is approached at bulk compositions, at which water is the minority component. In this strong adsorption regime the area-related surface excess amount of adsorbed water decreases with decreasing pore width, while the shift in the volume-related mean composition of the pore liquid shows an opposite trend, i.e., greatest deviation from bulk composition occurring in the most narrow pores. A simple mean-field lattice model of a liquid mixture confined by parallel walls is adopted to rationalize these experimental findings. This model reproduces the main findings of the confinement effect on the adsorption near liquid/liquid phase separation.

Journal Article↗

PubMed2003

Structural changes of poly(butadiene)-poly(ethyleneoxide) diblock-copolymer micelles induced by a cationic surfactant: scattering and cryogenic transmission electron microscopy studies.

Micelles of the diblock copolymer poly(butadiene)-poly(ethyleneoxide) (B40-b-EO62) and mixed micelles of this polymer with the cationic surfactant dodecyltrimethylammonium bromide (C12TAB) were investigated using static and dynamic light scattering and small-angle neutron scattering. It is shown that the surfactant induces a major structural change from large mainly rodlike aggregates to smaller spherical mixed micelles. The rodlike assemblies found in the absence of surfactant have a contour length L of ca. 500 nm and a diameter d approximately 30 nm. The spherical mixed micelles obtained upon addition of C12TAB possess a hydrodynamic radius of 15 nm and still contain several polymer molecules. The results of the scattering experiments are consistent with observations of the aggregates by cryogenic transmission electron microscopy.

Biophysical Phenomena↗