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Antimicrobial activity of secondary and tertiary poly(diallylammonium) salts (PDAAs) had not been reported before. Due to difficulties with preparation of polymers from the monomers of the diallylamine (DAA) series in the nonquaternary form, up to recently it was not possible to obtain PDAAs with a sufficiently high molecular mass. Here, we describe the investigations of antimicrobial activity of novel water-soluble cationic polyelectrolytes of the PDAA series, namely secondary poly(diallylammonium trifluoroacetate) (PDAATFA) and tertiary poly(diallylmethylammonium trifluoroacetate) (PDAMATFA), in synthesis of which we have recently succeeded, against gram-positive and gram-negative bacteria, and fungi. We have studied the effect of molecular weight (polymeric chain length) and ionic strength of solution on the biocidal efficiency of those polymers; in addition, the concentration dependences of PDAATFA reduced viscosity in salt-free and KCl aqueous solutions have been investigated. The antimicrobial properties of polybase polydiallylamine (BPDAA), which was obtained in an aqueous solution of PDAATFA in presence of alkali, have been also studied as well as biocidal activity of commercial open-chain polybase branched PEI. Those PDAATFA, BPDAA and PEI polymers served as the systems to study the structure-activity relationships. Transmission electronic microscopy study was carried out to characterize the mode of antimicrobial action of PDAATFA using E. coli . It was shown that the synthesized PDAATFA and PDAMATFA exhibit, unlike the quaternary polymers of this series, a rather high biocidal efficiency that is comparable with the activity of known effective cationic polymer biocides or exceeds it. Novel polyelectrolytes exhibit quite strong biocidal properties at different conditions including aqueous solutions of moderate ionic strength (serum, 0.01 M/0.1 M) and aqueous-alkaline solutions (pH 10.5) until the macrochain retains some positive charge, but complete neutralization of the polyelectrolyte in a 1 M salt solution results in the loss of its biocidal activity. The obtained results evidence that the structure of links, which combine the hydrophobic pyrrolidinium rings with the hydrophilic secondary/tertiary ammonium groups, is responsible for the high biocidal activity of the PDAAs. Polymeric nature of the synthesized compounds is one of the most significant factors of their bactericidal efficiency, unlike their high fungicidal activity, which is evidently related to the secondary/tertiary pyrrolidinium cycle.

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A total of 750 images of individual ultra-high molecular weight polyethylene (UHMWPE) particles isolated from periprosthetic failed hip, knee, and shoulder arthroplasties were extracted from archival scanning electron micrographs. Particle size and morphology was subsequently analyzed using computerized image analysis software utilizing five descriptors found in ASTM F1877-98, a standard for quantitative description of wear debris. An online survey application was developed to display particle images, and allowed ten respondents to classify particle morphologies according to commonly used terminology as fibers, flakes, or granules. Particles were categorized based on a simple majority of responses. All descriptors were evaluated using a one-way ANOVA and Tukey-Kramer test for all-pairs comparison among each class of particles. A logistic regression model using half of the particles included in the survey was then used to develop a mathematical scheme to predict whether a given particle should be classified as a fiber, flake, or granule based on its quantitative measurements. The validity of the model was then assessed using the other half of the survey particles and compared with human responses. Comparison of the quantitative measurements of isolated particles showed that the morphologies of each particle type classified by respondents were statistically different from one another (p<0.05). The average agreement between mathematical prediction and human respondents was 83.5% (standard error 0.16%). These data suggest that computerized descriptors can be feasibly correlated with subjective terminology, thus providing a basis for a common vocabulary for particle description which can be translated into quantitative dimensions.

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Recently, highly crosslinked UHMWPE components have been promoted for their high abrasive wear resistance over conventional UHMWPE (PE) in total joint replacement (TJR) prostheses to minimize osteolysis and consequent implant loosening. This study was aimed at investigating the role of friction gradients induced by localized coefficients of friction at both crystalline and amorphous nanoregions in PE, and crystalline and crosslinked nanoregions in crosslinked UHMWPE (XPE), in submicron wear debris generation. An abrasive wear study performed on both XPE and PE using atomic force microscopy (AFM) illustrated that the onset of plastic deformation for XPE occurred at a normal load that was approximately 3 times higher when compared to PE. Coefficients of friction (mu d) of 0.2, 0.35, and 0.61, experimentally derived using AFM, were used as representative mu d for crystalline, amorphous, and crosslinked nanoregions, respectively, in a numerical Hertzian model. An increase in mu (0.2 +/- 0.02, 0.35 +/- 0.01 and 0.6 +/- 0.04) was observed with a decrease in crystallinity and storage modulus at 22 degrees C. Using the Hertzian contact model, it was observed that variability in friction between nanoregions contributed to higher magnitude stresses for XPE (0.2 to 0.61; maximum sigma eff = 2.8) compared to PE (0.2 to 0.35; maximum sigma eff = 1.1) over a negligible thickness of the interfacial zone (IZ) between nanoregions. The experimentally observed increase in abrasive wear resistance of XPE could be attributed to an increase in the thickness of the interfacial zone between nanoregions with mu changing gradually from crystalline to crosslinked nanoregions, a situation that may not be observed with PE. This would cause a decrease in the friction gradient and resulting stresses thereby agreeing with the observed experimental higher abrasive wear resistance for XPE. However, in both PE and XPE, the presence of stress concentrations over a period of time could lead to irreversible damage of the material eventually generating submicron wear debris. Hence, semicrystalline, inhomogenous UHMWPE with several nanoregions (amorphous and crystalline) would be at a disadvantage for bearing application in terms of abrasive wear resistance compared to UHMWPE with relatively lower number of nanoregions and crosslinked nanoregions.

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Femoral lift-off has been reported in total knee arthroplasty using dynamic fluoroscopic analysis. However, the effect of femoral lift-off on ultra-high-molecular-weight polyethylene (UHMWPE) is not clear. The objective of this study was to evaluate the effect of lift-off movement on the wear of UHMWPE using a pin-on-disc testing machine. Using oxidised UHMWPE, delamination was observed in 70% of the discs with lift-off movement, as against none in without lift-off movement (p=0.0603). In non-oxidised UHMWPE the depth of the wear track was increased in the impact area after lift-off, but there was no delamination and no increase in wear as measured by weight loss. UHMWPE can sustain the impact of after lift-off with neither delamination nor wear by other mechanisms. In contrast, degraded (i.e., oxidised) UHMWPE undergoes delamination after lift-off. Since it is probable that lift-off cannot be prevented, oxidised UHMWPE should never be used in TKA.

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Osteolysis induced by ultrahigh molecular weight polyethylene wear debris has been recognized as the major cause of long-term failure in total joint arthroplasties. In a previous study, the prevalence of intraoperatively identified osteolysis during primary revision surgery was much higher in mobile bearing knee replacements (47%) than in fixed bearing knee replacements (13%). We postulated that mobile bearing knee implants tend to produce smaller sized particles. In our current study, we compared the particle size and morphology of polyethylene wear debris between failed mobile bearing and fixed bearing knees. Tissue specimens from interfacial and lytic regions were extracted during revision surgery of 10 mobile bearing knees (all of the low contact stress (LCS) design) and 17 fixed bearing knees (10 of the porous-coated anatomic (PCA) and 7 of the Miller/Galante design). Polyethylene particles were isolated from the tissue specimens and examined using both scanning electron microscopy and light-scattering analyses. The LCS mobile bearing knees produced smaller particulate debris (mean equivalent spherical diameter: 0.58 microm in LCS, 1.17 microm in PCA and 5.23 microm in M/G) and more granular debris (mean value: 93% in LCS, 77% in PCA and 15% in M/G).

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A novel pin-on-disk type wear tester is described allowing a rapid screening of different types of polyethylene under both unidirectional and multidirectional sliding motion. The wear of four polyethylene materials sliding against a roughened CoCrMo alloy was evaluated: a non-irradiated UHMWPE, a UHMWPE irradiated with a dose of 25 kGy in air, and two types of crosslinked UHMWPE (100 kGy, air), which were subjected to a stabilization heat treatment in nitrogen at 155 degrees C for 72 hours (XLPE I) and in water at 130 degrees C for 72 hours (XLPE II), respectively.Under multidirectional sliding conditions both types of XLPE exhibited significantly less wear with respect to the 25 kGy irradiated UHMWPE and the non-irradiated UHMWPE, even under the rough counterface conditions applied. Under unidirectional sliding motion both types of XLPE exhibited the highest wear of all materials tested, because the orientation hardening effect acting under linear lubricated condition is less pronounced for crosslinked polyethylene.

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Ultra high molecular weight polyethylene (UHMWPE) is routinely used as one half of a bearing couple in clinical orthopaedic applications. This material is generally one of two grades, compression moulded GUR 1120, with a molecular weight of 4.4x 10(6) g mol(-1), or ram extruded GUR 4150HP with a molecular weight of 7.3x10(6) g mol(-1) although other grades are used as well. This study examines the effect of molecular weight and processing method by comparing the wear resistance of these two materials together with a non-standard extruded form of GUR 1120. Wear studies have been conducted against counterface surfaces which represent new and scratch-damaged femoral heads with bovine serum lubricant in a uniaxial reciprocating test configuration. No difference in the wear resistance was found between any material when tested against smooth cobalt chrome counterfaces. On rough cobalt chrome counterfaces, although no statistically significant difference (P>0.05) was found between the extruded and compression moulded GUR 1120, the extruded GUR 4150HP had a consistently better wear resistance. These results are discussed with reference to previous wear studies as well as the physical and mechanical properties of these materials.

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Foi estudada a degradaçäo de um corante sólido, obtido pela extraçäo alcoólica das sementes de urucum (Bixa orellana, L), contendo inicialmente 31,36 por cento de bixina, em embalagens com diferentes taxas de permeabilidade ao oxigênio: filme laminado com alumínio, filme metalizado, filme co-extrusado de nylon e polietileno de baixa densidade e filme de polietileno de baixa densidade. O estudo de estabilidade foi realizado a 30 graus centígrados por um periodo de 368 dias, com avaliaçöes periódicas de teor de pigmento. Observou-se que o teor de bixina diminuiu significativamente entre as 2 a 3 semanas, em todas as embalagens. A partir de entäo, manteve-se, com exceçäo da embalagem de polietileno, um teor médio de 28,33 por cento de bixina. No corante acondicionado nas embalagens de polietileno de baixa densidade verificou-se uma taxa de degradaçäo de bixina de aproximadamente 0,04 por cento ao dia, durante todo o restante do estudo

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