A time-resolved SAXS study has been carried out on the formation of amorphous calcium carbonate from supersaturated aqueous solutions at an initial concentration of 5 mmol/L CaCO(3). Particle formation was induced by mixing equal volumes of equinormal CaCl(2) and Na(2)CO(3) solutions with a stopped-flow device installed at the SAXS beamline. The resulting scattering curves were analyzed without any model assumption with respect to the particle shape. The analysis is based on the intercept of the scattering curve, its initial slope, and the Porod invariant. These parameters give access to the average particle mass, the average particle size, and the mass concentration of the particles, respectively. The evolution of particle mass and concentration with time gives access to the trend in the particle number density. The size and mass values were found to be correlated by characteristic exponents. Two different mass values can be used for this correlation: direct use of the intercept of the scattering curve or alternatively a ratio of this intercept with the corresponding Porod invariant. The resulting exponents depend on the particle growth mechanism. These exponents, together with the evolution of the number density, are capable of discriminating between a monomer-addition mechanism and a particle-particle coagulation mechanism as two alternative building mechanisms for the resulting amorphous CaCO(3) nanoparticles. A detailed description of the data analysis and its merit in establishing a particle growth mechanism is presented.
We use time-resolved cryogenic transmission electron microscopy (TR-cryo-TEM) on a supersaturated solution of calcium sulfate hemihydrate to examine the early stages of particle formation during the hydration of the hemihydrate. As hydration proceeds, we observe nanoscale amorphous clusters that evolve to amorphous particles and then reorganize to crystalline gypsum within tens of seconds. Our results indicate that a multistep particle formation model, where an amorphous phase forms first, followed by the transformation into a crystalline product, is applicable even at time scales of the order of tens of seconds for this system. The addition of a small amount of citric acid significantly delays the reorganization to gypsum crystals. We hypothesize that available calcium ions form complexes with the acid by binding to the carboxylic groups. Their incorporation into a growing particle produces disorder and extends the time over which the amorphous phase exists. We see evidence of patches of "trapped" amorphous phase within the growing gypsum crystals at time scales of the order of 24 h. This is confirmed by complementary X-ray diffraction experiments. Direct imaging of nanoscale samples by TR-cryo-TEM is a powerful technique for a fundamental understanding of crystallization and many other evolving systems.
The understanding of biomolecular interactions on solid surfaces is of importance for the design of new biomaterials and medical devices. In this work, the adsorption behavior of creatine phosphokinase (CPK) onto hydrophilic (silicon wafers and amino-terminated surfaces), hydrophobic (polystyrene), and charged (sulfonated polystyrene films) substrates was investigated by means of in situ ellipsometry, contact angle measurements, and atomic force microscopy. CPK is an interesting biomolecule due to its large application in the diagnosis for myocardial infarction and muscle disorders. In the dilute regime (c ∼ 0.005 g/L) the ellipsometric measurements revealed that the kinetics adsorption process of CPK onto silicon wafers and amino-terminated surfaces can be divided into four stages: (i) a diffusive one, (ii) adsorption and rearrangement, (iii) formation of a monolayer, and (iv) continuous and irreversible adsorption caused by relaxation process and cooperative binding. This seems to be the first time that such a behavior has been experimentally observed. For more concentrated solutions, the CPK formed aggregates in solution and, therefore, the adsorption increased continuously with time. CPK adsorbed irreversibly either on hydrophilic or on hydrophobic substrates. The adsorption isotherms showed a preferential adhesion of CPK onto the hydrophilic substrates. Since hydrophilic segments predominate the CPK structure, hydrogen bonding seems to play a major role in the adsorption process.
A detailed in situ scattering study has been carried out on the formation of amorphous calcium carbonate (ACC) particles modulated by the presence of small amounts of sodium polyacrylate chains. The work is aiming at an insight into the modulation of ACC formation by means of two polyacrylate samples differing in their molecular weight by a factor of 50. The ACC formation process was initiated by an in situ generation of CO(3)(2-) ions via hydrolysis of 10 mM dimethylcarbonate in the presence of 10 mM CaCl(2). Analysis of the formation process by means of time-resolved small-angle X-ray and light scattering in the absence of any additives provided evidence for a monomer addition mechanism for the growth of ACC particles. ACC formation under these conditions sets in after a lag-period of some 350 s. In the presence of sodium polyacrylate chains, calcium polyacrylate aggregates are formed during the lag-period, succeeded by a modulated ACC growth in a second step. The presence of anionic polyacrylate chains changed the shape of the growing particles toward loose and less homogeneous entities. In the case of low amounts (1.5-7.5 mg/L) of the long chain additive with 97 kDa, the size of the aggregates is comparable to the size of the successively formed hybrid particles. No variation of the lag-period has been observed in this case. Use of the short chain additive with 2 kDa enabled increase of the additive concentration up to 100 mg/L and resulted in a significant increase of the lag-period. This fact, together with the finding that the resulting hybrid particles remained stable in the latter case, identified short chain sodium polyacrylates as more efficient modulators than long chain polyacrylates.
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