Enhanced Polymer Grafting from Multiwalled Carbon Nanotubes through Living Anionic Surface-Initiated Polymerization

Anionic surface-initiated polymerization of ethylene oxide and styrene has been performed using multiwalled carbon nanotubes (MWNTs) functionalized with anionic initiators. The surface of MWNTs was modified via covalent attachment of precursor anions such as 4-hydroxyethyl benzocyclobutene (BCBEO) and 1-benzocyclobutene-1′-phenylethylene (BCB-PE) through Diels-Alder cycloaddition at 235 °C. Surface-functionalized MWNTs-g-(BCB-EO) n and MWNTs-g-(BCB-PE) n with 23 and 54 wt % precursor initiators, respectively, were used for the polymerizations. Alkoxide anion on the surface of MWNTs-g-(BCB-EO) n was generated through reaction with potassium triphenylmethane for the polymerization of ethylene oxide in tetrahydrofuran and phenyl substituted alkyllithium was generated from the surface of MWNTs-g-(BCB-PE) n using sec-butyllithium for the polymerization of styrene in benzene. In both cases, the initiation was found to be very slow because of the heterogeneous reaction medium. However, the MWNTs gradually dispersed in the reaction medium during the polymerization. A pale green color was noticed in the case of ethylene oxide polymerization and the color of initiator as well as the propagating anions was not discernible visually in styrene polymerization. Polymer grafted nanocomposites, MWNTs-g-(BCB-PEO) n and MWNTs-g-(BCB-PS) n containing a very high percentage of hairy polymer with a small fraction of MWNTs (<1 wt %) were obtained. The conversion of ethylene oxide and the weight percent of PEO on the surface of the MWNTs increased with increasing reaction time indicating a controlled polymerization. The polymer-grafted MWNTs were characterized using FTIR, 1H NMR, Raman spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and transmission electron microscopy (TEM). Size exclusion chromatography of the polymer grafted MWNTs revealed broad molecular weight distributions (1.3 < Mw/Mn < 1.8) indicating the presence of different sizes of polymer nanocomposites. The TEM images showed the presence of thick layers of polymer up to 30 nm around the MWNTs. The living nature of the growing polystyryllithium was used to produce diblock copolymer grafts using sequential polymerization of isoprene on the surface of MWNTs.

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.

Well-Defined Poly(4-vinylbenzocyclobutene): Synthesis by Living Anionic Polymerization and Characterization

Living anionic polymerization of 4-vinylbenzocylobutene was performed in benzene at room temperature using sec-butyllithium as the initiator. Results of the kinetic studies indicated the termination- and transfer-free nature of the polymerization. Homopolymers with predictable molecular weights and narrow molecular weight distributions were produced, excluding the interference of the cyclobutene rings during initiation and propagation. Thermogravimetric analysis of poly(4-vinylbenzocyclobutene) in air showed a small weight gain at ~200 °C, a rapid decomposition at ~455 °C, and a gradual decomposition at ~566 °C. This behavior was attributed to the formation of radicals from the pendent benzocyclobutene functionality through o-quinodimethane intermediates and simultaneous decomposition/cross-linking reactions at high temperature. The living nature of the polymerization was also examined via sequential copolymerization with butadiene to form diblock copolymers.

Spatial Relationships Among Young Cercocarpus ledifolius (Curlleaf Mountain Ylahogany)

This study analyzed spatial location patterns of Cercocarpus ledifolius Nutt. (curlleaf mountain mahogany) plants, classified as current-year seedling, established seedling, juvenile, and immature individuals, at a central Nevada study site. Most current-year seedlings were located in mahogany stands in which large, mature individuals had the greatest abundance. These stands had greater litter cover and a thicker layer of litter than areas with few current- year seedlings. Most established young Cercocarpus were located in adjacent Artemisia tridentata ssp. vaseyana (mountain big sagebrush) communities, or in infrequent canopy gaps between relatively few large, mature Cercocarpus. We discuss potential roles of plant litter, root growth characteristics, nurse plants, and herbivory in the establishment and renewal of Cercocarpus communities.

Development of 10 Polymorphic Microsatellite Loci Isolated From The Mountain Beaver, Aplodontia rufa rufa (Rafinesque)

We developed 10 microsatellite markers for the mountain beaver, Aplodontia rufa rufa. In three populations of A. r. rufa, the number of alleles for these loci ranged from monomorphic to nine. Average observed heterozygosities in these populations ranged from 0.29 to 0.60. We also tested previously published markers from the endangered subspecies A. r. nigra in A. r. rufa populations.

Increased Risk of Chronic Wasting Disease in Rocky Mountain Elk Associated With Decreased Magnesium and Increased Manganese in Brain Tissue

Chronic wasting disease (CWD) is a transmissible spongiform encephalopathy (TSE) of Rocky Mountain elk in North America. Recent studies suggest that tissue and blood mineral levels may be valuable in assessing TSE infection in sheep and cattle. The objectives of this study were to examine baseline levels of copper, manganese, magnesium, zinc, selenium, and molybdenum in the brains of Rocky Mountain elk with differing prion genotypes and to assess the association of mineral levels with CWD infection. Elk with leucine at prion position 132 had significantly lower magnesium levels than elk with 2 copies of methionine. Chronic wasting disease-positive elk had significantly lower magnesium than control elk. The incorporation of manganese levels in addition to magnesium significantly refined explanatory ability, even though manganese alone was not significantly associated with CWD. This study demonstrated that mineral analysis may provide an additional disease correlate for assessing CWD risk, particularly in conjunction with genotype.

Use of Confined Dogs for Reducing Deer Damage to Apple Orchards

We assessed the efficacy of free-ranging dogs, confined by buried fences and electronic collars, for reducing deer damage to apple trees in three commercial apple orchards in Oswego County, New York State. During 1995 and 1996, we monitored paired dog-protected and control plots in each orchard. Within dog-protected areas, the percentage of damaged buds was lower, and fruit yield was higher in both 1995 and 1996 than for control plots. Gross economic returns were higher from dog-protected than control plots in both 1995 (by 51%) and 1996 (by 184%). After two seasons of growth, trees planted in May 1995 had nearly three times the cross-sectional area, and were 60% taller if they were in dog-protected rather than control plots. Dogs provided increased economic returns for growers at much lower cost than conventional barrier fencing.

Late Pleistocene and Holocene Paleolimnology of Two Mountain Lakes in Western Tasmania

The analysis of diatoms from two lake-sediment cores from southwestern Tasmania that span the Pleistocene-Holocene boundary provides insight about paleolimnological and paleoclimatic change in this region. Both Lake Vera (550 m elevation), in west-central Tasmania, and Eagle Tarn (1,033 m elevation), in south-central Tasmania, have lacustrine records that begin about 12,000 years ago. Despite significant differences in location, elevation, and geologic terrane, both lakes have, had similar, as well as synchronous, limnological histories. Each appears to have been larger and more alkaline 12,000 years ago than at present, and both became shallower through time. Fossil diatom assemblages about 11,500 years old indicate shallow-water environments that fluctuated in pH between acidic and alkaline, and between dilute and possibly slightly saline hydrochemical conditions ( The synchroneity and similar character of the paleolimnological changes at these separate and distinctive sites suggests a regional paleoclimatic cause rather than local environmental effects. Latest Pleistocene climates were apparently more continental and drier than Holocene climates in southwestern Tasmania.

Phytoplankton Dynamics in Three Rocky Mountain Lakes, Colorado, U.S.A.

In 1984 and 1985 seasonal changes in phytoplankton were studied in a system of three lakes in Loch Vale, Rocky Mountain National Park, Colorado. Three periods were evident: (1) A spring bloom, during snowmelt, of the planktonic diatom Asterionella Formosa, (2) a mid- summer period of minimal algal abundance, and (3) a fall bloom of the blue-green alga Oscillatoria limnetica. Seasonal phytoplankton dynamics in these lakes are controlled partially by the rapid flushing rate during snowmelt and the transport of phytoplankton from the highest lake to the lower lakes by the stream, Icy Brook. During snowmelt, the A. formosa population in the most downstream lake has a net rate of increase of 0.34 d-1, which is calculated from the flushing rate and from the A. formosa abundance in the inflow from the upstream lake and in the downstream lake. Measurement of photosynthetic rates at different depths during the three periods confirmed the rapid growth of A. formosa during the spring. The decline in A. formosa after snowmelt may be related to grazing by developing zooplankton populations. The possible importance of the seasonal variations in nitrate concentrations were evaluated in situ enrichment experiments. For A. formosa and O. limnetica populations, growth stimulation resulted from 8- or 16-micromolar amendments of calcium nitrate and sulfuric acid, but the reason for this stimulation could not be determined from these experiments.

Deterministic Solutions for a Step-growth Polymerization

Chain topology, including branch node, chain link and cross-link dynamics that contribute to the number of elastically active strands and junctions, are calculated using purely deterministic derivations. Solutions are not coupled to population density distributions. An eigenzeit transformation assists in the conversion of expressions derived by chemical reaction principles from time to conversion space, yielding transport phenomena type expressions where the rate of change in the molar concentrations of branch nodes with respect to conversion is expressed as functions of the fraction of reactive sites on precursors and reactants. Analogies are hypothesized to exist in cross-linking space that effectively distribute branch nodes with i reacted moieties between cross-links having j bonds extending to the gel. To obtain solutions, reacted sites on nodes or links with finite chain extensions are examined in terms of stoichiometry associated with covalent bonding. Solutions replicate published results based on Miller and Macosko’s recursive procedure and results obtained from truncated weighted sums of population density distributions as suggested by Flory.

Estudo da formação de domínios em membranas modelos induzidos por peptídeos antimicrobianos e sua ação interfacial

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins

Objectives. The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems. Methods. A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1 mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p-toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV-Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate (R-p(max)) profile of the model resin. Results. In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region, whereas that of CQ is in the visible range. With respect to binary systems, CQ + EDAB exhibited higher DC and R-p(max) values. In formulations that contained ternary initiator systems, the group CQ + QTX + EDAB was the only one of the investigated experimental groups that exhibited an R-p(max) value greater than that of CQ + EDAB. The groups QTX + EDAB + DPIHFP and QTX + DPIHFP + SULF exhibited values similar to those of CQ + EDAB with respect to the final DC; however, they also exhibited lower reactivity. Significance. Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A comparative study between crack analysis and a mechanical test for assessing the polymerization stress of restorative composites

Objectives. To verify the hypothesis that crack analysis and a mechanical test would rank a series of composites in a similar order with respect to polymerization stress. Also, both tests would show similar relationships between stress and composite elastic modulus and/or shrinkage. Methods. Soda-lime glass discs (2-mm thick) with a central perforation (3.5-mm diameter) received four Vickers indentations 500 mu m from the cavity margin. The indent cracks were measured (500x) prior and 10 min after the cavity was restored with one of six materials (Kalore/KL, Gradia/GR, Ice/IC, Wave/WV, Majesty Flow/MF, and Majesty Posterior/MP). Stresses at the indent site were calculated based on glass fracture toughness and increase in crack length. Stress at the bonded interface was calculated using the equation for an internally pressurized cylinder. The mechanical test used a universal testing machine and glass rods (5-mm diameter) as substrate. An extensometer monitored specimen height (2 mm). Nominal stress was calculated dividing the maximum shrinkage force by the specimen cross-sectional area. Composite elastic modulus was determined by nanoindentation and post-gel shrinkage was measured using strain gages. Data were subjected to one-way ANOVA/Tukey or Kruskal-Wallis/Mann-Whitney tests (alpha: 5%). Results. Both tests grouped the composites in three statistical subsets, with small differences in overlapping between the intermediate subset (MF, WV) and the highest (MP, IC) or the lowest stress materials (KL, GR). Higher stresses were developed by composites with high modulus and/or high shrinkage. Significance. Crack analysis demonstrated to be as effective as the mechanical test to rank composites regarding polymerization stress. (c) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A comparative evaluation of polymerization stress data obtained with four different mechanical testing systems

Objectives. The null hypothesis was that mechanical testing systems used to determine polymerization stress (sigma(pol)) would rank a series of composites similarly. Methods. Two series of composites were tested in the following systems: universal testing machine (UTM) using glass rods as bonding substrate, UTM/acrylic rods, "low compliance device", and single cantilever device ("Bioman"). One series had five experimental composites containing BisGMA:TEGDMA in equimolar concentrations and 60, 65, 70, 75 or 80 wt% of filler. The other series had five commercial composites: Filtek Z250 (3M ESPE), Filtek A110 (3M ESPE), Tetric Ceram (Ivoclar), Heliomolar (Ivoclar) and Point 4 (Kerr). Specimen geometry, dimensions and curing conditions were similar in all systems. sigma(pol) was monitored for 10 min. Volumetric shrinkage (VS) was measured in a mercury dilatometer and elastic modulus (E) was determined by three-point bending. Shrinkage rate was used as a measure of reaction kinetics. ANOVA/Tukey test was performed for each variable, separately for each series. Results. For the experimental composites, sigma(pol) decreased with filler content in all systems, following the variation in VS. For commercial materials, sigma(pol) did not vary in the UTM/acrylic system and showed very few similarities in rankings in the others tests system. Also, no clear relationships were observed between sigma(pol) and VS or E. Significance. The testing systems showed a good agreement for the experimental composites, but very few similarities for the commercial composites. Therefore, comparison of polymerization stress results from different devices must be done carefully. (c) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.