Although atom transfer radical polymerization (ATRP) is often a controlled/ living process, the growth rate of polymer films during surface-initiated ATRP frequently decreases with time. This article investigates the mechanism behind the termination of film growth. Studies of methyl methacrylate and methyl acrylate polymerization with a Cu/tris[2-(dimethylamino)ethyl]amine catalyst system show a constant but slow growth rate at low catalyst concentrations and rapid growth followed by early termination at higher catalyst concentrations. For a given polymerization time, there is, therefore, an optimum intermediate catalyst concentration for achieving maximum film thickness. Simulations of polymerization that consider activation, deactivation, and termination show trends similar to those of the experimental data, and the addition of Cu(II) to polymerization solutions results in a more constant rate of film growth by decreasing the concentration of radicals on the surface. Taken together, these studies suggest that at high concentrations of radicals, termination of polymerization by radical recombination limits film growth. Interestingly, stirring of polymerization solutions decreases film thickness in some cases, presumably because chain motion facilitates radical recombination.

We report the use of a variety of polyelectrolyte multilayers (PEMs) as selective skins in composite membranes for nanofiltration (NF) and diffusion dialysis. Deposition of PEMs occurs through simple alternating adsorption of polycations and polyanions, and separations can be optimized by varying the constituent polyelectrolytes as well as deposition conditions. In general, the use of polycations and polyanions with lower charge densities allows separation of larger analytes. Depending on the polyelectrolytes employed, PEM membranes can remove salt from sugar solutions, separate proteins, or allow size-selective passage of specific sugars. Additionally, because of the minimal thickness of PEMs, NF pure water fluxes through these membranes typically range from 1.5 to 3 m3/(m2 day) at 4.8 bar. Specifically, to separate sugars, we employed poly(styrene sulfonate) (PSS)/poly(diallyldimethylammonium chloride) (PDADMAC) films, which allow 42% passage of glucose along with a 98% rejection of raffinose and a pure water flux of 2.4 m3/(m2 day). PSS/PDADMAC membranes are also capable of separating NaCl and sucrose (selectivity of approximately 10), while high-flux chitosan/hyaluronic acid membranes [pure water flux of 5 m3/(m2 day) at 4.8 bar] may prove useful in protein separations.

a b s t r a c tNon-isocyanate thermoplastic polyhydroxyurethane (PHU) elastomers were synthesized from cyclic carbonate aminolysis using polytetramethylene oxide (PTMO) as soft segment and divinylbenzene dicyclocarbonate and three diamine chain extenders as hard segment with a range of hard-segment content. Characterization was done via Fourier transform infrared spectroscopy, small-angle X-ray scattering (SAXS), uniaxial tensile testing, and dynamic mechanical analysis (DMA). SAXS reveals that these PHUs possess nanophaseseparated morphology with 10-20 nm interdomain spacings. These PHUs display elastomeric response and tunable tensile properties with Young's modulus ranging from 27 to 200 MPa, tensile strength from 0.3 to 9.7 MPa and elongation at break ranging up to greater than 2000%. DMA reveals that nanophase separation in these PHUs is accompanied by broad interphases having a wide range of local composition; this nanophase separation differs significantly from that manifested by thermoplastic polyurethane elastomer (TPU) due to hydrogen bonding of hydroxyl groups in the hard segments to the PTMO soft segment. These PHUs show very good damping performance with tan d P 0.30 over broad temperature ranges (P60°C), which are tunable through simple variation of hardsegment content and chain extender structures.

Background:The microscopic agglutination test (MAT) is commonly used for the diagnosis of canine leptospirosis. In dogs it is sometimes suggested that the serogroup with the highest MAT titer is the infecting serogroup; however, this is not true in humans with confirmed leptospirosis. We sought to investigate the value of MAT results in predicting the infecting serogroup by comparing results across several laboratories and within individual dogs over time.Objectives: To examine the variability in MAT results across different laboratories in dogs recently vaccinated against leptospirosis, and in dogs with clinical leptospirosis, and to investigate variability over time in MAT results in individual dogs with leptospirosis.Animals: Eighteen dogs from a research colony, 9 of which had been vaccinated against leptospirosis, and 17 dogs clinically diagnosed with leptospirosis.Methods: Serum samples were submitted to up to 5 veterinary diagnostic laboratories for MAT titers from each dog on at least 1 occasion. MAT results also were followed over time in 6 dogs diagnosed with leptospirosis.Results: MAT results were discordant across different laboratories in dogs recently vaccinated against leptospirosis and in dogs with clinical leptospirosis. MAT results varied over time in individual dogs with the disease.Conclusions and Clinical Importance: The MAT is a valuable test for the diagnosis of leptospirosis in dogs, but it is unlikely that test results can be used to predict the infecting serogroup. Laboratories offering the MAT should consider participation in a proficiency scheme.