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Mary K Cowman

Publications and source records attributed to Mary K Cowman.

6 recordsLinked to original sources

Experimental approaches to hyaluronan structure.

A review of the literature describing experimental studies on hyaluronan (HA) is presented. Methods sensitive to the hydrodynamic properties of HA, analyzed in neutral aqueous solution containing NaCl at physiological concentration, can be shown to fit the expected behavior of a high molecular weight linear semi-flexible polymer. The significant nonideality of HA solutions can be predicted by a simple treatment for hydrodynamic interactions between polymer chains. Nuclear magnetic resonance and circular dichroism studies of HA are also in agreement with a model incorporating dynamically formed and broken hydrogen bonds, contributing to the semi-flexibility of the polymer chain, and segmental motions on the nanosecond time scale. HA shows the capability for self-association in the formation of a viscoelastic putty state at pH 2.5 in the presence of salt, and a gel state at pH 2.5 in mixed organic/aqueous solution containing salt. Ordered and associated structures have also been observed for HA on the surfaces, especially in the presence of surface-structured water. These phenomena can be understood in terms of counterion-mediated polyelectrolyte interactions. The possibility that hyaluronan exists in vivo in environments that induce ordered structures and assemblies is discussed.

Carbohydrate Conformation↗

Hyaluronan conformations on surfaces: effect of surface charge and hydrophobicity.

Extended, relaxed, condensed, and interacting forms of the polysaccharide hyaluronan have been observed by atomic force microscopy (AFM). The types of images obtained depend on the properties of the surfaces used. We have investigated several different surface conditions for HA imaging, including unmodified mica, mica chemically modified with two different kinds of amino-terminated silanes (3-aminopropyltriethoxysilane and N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride), and highly oriented pyrolytic graphite. We found the degree of HA molecular extension or condensation to be variable, and the number of bound chains per unit area was low, for all of the mica-based surfaces. HA was more easily imaged on graphite, a hydrophobic surface. Chains were frequently observed in high degrees of extension, maintained by favorable interaction with the surface after molecular combing. This observation suggests that the HA macromolecule interacts with graphite through hydrophobic patches along its surface. AFM studies of HA behavior on differing surfaces under well-controlled environmental conditions provides useful insight into the variety of conformations and interactions likely to be found under differing physiological conditions.

Aluminum Silicates↗

Extended, relaxed, and condensed conformations of hyaluronan observed by atomic force microscopy.

The conformation of the polysaccharide hyaluronan (HA) has been investigated by tapping mode atomic force microscopy in air. HA deposited on a prehydrated mica surface favored an extended conformation, attributed to molecular combing and inhibition of subsequent chain recoil by adhesion to the structured water layer covering the surface. HA deposited on freshly cleaved mica served as a defect in a partially structured water layer, and favored relaxed, weakly helical, coiled conformations. Intramolecularly condensed forms of HA were also observed, ranging from pearl necklace forms to thick rods. The condensation is attributed to weak adhesion to the mica surface, counterion-mediated attractive electrostatic interactions between polyelectrolytes, and hydration effects. Intermolecular association of both extended and condensed forms of HA was observed to result in the formation of networks and twisted fibers, in which the chain direction is not necessarily parallel to the fiber direction. Whereas the relaxed coil and partially condensed conformations of HA are relevant to the native structure of liquid connective tissues, fully condensed rods may be more relevant for HA tethered to a cell surface or intracellular HA, and fibrous forms may be relevant for HA subjected to shear flow in tight intercellular spaces or in protein-HA complexes.

Aluminum Silicates↗

Structure of carbohydrate-bound polynuclear iron oxyhydroxide nanoparticles in parenteral formulations.

Intravenous iron therapy is used to treat anemia associated with chronic kidney disease. The chemical structures of parenteral iron agents have not been characterized in detail, and correlations between structure, efficiency of iron delivery, and toxicity via catalysis of oxygen-derived free radical creation remain to be established. In this study, two formulations of parenteral iron have been characterized by absorption spectroscopy, X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM), and elemental analysis. The samples studied were Venofer (Iron Sucrose Injection, USP) and Ferrlecit (Sodium Ferric Gluconate in Sucrose Injection). The 250-800-nm absorption spectra and the XRD patterns showed that both formulations contain a mineral core composed of iron oxyhydroxide in the beta-FeOOH mineral polymorph known as akaganeite. This was further confirmed for each formulation by imaging using TEM and AFM. The average core size for the nanoparticles, after dialysis to remove unbound or loosely bound carbohydrate, was approximately 3+/-2 nm for the iron-sucrose, and approximately 2+/-1 nm for the iron-gluconate. Each of the nanoparticles consists of a mineral core, surrounded by a layer of bound carbohydrate. The overall diameter of the average bead in the dialyzed preparations was approximately 7+/-4 nm for the iron-sucrose, and 3+/-1 nm for the iron-gluconate. Undialyzed preparations have particles with larger average sizes, depending on the extent of dilution of unbound and loosely bound carbohydrate. At a dilution corresponding to a final Fe concentration of 5 mg/mL, the average particle diameter in the iron-sucrose formulation was approximately 22+/-9 nm, whereas that of the iron-gluconate formulation was approximately 12+/-5 nm.

Journal Article↗

Imaging structured water and bound polysaccharide on mica surface at ambient temperature.

The presence of a water layer on the surface of muscovite mica under ambient conditions is well established. The water molecules are well ordered and seem to be oriented, leading to an icelike monolayer (probably ferroelectric) in epitaxial relation with the mica surface. We have imaged and characterized the height and contact angle of ordered water layer(s) formed by wetting and de-wetting processes on mica surfaces at different states of hydration by tapping mode atomic force microscopy. Implications that the presence of such an ordered water layer may have for imaging of biological samples are also discussed, with consideration of data for the polysaccharide hyaluronan.

Aluminum Silicates↗

Poly(vinyl alcohol) as versatile biomaterial for potential biomedical applications.

In this paper, we present some new case examples where the chemical versatility of poly (vinyl alcohol) (PVA) can be used for potential biomedical applications. PVA, the polymeric material used for designing new nanostructured devices, is water soluble, biocompatible and has excellent physical properties. We point out the possibility of obtaining wall-to-wall chemical hydrogels as well as microgels without diminishing the biocompatibility available in the starting PVA material. Injectability is another important factor to take into account in controlled drug delivery for gene therapy. In this respect, in this paper, established and more innovative methods are prospected in order to obtain particles with dimensions suitable for these applications.

Journal Article↗