Label free electrochemiluminescence protocol for sensitive DNA detection with a tris(2,2'-bipyridyl)ruthenium(II) modified electrode based on nucleic acid oxidation

Label free electrochemiluminescence (ECL) DNA detection based on catalytic guanine and adenine bases oxidation using tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)] modified glassy carbon (GC) electrode was demonstrated in this work. The modified GC electrode was prepared by casting carbon nanotubes (CNT)/Nafion/Ru(bpy)(3)(2+) composite film on the electrode surface. ECL signals of doublestranded DNA and their thermally denatured counterparts can be distinctly discriminated using cyclic voltammetry (CV) with a low concentration (3.04 x 10(-8) mol/L for Salmon Testes-DNA). Most importantly, sensitive single-base mismatch detection of p53 gene sequence segment was realized with 3.93 x 10(-10) mol/L employing CV stimulation (ECL signal of C/A mismatched DNA oligonucleotides was 1.5-fold higher than that of fully base-paired DNA oligonucleotides). Label free, high sensitivity and simplicity for single-base mismatch discrimination were the main advantages of the present ECL technique for DNA detection over the traditional DNA sensors.

A genetically engineered thermally responsive sustained release curcumin depot to treat neuroinflammation.

Radiculopathy, a painful neuroinflammation that can accompany intervertebral disc herniation, is associated with locally increased levels of the pro-inflammatory cytokine tumor necrosis factor alpha (TNFα). Systemic administration of TNF antagonists for radiculopathy in the clinic has shown mixed results, and there is growing interest in the local delivery of anti-inflammatory drugs to treat this pathology as well as similar inflammatory events of peripheral nerve injury. Curcumin, a known antagonist of TNFα in multiple cell types and tissues, was chemically modified and conjugated to a thermally responsive elastin-like polypeptide (ELP) to create an injectable depot for sustained, local delivery of curcumin to treat neuroinflammation. ELPs are biopolymers capable of thermally-triggered in situ depot formation that have been successfully employed as drug carriers and biomaterials in several applications. ELP-curcumin conjugates were shown to display high drug loading, rapidly release curcumin in vitro via degradable carbamate bonds, and retain in vitro bioactivity against TNFα-induced cytotoxicity and monocyte activation with IC50 only two-fold higher than curcumin. When injected proximal to the sciatic nerve in mice via intramuscular (i.m.) injection, ELP-curcumin conjugates underwent a thermally triggered soluble-insoluble phase transition, leading to in situ formation of a depot that released curcumin over 4days post-injection and decreased plasma AUC 7-fold.

Temperature and water potential relations of tropical Trametes and other wood-decay fungi from the indigenous forests of Zimbabwe

Three isolates each, of nine different Trametes and five other wood inhabiting basidiomycetes, were collected from the indigenous forests of Zimbabwe, and the impact of temperature (20-60 degrees C), osmotic and matric potential (-0.5 to - 8.0 MPa), and their interactions on in vitro growth compared. Generally, there was no significant difference between growth of isolates of the same species in relation to temperature. Temperature relationships of the species studied correlated well with their geographic distributions. Species occurring in hot, dry regions tolerated a wide temperature range, with some showing unusually high thermotolerance (55 degrees, T. socotrana, T. cingulata and T. cervina). There were significant intra-strain differences for individual species in relation to solute potential on glycerol-modified media. Generally, growth of ail species was better on glycerol- and KCl-modified osmotic media than on a metrically-modified medium (PEG 8000) at 25, 30 and 37 degrees. The limits for growth on the osmotic media were significantly wider than matric medium, being - 4.5 to - 5.0 and - 2.5 to - 4.5 MPa, respectively. An Irpex sp. grew at lower water potentials than all other species, with good growth at - 7.0 MPa. This study suggests that the capacity of these fungi for effective growth over a range of temperatures, osmotic and matric potentials contributes to their rapid wood decay capacities in tropical climates.

Interpretation of electrochemical measurements made during micro-scale abrasion-corrosion

This paper brings together and analyzes recent work based on the interpretation of the electrochemical measurements made on a modified micro-abrasion-corrosion tester used in several research programmes. These programmes investigated the role of abradant size, test solution pH in abrasion-corrosion of biomaterials, the abrasion-corrosion performance of sintered and thermally sprayed tungsten carbide surfaces under downhole drilling environments and the abrasion-corrosion of UNS S32205 duplex stainless steel. Various abrasion tests were conducted under two-body grooving, three-body rolling and mixed grooving-rolling abrasion conditions, with and without abrasives, on cast F75 cobalt-chromium-molybdenum (CoCrMo) alloy in simulated body fluids, 2205 in chloride containing solutions as well as sprayed and sintered tungsten carbide surfaces in simulated downhole fluids. Pre- and post-test inspections based on optical and scanning electron microscopy analysis are used to help interpret the electrochemical response and current noise measurements made in situ during micro-abrasion-corrosion tests. The complex wear and corrosion mechanisms and their dependence on the microstructure and surface composition as a function of the pH, abrasive concentration, size and type are detailed and linked to the electrochemical signals. The electrochemical versus mechanical processes are plotted for different test parameters and this new approach is used to interpret tribo-corrosion test data to give greater insights into different tribo-corrosion systems. Thus new approaches to interpreting in-situ electrochemical responses to surfaces under different abrasive wear rates, different abrasives and liquid environments (pH and NaCl levels) are made. This representation is directly related to the mechano-electrochemical processes on the surface and avoids quantification of numerous synergistic, antagonistic and additive terms associated with repeat experiments. (C) 2010 Elsevier Ltd. All rights reserved.

Elastomeric Composites Based on Ethylene-Propylene-Diene Monomer Rubber and Conducting Polymer-Modified Carbon Black

Thermally stable elastomeric composites based on ethylene-propylene-diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via ""in situ"" deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300 degrees C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5-10 phr depending on the formulation and electrical dc conductivity values in the range of 1 x 10(-3) to 1 x 10(-2) S cm(-1) above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 30:897-906, 2009. (C) 2008 Society of Plastics Engineers

Sisal chemically modified with lignins: Correlation between fibers and phenolic composites properties

Sisal fibers have been chemically modified by reaction with lignins, extracted from sugarcane bagasse and Pinus-type wood and then hydroxymethylated, to increase adhesion in resol-type phenolic thermoset matrices. Inverse gas chromatography (IGC) results showed that acidic sites predominate for unmodified/modified sisal fibers and for phenolic thermoset, indicating that the phenolic matrix has properties that favor the interaction with sisal fibers. The IGC results also showed that the phenolic thermoset has a dispersive component closer to those of the modified fibers suggesting that thermoset interactions with the less polar modified fibers are favored. Surface SEM images of the modified fibers showed that the fiber bundle deaggregation increased after the treatment, making the interfibrillar structure less dense in comparison with that of unmodified fibers, which increased the contact area and encouraged microbial biodegradation in simulated soil. Water diffusion was observed to be faster for composites reinforced with modified fibers, since the phenolic resin penetrated better into modified fibers, thereby blocking water passage through their channels. Overall, composites` properties showed that modified fibers promote a significant reduction in the hydrophilic character, and consequently of the reinforced composite without a major effect on impact strength and with increased storage modulus. (c) 2008 Elsevier Ltd. All rights reserved.

Thermally flexible epoxy/cellulose blends mediated by an ionic liquid

Blends between the widely used thermoset resin, epoxy, and the most abundant organic material, natural cellulose are demonstrated for the first time. The blending modification induced by charge transfer complexes using a room temperature ionic liquid, leads to the formation of thermally flexible thermoset materials. The blend materials containing low concentrations of cellulose were optically transparent which indicates the miscibility at these compositions. We observed the existence of intermolecular hydrogen bonding between epoxy and cellulose in the presence of the ionic liquid, leading to partial miscibility between these two polymers. The addition of cellulose improves the tensile mechanical properties of epoxy. This study reveals the use of ionic liquids as a compatible processing medium to prepare epoxy thermosets modified with natural polymers.

Adsorption of CuX2 (X = Cl-, Br-, and ClO4-) on a silica gel surface chemically modified with thiazolidine-2-thione from acetone and ethanol solutions

The isotherms of adsorption of CuX2 (X = Cl-, Br, ClO4-,) by silica gel chemically modified with thiazolidine-2-thione were studied in acetone (ac) and ethanol (eth) solutions at 25 degrees C. The following equilibrium constants (in 1 mol(-1)) were determined: a) CuCl2, 1.9 x 10(3) (ac), 1.6 x 10(3) (eth); b) CuBr2, 1.7 x 10(3) (ac), 1.2 x 10(3) (eth); c) Cu(ClO4)(2), 1.1 x 10(3) (ac), 1.0 x 10(3) (eth). The electron spin resonance spectra of the surface complexes indicate a tetragonal distorted structure in the case of lower degrees of metal loading on the chemically modified surface. The d-d electronic transition spectra show that for the ClO4- complex, the peak of absorption did not change for any degree of metal loading, and for Cl- and Br complexes, the peak maxima shift to higher energy with lower metal loading.

Bioactive coating on titanium implants modified by Nd:YVO4 laser

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Collision free region determination by modified polygonal Boolean operations

Cutting and packing problems are found in numerous industries such as garment, wood and shipbuilding. The collision free region concept is presented, as it represents all the translations possible for an item to be inserted into a container with already placed items. The often adopted nofit polygon concept and its analogous concept inner fit polygon are used to determine the collision free region. Boolean operations involving nofit polygons and inner fit polygons are used to determine the collision free region. New robust non-regularized Boolean operations algorithm is proposed to determine the collision free region. The algorithm is capable of dealing with degenerated boundaries. This capability is important because degenerated boundaries often represent local optimal placements. A parallelized version of the algorithm is also proposed and tests are performed in order to determine the execution times of both the serial and parallel versions of the algorithm.

CHARACTERIZATION OF ASPHALT MATERIALS CONTAINING BIO OIL FROM MICHIGAN WOOD

The objective of this research is to develop sustainable wood-blend bioasphalt and characterize the atomic, molecular and bulk-scale behavior necessary to produce advanced asphalt paving mixtures. Bioasphalt was manufactured from Aspen, Basswood, Red Maple, Balsam, Maple, Pine, Beech and Magnolia wood via a 25 KWt fast-pyrolysis plant at 500 °C and refined into two distinct end forms - non-treated (5.54% moisture) and treated bioasphalt (1% moisture). Michigan petroleum-based asphalt, Performance Grade (PG) 58-28 was modified with 2, 5 and 10% of the bioasphalt by weight of base asphalt and characterized with the gas chromatography-mass spectroscopy (GC-MS), Fourier Transform Infra-red (FTIR) spectroscopy and the automated flocculation titrimetry techniques. The GC-MS method was used to characterize the Carbon-Hydrogen-Nitrogen (CHN) elemental ratio whiles the FTIR and the AFT were used to characterize the oxidative aging performance and the solubility parameters, respectively. For rheological characterization, the rotational viscosity, dynamic shear modulus and flexural bending methods are used in evaluating the low, intermediate and high temperature performance of the bio-modified asphalt materials. 54 5E3 (maximum of 3 million expected equivalent standard axle traffic loads) asphalt paving mixes were then prepared and characterized to investigate their laboratory permanent deformation, dynamic mix stiffness, moisture susceptibility, workability and constructability performance. From the research investigations, it was concluded that: 1) levo, 2, 6 dimethoxyphenol, 2 methoxy 4 vinylphenol, 2 methyl 1-2 cyclopentandione and 4-allyl-2, 6 dimetoxyphenol are the dominant chemical functional groups; 2) bioasphalt increases the viscosity and dynamic shear modulus of traditional asphalt binders; 3) Bio-modified petroleum asphalt can provide low-temperature cracking resistance benefits at -18 °C but is susceptible to cracking at -24 °C; 3) Carbonyl and sulphoxide oxidation in petroleum-based asphalt increases with increasing bioasphalt modifiers; 4) bioasphalt causes the asphaltene fractions in petroleum-based asphalt to precipitate out of the solvent maltene fractions; 5) there is no definite improvement or decline in the dynamic mix behavior of bio-modified mixes at low temperatures; 6) bio-modified asphalt mixes exhibit better rutting performance than traditional asphalt mixes; 7) bio-modified asphalt mixes have lower susceptibility to moisture damage; 8) more field compaction energy is needed to compact bio-modified mixes.

Oligodeoxynucleotide Duplexes Containing (5′S)-5′-C-Alkyl-Modified 2′-Deoxynucleosides: Can an Alkyl Zipper across the DNA Minor-Groove Enhance Duplex Stability?

10.1002/hlca.200390311.abs A series of oligonucleotides containing (5′S)-5′-C-butyl- and (5′S)-5′-C-isopentyl-substituted 2′-deoxyribonucleosides were designed, prepared, and characterized with the intention to explore alkyl-zipper formation between opposing alkyl chains across the minor groove of oligonucleotide duplexes as a means to modulate DNA-duplex stability. From four possible arrangements of the alkyl groups that differ in the density of packing of the alkyl chains across the minor groove, three (duplex types I–III, Fig. 2) could experimentally be realized and their duplex-forming properties analyzed by UV-melting curves, CD spectroscopy, and isothermal titration calorimetry (ITC), as well as by molecular modeling. The results show that all arrangements of alkyl residues within the minor groove of DNA are thermally destabilizing by 1.5–3°/modification in Tm. We found that, within the proposed duplexes with more loosely packed alkyl groups (type-III duplexes), accommodation of alkyl residues without extended distorsion of the helical parameters of B-DNA is possible but does not lead to higher thermodynamic stability. The more densely packed and more unevenly distributed arrangement (type-II duplexes) seems to suffer from ecliptic positioning of opposite alkyl groups, which might account for a systematic negative contribution to stability due to steric interactions. The decreased stability in the type-III duplexes described here may be due either to missing hydrophobic interactions of the alkyl groups (not bulky enough to make close contacts), or to an overcompensation of favorable alkyl-zipper formation presumably by loss of structured H2O in the minor groove.

Pond-Breeding Amphibian Species Distributions in a Beaver-Modified Landscape, Acadia National Park, Mount Desert Island, Maine

In order to maintain pond-breeding amphibian species richness, it is important to understand how both natural and anthropogenic disturbances affect species assemblages and individual species distributions both at the scale of individual ponds and at a larger landscape scale. The goal of this project was to investigate what characteristics of ponds and the surrounding wetland landscape were most effective in predicting pond-breeding species richness and the individual occurrence of wood frog (Rana sylvatica), bullfrog (Rana catesbeiana) and pickerel frog (Rana palustris) breeding sites in a beaver-modified landscape and how this landscape has changed over time. The wetland landscape of Acadia National Park was historically modified by the natural disturbance cycles of beaver (Castor cazadensis), and since their reintroduction to the island in 1921, beaver have played a large role in creating and maintaining palustrine wetlands. In 2000 and 2001, I studied pond-breeding amphibian assemblages at 71 palustrine wetlands in Acadia National Park, Mount Desert Island, Maine. I determined breeding presence of 7 amphibian species and quantified 15 variables describing local pond conditions and characteristics of the wetland landscape. I developed a priori models to predict sites with high amphibian species and used model selection with Akaike's Information Criterion (AIC) to identify important variables. Single species models were also developed to predict wood frog, bullfrog and pickerel frogs breeding presence. The variables for wetland connectivity by stream corridors and the presence of beaver disturbance were the most effective variables to predict sites with high amphibian richness. Wood frog breeding was best predicted by local scale variables describing temporary, fishless wetlands and the absence of active beaver disturbance. Abandoned beaver sites provided wood frog breeding habitat (70%) in a similar proportion to that found in non beaver-influenced sites (79%). In contrast, bullfrog breeding presence was limited to active beaver wetlands with fish and permanent water, and 80% of breeding sites were large (≥2ha in size). Pickerel frog breeding site selection was predicted best by the connectivity of sites in the landscape by stream corridors. Models including the presence of beaver disturbance, greater wetland perimeter and greater depth were included in the confidence set of pickerel frog models but showed considerably less support. Analysis of historic aerial photographs showed an 89% increase in the total number of ponded wetlands available in the landscape between the years of 1944 and 1997. Beaver colonization generally converted forested wetlands and riparian areas to open water and emergent wetlands. Temporal colonization of beaver wetlands favored large sites low in the watersheds and sites that were impounded later were generally smaller, higher in the watershed, and more likely to be abandoned. These results suggest that beaver have not only increased the number of available breeding sites in the landscape for pond-breeding amphibians, but the resulting mosaic of active and abandoned beaver wetlands also provides suitable breeding habitat for species with differing habitat requirements.

Novel organo-modifier for thermally-stable polymer-layered silicate nanocomposites

A new novel approach for the stabilisation of polymer-clay nanocomposites has been investigated based on reacting chemically an antioxidant function, a hindered phenol moiety, with an organic modifier based on a quaternary ammonium salt. The chemically linked antioxidant-containing organic modifier (AO-OM) was then introduced into natural montmorillonite (MMt) through a cation-exchange reaction resulting in antioxidant-containing organo-modified clay (AO-OM-MMt). The new antioxidant-containing modified clay, along with other organo-modified clays having a similar organo-modifier but without the reacted antioxidant, were characterised by spectroscopic, thermogravimetric and x-ray diffraction techniques and tested for their thermo-oxidative stability. PA11-based clay nanocomposites samples containing the AO-OM-MMt and the other organo-modified clays, both without and with an added (i.e. not chemically reacted) hindered phenol antioxidant (similar to the one used in the AO-OM) were prepared by melt processing and examined for their processing and long-term thermal-oxidative stability at high temperatures. It was shown that although the new organo-modifier, AO-OM, was also susceptible to the Hoffman elimination reaction, the nanocomposites containing this newly modified clay (PA11/AO-OM-MMt) showed higher melt processing and long-term thermo-oxidative stability, along with excellent clay dispersion and exfoliation, compared to the other PA11-nanocomposites examined here (with and without the conventionally added antioxidant). It is suggested here that the excellent overall performance observed for the PA11/AO-OM-MMt nanocomposites is due to an in-situ partial release of low molecular weight antioxidant species having stabilising functionalities that are capable of acting locally at the interface between the inorganic clay platelets and the polymeric matrix which is a critical area for the onset of degradation processes.

Urban Ponds as an Aquatic Biodiversity Resource in Modified Landscapes

Urbanization is a global process contributing to the loss and fragmentation of natural habitats. Many studies have focused on the biological response of terrestrial taxa and habitats to urbanization. However, little is known regarding the consequences of urbanization on freshwater habitats, especially small lentic systems. In this study we examined aquatic macroinvertebrate diversity (family and species level) and variation in community composition between 240 urban and 782 non-urban ponds distributed across the UK. Contrary to predictions, urban ponds supported similar numbers of invertebrate species and families compared to non-urban ponds. Similar gamma diversity was found between the two groups at both family and species taxonomic levels. The biological communities of urban ponds were markedly different to those of non-urban ponds and the variability in urban pond community composition was greater than that in non-urban ponds, contrary to previous work showing homogenisation of communities in urban areas. Positive spatial autocorrelation was recorded for urban and non-urban ponds at 0-50 km (distance between pond study sites) and negative spatial autocorrelation was observed at 100-150 km, and was stronger in urban ponds in both cases. Ponds do not follow the same ecological patterns as terrestrial and lotic habitats (reduced taxonomic richness) in urban environments; in contrast they support high taxonomic richness and contribute significantly to regional faunal diversity. Individual cities are complex structural mosaics which evolve over long periods of time and are managed in diverse ways, promoting the development of a wide-range of environmental conditions and habitat niches in urban ponds which can promote greater heterogeneity between pond communities at larger scales. Ponds provide an opportunity for managers and environmental regulators to conserve and enhance freshwater biodiversity in urbanized landscapes whilst also facilitating key ecosystem services including storm water storage and water treatment.