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Biomedical subjects

J J De Yoreo

Publications and source records attributed to J J De Yoreo.

5 recordsLinked to original sources

Role of molecular charge and hydrophilicity in regulating the kinetics of crystal growth.

The composition of biologic molecules isolated from biominerals suggests that control of mineral growth is linked to biochemical features. Here, we define a systematic relationship between the ability of biomolecules in solution to promote the growth of calcite (CaCO3) and their net negative molecular charge and hydrophilicity. The degree of enhancement depends on peptide composition, but not on peptide sequence. Data analysis shows that this rate enhancement arises from an increase in the kinetic coefficient. We interpret the mechanism of growth enhancement to be a catalytic process whereby biomolecules reduce the magnitude of the diffusive barrier, Ek, by perturbations that displace water molecules. The result is a decrease in the energy barrier for attachment of solutes to the solid phase. This previously unrecognized relationship also rationalizes recently reported data showing acceleration of calcite growth rates over rates measured in the pure system by nanomolar levels of abalone nacre proteins. These findings show that the growth-modifying properties of small model peptides may be scaled up to analyze mineralization processes that are mediated by more complex proteins. We suggest that enhancement of calcite growth may now be estimated a priori from the composition of peptide sequences and the calculated values of hydrophilicity and net molecular charge. This insight may contribute to an improved understanding of diverse systems of biomineralization and design of new synthetic growth modulators.

Aspartic Acid↗

Molecular modulation of calcium oxalate crystallization by osteopontin and citrate.

Calcium oxalate monohydrate (COM), which plays a functional role in plant physiology, is a source of chronic human disease, forming the major inorganic component of kidney stones. Understanding molecular mechanisms of biological control over COM crystallization is central to development of effective stone disease therapies and can help define general strategies for synthesizing biologically inspired materials. To date, research on COM modification by proteins and small molecules has not resolved the molecular-scale control mechanisms. Moreover, because proteins directing COM inhibition have been identified and sequenced, they provide a basis for general physiochemical investigations of biomineralization. Here, we report molecular-scale views of COM modulation by two urinary constituents, the protein osteopontin and citrate, a common therapeutic agent. Combining force microscopy with molecular modeling, we show that each controls growth habit and kinetics by pinning step motion on different faces through specific interactions in which both size and structure determine the effectiveness. Moreover, the results suggest potential for additive effects of simultaneous action by both modifiers to inhibit the overall growth of the crystal and demonstrate the utility of combining molecular imaging and modeling tools for understanding events underlying aberrant crystallization in disease.

Calcium Oxalate↗

Effect of dissolution kinetics on feature size in dip-pen nanolithography.

We have investigated the effects of humidity, tip speed, and dwell time on feature size during dip pen nanolithography. Our results indicate a transition between two distinct deposition regimes occurs at a dwell time independent of humidity. While feature size increases with humidity, the relative increase is independent of dwell time. The results are described by a model that accounts for detachment and reattachment at the tip. The model suggests that, at short dwell times (high speed), the most important parameter controlling the feature size is the activation energy for thiol detachment.

Journal Article↗

The role of Mg2+ as an impurity in calcite growth.

Magnesium is a key determinant in CaCO3 mineralization; however, macroscopic observations have failed to provide a clear physical understanding of how magnesium modifies carbonate growth. Atomic force microscopy was used to resolve the mechanism of calcite inhibition by magnesium through molecular-scale determination of the thermodynamic and kinetic controls of magnesium on calcite formation. Comparison of directly measured step velocities to standard impurity models demonstrated that enhanced mineral solubility through magnesium incorporation inhibited calcite growth. Terrace width measurements on calcite growth spirals were consistent with a decrease in effective supersaturation due to magnesium incorporation. Ca(1-x)Mg(x)CO3 solubilities determined from microscopic observations of step dynamics can thus be linked to macroscopic measurements.

Journal Article↗

A microcantilever-based pathogen detector.

The ability to detect small amounts of materials, especially bacterial organisms, is important for medical diagnostics and national security issues. Engineered micromechanical systems provide one approach for constructing multifunctional, highly sensitive, real-time, immunospecific biological detectors. We present qualitative detection of specific Salmonella enterica strains using a functionalized silicon nitride microcantilever. Detection is achieved due to a change in the surface stress on the cantilever surface in situ upon binding of a small number of bacteria. Scanning electron micrographs indicate that less than 25 adsorbed bacteria are required for detection.

Antibodies, Bacterial↗