Effects of Secondary Metal Carbonate Addition on the Porous Character of Resorcinol-Formaldehyde Xerogels.

A deeper understanding of the chemistry and physics of growth, aggregation, and gelation processes involved in the formation of xerogels is key to providing greater control of the porous characteristics of such materials, increasing the range of applications for which they may be utilized. Time-resolved dynamic light scattering has been used to study the formation of resorcinol-formaldehyde gels in the presence of combinations of Group I (Na and Cs) and Group II (Ca and Ba) metal carbonates. It was found that the combined catalyst composition, including species and times of addition, is crucial in determining the end properties of the xerogels via its effect on growth of clusters involved in formation of the gel network. Combination materials have textural characteristics within the full gamut offered by each catalyst alone; however, in addition, combination materials that retain the small pores associated with sodium carbonate catalyzed xerogels exhibit a narrowing of the pore size distribution, providing an increased pore volume within an application-specific range of pore sizes. We also show evidence of pore size tunability while maintaining ionic strength, which significantly increases the potential of such systems for biological applications.

Gelation mechanism of resorcinol-formaldehyde gels investigated by dynamic light scattering.

Xerogels and porous materials for specific applications such as catalyst supports, CO2 capture, pollutant adsorption, and selective membrane design require fine control of pore structure, which in turn requires improved understanding of the chemistry and physics of growth, aggregation, and gelation processes governing nanostructure formation in these materials. We used time-resolved dynamic light scattering to study the formation of resorcinol-formaldehyde gels through a sol-gel process in the presence of Group I metal carbonates. We showed that an underlying nanoscale phase transition (independent of carbonate concentration or metal type) controls the size of primary clusters during the preaggregation phase; while the amount of carbonate determines the number concentration of clusters and, hence, the size to which clusters grow before filling space to form the gel. This novel physical insight, based on a close relationship between cluster size at the onset of gelation and average pore size in the final xerogel results in a well-defined master curve, directly linking final gel properties to process conditions, facilitating the rational design of porous gels with properties specifically tuned for particular applications. Interestingly, although results for lithium, sodium, and potassium carbonate fall on the same master curve, cesium carbonate gels have significantly larger average pore size and cluster size at gelation, providing an extended range of tunable pore size for further adsorption applications.

Molecular speciation and mesoscale clustering in formaldehyde-methanol-water solutions in the presence of sodium carbonate.

Nanoporous organic gels can be synthesized from aqueous solutions of formaldehyde and resorcinol in the presence of basic electrolytes such as sodium carbonate. It is well known that formaldehyde is present in the form of methylene glycols or methoxy-glycols in aqueous and methanolic solutions, but influence of pH or electrolytes on speciation in these solutions has not been previously studied. Here we investigated effects of sodium carbonate on the speciation and colloidal scale clustering in formaldehyde-methanol-water solutions in the absence of resorcinol. We used (13)C NMR spectroscopy to quantitatively characterize molecular speciation in solutions and to estimate corresponding equilibrium constants for glycol dimerization and methoxylation. We found that species distribution is essentially independent of carbonate concentration for pH values between 3.4 (no carbonate) and 10.6. This was also consistent with ATR IR measurements of the same solutions. However, NMR spin-spin relaxation time measurements showed an unexpected behavior for glycols and especially for diglycol (but not for methanol), with relaxation times strongly decreasing with increasing carbonate concentration, indicating differences in local molecular environment of glycols. We further used dynamic light scattering to confirm the presence of mesoscale clustering in formaldehyde-methanol-water (for both H2O and D2O) solutions in the presence of sodium carbonate. We propose that the observed phenomena are due to glycol-rich cluster mesospecies in equilibrium bulk solution, together forming a thermodynamically stable mesostructured liquid phase.

Mechanism and kinetics of nanostructure evolution during early stages of resorcinol-formaldehyde polymerisation.

Resorcinol and formaldehyde react in aqueous solutions to form nanoporous organic gels well suited for a wide range of applications from supercapacitors and batteries to adsorbents and catalyst supports. In this work, we investigated the mechanism and kinetics of formation of primary clusters in the early stages of formation of resorcinol-formaldehyde gels in the presence of dissolved sodium carbonate. Dynamic Light Scattering measurements showed that size of freely diffusing primary clusters was independent of both reactant and carbonate concentrations at a given temperature, reaching the mean hydrodynamic radius of several nanometres before further changes were observed. However, more primary clusters formed at higher carbonate concentrations, and cluster numbers were steadily increasing over time. Our results indicate that the size of primary clusters appears to be thermodynamically controlled, where a solubility/miscibility limit is reached due to formation of certain reaction intermediates resulting in approximately monodisperse primary clusters, most likely liquid-like, similar to formation of micelles or spontaneous nanoemulsions. Primary clusters eventually form a particulate network through subsequent aggregation and/or coalescence and further polymerisation, leading to nanoscale morphologies of resulting wet gels. Analogous formation mechanisms have been previously proposed for several polymerisation and sol-gel systems, including monodisperse silica, organosilicates and zeolites.

Salt-induced control of supramolecular order in biocatalytic hydrogelation.

Biocatalytic action and specific ion effects are both known to have dramatic effects on molecular self-assembly and hydrogelation. In this paper, we demonstrate that these effects are highly cooperative. Biocatalytic hydrogelation of Fmoc peptides in the presence of salts combines kinetic (through enzymatic catalysis) and thermodynamic (specific ion and protein templating) contributions when applied in combination. Spectroscopic data (obtained by fluorescence spectroscopy and circular dichroism) revealed that hydrophobic interactions are greatly affected, giving rise to differential chiral organization and supramolecular structure formation. The kinetic effects of catalytic action could be removed from the system by applying a heat/cool cycle, giving insight into the thermodynamic influence of both protein and salt on these systems and showing that the effects of catalysis, templating, and salts are cooperative. The variable molecular interactions are expressed as variable material properties, such as thermal stability and mechanical strength of the final gel-phase material. To gain more insight into the role of the enzyme, beyond catalysis, in the underlying mechanism, static light scattering is performed, which indicates the different mode of aggregation of the enzyme molecules in the presence of different salts in aqueous solution that may play a role to direct the assembly via templating. Overall, the results show that the combination of specific salts and enzymatic hydrogelation can give rise to complex self-assembly behaviors that may be exploited to tune hydrogel properties.

Towards a correlation between drug properties and in vitro transdermal flux variability.

Over recent years, there has been growing evidence that the permeability coefficient variability describing any specific transdermal drug delivery system is not always normally distributed. However, since different researchers have used different test compounds, methodologies and skin types, it has been difficult to identify any general correlation between drug properties and flux variability. The aim of the present study was to investigate whether there was a relationship between these two variables. To this end, six different compounds (sucrose, adenosine, aldosterone, corticosterone, oestradiol and testosterone) exhibiting a range of partition coefficients but relatively similar molecular weights were screened by taking multiple replicate measurements of their permeation profiles as they penetrated across porcine skin in vitro. It was found that for relatively hydrophilic solutes (log P(o/w)< or = approximately 2.5), physicochemical properties that facilitated slow transdermal flux were associated with more positively skewed permeability coefficient distributions while rapid flux was associated with more symmetric distributions. However, no correlation could be found between molecular properties and the extent of statistical fit to either the normal or log-normal distribution.