Biomedical subjects

P A Williams

Publications and source records attributed to P A Williams.

At least 19 recordsLinked to original sources

PubMed2006

'Severe' wear challenge to 'as-cast' and 'double heat-treated' large-diameter metal-on-metal hip bearings.

The wear generation of double-heat-treated and as-cast large-diameter metal-on-metal (MOM) hip bearings was investigated using standard- and 'severe'-gait simulations. The test hypothesis was that double heat treatment would change MOM hip wear compared with the as-cast condition. Two groups of high-carbon MOM bearings of 40 mm diameter were manufactured and subjected to either hot isostatic pressing (HIP) and solution annealing (SA) or no heat treatment (as cast). The results showed no statistical difference between the two groups under both running-in and steady state conditions. Even under the most 'severe'-gait simulation published to date, the mean volumetric wear rates were 2.9 and 3.9 mm3 per 10(6) cycles for the HIP-SA and as-cast bearings respectively, showing a ten-fold increase in wear compared with walking. These differences were not statistically different; therefore our hypothesis was negated. Changes in alloy microstructure do not appear to influence the wear behaviour of high-carbon cast MOM articulations with similar chemical compositions. This is in sharp contrast with the published significance of bearing diameter and radial clearance on the wear of MOM hip bearings.

Biocompatible Materials↗

PubMed2006

Metal-on-metal hip simulator study of increased wear particle surface area due to 'severe' patient activity.

This study investigated changes in metal-on-metal (MOM) hip wear and wear particle characteristics arising from a more aggressive patient activity level compared with normal walking. The test hypothesis was that 'severe'-gait conditions will change wear, wear particle sizes, and morphology owing to a decline in joint lubrication. Four carbon MOM hip bearings 40 mm high were subjected to normal-walking and fast-jogging simulations in an orbital hip joint simulator with 25 per cent alpha-calf serum as a lubricant. Co-Cr-Mo wear particles were extracted using an enzymatic method, and prolate ellipsoid equations were used to estimate particle volume and surface area. Fast-jogging simulations generated a sevenfold increase in volumetric wear, a 33 per cent increase in mean wear particle size, and a threefold increase in the number of larger (needle) particles compared with walking. This resulted in a twentyfold increase in total wear particle surface area per 10(6) cycles compared with walking, thereby confirming our hypothesis. The clinical significance of this result suggests that highly active MOM patients may exhibit greater ion release than less active patients.

Biocompatible Materials↗

PubMed2005

Interaction of sodium dodecyl sulfate with methacrylate-PEG comb copolymers.

A series of sodium methacrylate and poly(ethylene glycol) (PEG) comb copolymers (MAA/PEG) with approximate PEG chain lengths of 7, 11, and 22 ethylene oxide units were synthesized by free radical polymerization. Their weight-average molecular mass was found to be approximately 66 000. A commercial sample of a PEG comb polymer with an acrylic backbone was also used in the studies (Sokalan HP 80). The interaction of the MAA/PEG comb polymers and pure sodium methacrylate (SPMA) with sodium dodecyl sulfate (SDS) was studied by ESR spectroscopy using 5-doxyl stearic acid (5-DSA) spin probe and by conductivity measurements. Surfactant aggregation in water occurred at SDS concentrations lower than the surfactant critical micelle concentration (cmc) and depended on the polymer concentration. The observations have been attributed to changes in the effective ionic strength of the systems due to the polymer itself, and it has been concluded that there is no interaction between the MAA/PEG comb copolymers or SPMA and SDS. This has been confirmed by the fact that the decrease in surfactant aggregation concentration is similar in magnitude to the decrease observed on adding NaCl when counterion ion condensation effects are taken into account. It is apparent that the electrostatic repulsions between the surfactant molecules and the methacrylate backbone of the MAA/PEG comb copolymers inhibit association of SDS with the PEG side chains.

Journal Article↗

PubMed2005

Elucidation of the emulsification properties of sugar beet pectin.

A protocol has been developed to fractionate sugar beet pectin using hydrophobic affinity chromatography. Three samples eluted from the column using 4 M NaCl as solvent (fractions 1A, 1B, and 1C), two fractions eluted using 2 M NaCl (fractions 2A and 2B), and one fraction eluted using water (fraction 3). The fractions were shown to be very polydisperse, and differences between the GPC refractive index and UV absorbance (214 nm) elution profiles demonstrated chemical heterogeneity. They were found to contain significantly different proportions of protein (1A, 2.79%; 1B, 0.97%; 1C, 0.77%; 2A, 1.41%; 2B, 5.09%; and 3, 5.89%) and ferulic acid (approximately 1A, 0.5%; 1B, 0.5%; 1C, 0.9%; 2B, 1.5%; and 3, 2%). The weight-average molecular mass, M(w), of the fractions also varied (1A, 153 kDa; 1B, 155 kDa; 1C, 306 kDa; 2A, 562 kDa; 2B, 470 kDa; 3, 282 kDa). Three fractions, that is, 1A, 1B, and 3, produced orange oil emulsions with a relatively small droplet size that were stable over a period of weeks. The other three fractions (1C, 2A, and 2B with higher M(w) values) produced emulsions with an initially larger droplet size, and the droplet size increased considerably over time. The increased droplet size may be influenced by the viscosity of the aqueous continuous phase. There was no simple relationship between protein or ferulic acid content and emulsification ability. For example, fraction 1B, which contained the lowest proportion of both protein and ferulic acid, produced stable emulsions of similar droplet size to fraction 3, which contained the largest proportion of protein and ferulic acid. The role of protein in the emulsification process was investigated by measuring the amount of protein in the aqueous phase before and after emulsification. It was clearly demonstrated that proteinaceous material adsorbed at the oil-water interface. It is evident that the emulsification properties of sugar beet pectin are influenced by the accessibility of the protein and ferulic acid groups to the surface of the oil droplets, the proportion of ester groups, and the molecular mass distribution of the fractions.

Amino Acids↗

PubMed2005

Low temperature bioremediation of oil-contaminated soil using biostimulation and bioaugmentation with a Pseudomonas sp. from maritime Antarctica.

AIMS: To identify native Antarctic bacteria capable of oil degradation at low temperatures. METHODS AND RESULTS: Oil contaminated and pristine soils from Signy Island (South Orkney Islands, Antarctica) were examined for bacteria capable of oil degradation at low temperatures. Of the 300 isolates cultured, Pseudomonas strain ST41 grew on the widest range of hydrocarbons at 4 degrees C. ST41 was used in microcosm studies of low temperature bioremediation of oil-contaminated soils. Microcosm experiments showed that at 4 degrees C the levels of oil degradation increased, relative to the controls, with (i) the addition of ST41 to the existing soil microbial population (bioaugmentation), (ii) the addition of nutrients (biostimulation) and to the greatest extent with (iii) a combination of both treatments (bioaugmentation and biostimulation). Addition of water to oil contaminated soil (hydration) also enhanced oil degradation, although less than the other treatments. Analysis of the dominant species in the microcosms after 12 weeks, using temporal temperature gradient gel electrophoresis, showed Pseudomonas species to be the dominant soil bacteria in both bioaugmented and biostimulated microcosms. CONCLUSIONS: Addition of water and nutrients may enhance oil degradation through the biostimulation of indigenous oil-degrading microbial populations within the soil. However, bioaugmentation with Antarctic bacteria capable of efficient low temperature hydrocarbon degradation may enhance the rate of bioremediation if applied soon after the spill. SIGNIFICANCE AND IMPACT OF THE STUDY: In the future, native soil bacteria could be of use in bioremediation technologies in Antarctica.

Alkanes↗

PubMed2004

The atomic resolution structure of methanol dehydrogenase from Methylobacterium extorquens.

The crystal structure of methanol dehydrogenase (MDH) from Methylobacterium extorquens has been refined without stereochemical restraints at a resolution of 1.2 A. The high-resolution data have defined the conformation of the tricyclic pyrroloquinoline quinone (PQQ) cofactor ring as entirely planar. The detailed definition of the active-site geometry has shown many features that are similar to the quinohaemo-protein alcohol dehydrogenases from Comamonas testosteroni and Pseudomonas putida, both of which possess MDH-like and cytochrome c-like domains. Conserved features between the two types of PQQ-containing enzyme suggest a common pathway for electron transfer between MDH and its physiological electron acceptor cytochrome cL. A pathway for proton transfer from the active site to the bulk solvent is also suggested.

Alcohol Dehydrogenase↗

PubMed2004

Resonant oscillators with carbon-nanotube torsion springs.

We report on the characterization of nanometer-scale resonators. Each device incorporates one multiwalled carbon nanotube (MWNT) as a torsional spring. The devices are actuated electrostatically, and their deflections, both low frequency and on resonance, are detected optically. These are some of the smallest electromechanical devices ever created and are a demonstration of practical integrated MWNT-based oscillators. The results also show surprising intershell mechanical coupling behavior in the MWNTs.

Journal Article↗

PubMed2004

Complement regulation at the molecular level: the structure of decay-accelerating factor.

The human complement regulator CD55 is a key molecule protecting self-cells from complement-mediated lysis. X-ray diffraction and analytical ultracentrifugation data reveal a rod-like arrangement of four short consensus repeat (SCR) domains in both the crystal and solution. The stalk linking the four SCR domains to the glycosylphosphatidylinositol anchor is extended by the addition of 11 highly charged O-glycans and positions the domains an estimated 177 A above the membrane. Mutation mapping and hydrophobic potential analysis suggest that the interaction with the convertase, and thus complement regulation, depends on the burial of a hydrophobic patch centered on the linker between SCR domains 2 and 3.

CD55 Antigens↗

PubMed2003

The structure of endothiapepsin complexed with the gem-diol inhibitor PD-135,040 at 1.37 A.

The crystal structure of endothiapepsin complexed with the gem-diol inhibitor PD-135,040 has been anisotropically refined to a resolution of 1.37 A. The structure of this inhibitor complex is in agreement with previous structures of endothiapepsin gem-diol inhibitor complexes that have been used to develop proposed catalytic mechanisms. However, the increase in resolution over previous structures confirms the presence of a number of short hydrogen bonds within the active site that are likely to play an important role in the catalytic mechanism. The presence of low-barrier hydrogen bonds was indicated in a previous one-dimensional H NMR spectrum.

Aspartic Acid Endopeptidases↗

PubMed2002

Torsional response and stiffening of individual multiwalled carbon nanotubes.

We report on the characterization of torsional oscillators which use multiwalled carbon nanotubes as the spring elements. Through atomic-force-microscope force-distance measurements we are able to apply torsional strains to the nanotubes and measure their torsional spring constants, and estimate their effective shear moduli. The data show that the nanotubes are stiffened by repeated flexing. We speculate that changes in the intershell mechanical coupling are responsible for the stiffening.

Journal Article↗

PubMed2001

Crystallographic and biochemical analyses of the metal-free Haemophilus influenzae Fe3+-binding protein.

The crystal structure of the iron-free (apo) form of the Haemophilus influenzae Fe(3+)-binding protein (hFbp) has been determined to 1.75 A resolution. Information from this structure complements that derived from the holo structure with respect to the delineation of the process of iron binding and release. A 21 degrees rotation separates the two structural domains when the apo form is compared with the holo conformer, indicating that upon release of iron, the protein undergoes a change in conformation by bending about the central beta-sheet hinge. A surprising finding in the apo-hFbp structure was that the ternary binding site anion, observed in the crystals as phosphate, remained bound. In solution, apo-hFbp bound phosphate with an affinity K(d) of 2.3 x 10(-3) M. The presence of this ternary binding site anion appears to arrange the C-terminal iron-binding residues conducive to complementary binding to Fe(3+), while residues in the N-terminal binding domain must undergo induced fit to accommodate the Fe(3+) ligand. These observations suggest a binding process, the first step of which is the binding of a synergistic anion such as phosphate to the C-terminal domain. Next, iron binds to the preordered half-site on the C-terminal domain. Finally, the presence of iron organizes the N-terminal half-site and closes the interdomain hinge. The use of the synergistic anion and this iron binding process results in an extremely high affinity of the Fe(3+)-binding proteins for Fe(3+) (nFbp K'(eff) = 2.4 x 10(18) M(-1)). This high-affinity ligand binding process is unique among the family of bacterial periplasmic binding proteins and has interesting implications in the mechanism of iron removal from the Fe(3+)-binding proteins during FbpABC-mediated iron transport across the cytoplasmic membrane.

Anions↗

PubMed2001

A rheological study of the order-disorder conformational transition of xanthan gum.

The rheological properties of a moderately concentrated solution of xanthan gum in both the ordered and the disordered state have been studied. Oscillatory shear, steady shear flow, and extensional flow experiments have been performed at different temperatures, covering the order-disorder transition determined by differential scanning calorimetry (DSC). The principle of time/temperature superposition was applied to the xanthan solutions for the different types of flow. Although a master curve covering six decades of frequency could be obtained for the storage modulus over the entire investigated temperature range, less agreement was found for the other modulus. This indicates that the order-disorder transition reflects changes on the molecular scale and slight modification of the physical network structure. To the authors' knowledge, this is the first time that this transition has been observed using these different rheological techniques.

Carbohydrate Conformation↗

PubMed2001

Comparative rheological behavior of hyaluronan from bacterial and animal sources with cross-linked hyaluronan (hylan) in aqueous solution.

Using a variety of rheological techniques, the behavior of hyaluronan (M(w) 0.8-2.2 x 10(6)), cross-linked hyaluronan (hylan) (M(w) 1.8-12.5 x 10(6)), and Healon (M(w) approximately 5 x 10(6)) (a proprietary hyaluronan) was studied over a large range of molecular weights. The object was to study the effect of the cross-links in hylan on the various rheological parameters, in comparison with linear hyaluronan. There are significant differences. The Huggins constant and the critical overlap parameter C*[eta] are considerably lower for hylan and an increase in moduli at low frequencies was observed for hylan compared with the hyaluronan samples at all molecular weights studied. The results point to a difference in structure in dilute solution for hylan due to the ability to form networks, which can be removed by pressure filtration. In contrast, we do not find an increase of the steady shear viscosity and elastic modulus at higher concentrations when a homogeneous entangled network is reached. We attribute this behavior to the semirigid character of the hyaluronan chain and to the predominance of entanglements over the cross-link points present in hylan in the semidilute domain. Due to the higher apparent molecular weights that are possible with hylan structures but not with the hyaluronans currently available, a wider range of applications can be achieved with hylans when viscoelasticity is required, particularly for the viscosupplementation of synovial fluid damaged by osteoarthritis.

Animals↗

PubMed2001

Effects of A-P translation and rotation on the wear of UHMWPE in a total knee joint simulator.

We developed a three-channel total knee joint simulator and studied the effect of tibial anterior-posterior translation and internal/external rotation on the wear of polyethylene tibial inserts in total knee replacements (Anatomic Graduated Component knees). The wear rate was the lowest in experiment (Exp.) 1, without translation and rotation [1.74 mg/million (mg/Mc) cycles]. In Exp. 2, with +/-5 degrees tibial rotation added, the wear rate increased to 10.6 mg/Mc. In Exp. 3, with rotation and -12 mm tibial translation added, the wear rate was 15.1 mg/Mc, whereas in Exp. 4, with rotation and +12 mm tibial translation, the wear rate was 18.7 mg/Mc. Internal/external rotation and anterior-posterior translation added a 6- to 11-fold increase in the wear rates of tibial knee inserts. The shapes of the tibial wear tracks were rectangular and the area of the track increased when rotation and translation were added.

Biomechanical Phenomena↗

PubMed2001

Replacement of the axial histidine ligand with imidazole in cytochrome c peroxidase. 1. Effects on structure.

Replacement of the axial histidine ligand with exogenous imidazole has been accomplished in a number of heme protein mutants, where it often serves to complement the functional properties of the protein. In this paper, we describe the effects of pH and buffer ion on the crystal structure of the H175G mutant of cytochrome c peroxidase, in which the histidine tether between the heme and the protein backbone is replaced by bound imidazole. The structures show that imidazole can occupy the proximal H175G cavity under a number of experimental conditions, but that the details of the interaction with the protein and the coordination to the heme are markedly dependent on conditions. Replacement of the tethered histidine ligand with imidazole permits the heme to shift slightly in its pocket, allowing it to adopt either a planar or distally domed conformation. H175G crystallized from both high phosphate and imidazole concentrations exists as a novel, 5-coordinate phosphate bound state, in which the proximal imidazole is dissociated and the distal phosphate is coordinated to the iron. To accommodate this bound phosphate, the side chains of His-52 and Asn-82 alter their positions and a significant conformational change in the surrounding protein backbone occurs. In the absence of phosphate, imidazole binds to the proximal H175G cavity in a pH-dependent fashion. At pH 7, imidazole is directly coordinated to the heme (d(Fe--Im) = 2.0 A) with a nearby distal water (d(Fe--HOH) = 2.4 A). This is similar to the structure of WT CCP except that the iron lies closer in the heme plane, and the hydrogen bond between imidazole and Asp-235 (d(Im--Asp) = 3.1 A) is longer than for WT CCP (d(His--Asp) = 2.9 A). As the pH is dropped to 5, imidazole dissociates from the heme (d(Fe--Im) = 2.9 A), but remains in the proximal cavity where it is strongly hydrogen bonded to Asp-235 (d(Im--Asp) = 2.8 A). In addition, the heme is significantly domed toward the distal pocket where it may coordinate a water molecule. Finally, the structure of H175G/Im, pH 6, at low temperature (100 K) is very similar to that at room temperature, except that the water above the distal heme face is not present. This study concludes that steric restrictions imposed by the covalently tethered histidine restrain the heme and its ligand coordination from distortions that would arise in the absence of the restricted tether. Coupled with the functional and spectroscopic properties described in the following paper in this issue, these structures help to illustrate how the delicate and critical interactions between protein, ligand, and metal modulate the function of heme enzymes.

Amino Acid Substitution↗

PubMed2001

Microwear phenomena of ultrahigh molecular weight polyethylene cups and debris morphology related to gamma radiation dose in simulator study.

Ultrahigh molecular weight polyethylene (PE) cups with 0, 2.5, 50, 100, and 150 Mrad radiation treatments were run in a hip simulator for comparison of the microwear phenomena on the cup surfaces with the corresponding debris morphology. In general, the size and frequency of the PE surface fibrils and the size of the retrieved PE debris decreased with increasing radiation dose. The fibril size and shape on the cup surfaces were well correlated with the radiation dose. The fibrillar shape and size were found to be proportional to the square root of the radiation dose. However, the trend for size and shape factors of the wear debris related to the radiation dose was weak at best. Thus, the morphology of the PE fibrils on the cup surfaces was more sensitive to variations in the radiation dose than the actual wear debris. The wear response appeared to be a three-step process, which was dependent on the formation of surface nodules or ripples, the teasing out of surface fibrils, and the toughness of the PE matrix in releasing a wear fibril to form a debris particle. The tougher PE became with increasing radiation dose, the harder it was for the PE fibrils to break out into wear particles.

Arthroplasty, Replacement, Hip↗

PubMed2001

Effects of a circuit weight training program on the body images of college students.

OBJECTIVE: The present investigation examined the extent to which participation in a 6-week circuit-weight training program produced changes in participants' body images relative to a matched control group. METHOD: The weight trainers consisted of 39 college students (27 women and 12 men). The control group of 39 individuals did not weight-train currently or within the past year. All participants were pre- and posttested on the Multidimensional Body Self-Relations Questionnaire, the Social Physique Anxiety Scale, and the Physical Self-Efficacy Scale. Weight trainers were also pre- and posttested on muscular strength and assessed on their motives for exercise. RESULTS: The program successfully increased upper- and lower-body strength. In contrast to the comparison group, weight trainers had a significantly improved evaluation of their appearance, greater body satisfaction, reduced social physique anxiety, and enhanced physical self-efficacy. Outcomes were unrelated to the extent of concurrent aerobic exercise and largely unrelated to exercise motives. DISCUSSION: Even a relatively brief weight training program can produce improvements in multiple aspects of body image. Further research should investigate weight training as an adjunct to psychosocial treatments of body dissatisfaction.

Adolescent↗

PubMed2001

Solution rheology of kappa-carrageenan in the ordered and disordered conformations.

The order-disorder conformational transition of kappa-carrageenan, induced by both electrolyte and temperature, was found to give rise to significantly different rheological properties under shear flow, extensional flow, and small deformation oscillation regimes. Shear flow displayed only shear thinning or Newtonian behavior, depending of the chain conformation. A larger range of properties was observed in elongational flow. Strain-thinning behavior was observed in the ordered conformation while strain thickening occurred in the disordered conformation. These results are discussed as a function of the chain conformation.

Carbohydrate Conformation↗