Silane functionalization of perfluoroether oligomers for reaction management and morphology control of two‐phase epoxy networks

Mixtures of an epoxy resin, hardener, and acid functionalized perfluoroether oligomers will readily undergo phase separation during curing. However, the conditions to bring about the growth of nuclei into microscopic particles have hitherto been found only for systems cured with anhydrides. In the present study perfluoroether oligomers were functionalized by established procedures to introduce both carboxylic acid groups and alkoxysilane groups in sites within the chain extended segments. The presence of alkoxysilane groups together with the prereaction step with an excess epoxy resin, prior to the addition of the aromatic amine hardener, induced phase separation by a nucleation‐and‐growth mechanism. The dual functionality in the perfluoroether oligomer was even more beneficial when the alkoxysilane groups were hydrolyzed prior to the addition of the amine hardener. Under such circumstances the precipitation of the perfluoroether oligomer occurred quantitatively, as indicated by the complete absence of any plasticization effects in the epoxy matrix. From electron microscopy examinations, thermal analysis, and measurements of mechanical properties it was possible to deduce a plausible mechanism for the formation of the typical core‐shell aggregates within the precipitated particles for these systems, which could also be applied to other systems, such as those using carboxylic‐acid‐terminated butadiene acrylonitrile oligomers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1036–1049, 2005     

Apparatus and procedure for measuring release rates from formulations of lepidopteran semiochemicals

An apparatus was developed wherein a vacuum source was used to pull air across a controlled-release-formulation dispenser or a planchet containing a known quantity of a semiochemical and into a collector filled with a polymeric adsorbent. After a set time, the semiochemical was eluted with solvent and was quantified by gas-liquid chromatography (GLC). High percentages of known quantities of the lepidopteran semiochemicals (Z)-7-dodecen-l -ol acetate (Z7DDA), boiling point (bp) 275 ° C/1 atm, (Z)-9-tetradecen-1-ol formate (Z9TDF), bp 289 °C/1 atm, and (Z,Z)-3,13-octadecadien-1-ol acetate (ZZODDA), bp 490 °C/1 atm, were recovered. The semiochemicals did not oxidize and were recovered quantitatively from the adsorbent. The release rates of Z9TDF from a controlled-release dispenser were found to be directly proportional to the airflow rates. Release rate measurements on the Z9TDF dispensers were made for the purpose of estimating the method's precision. The method was shown to give internally consistent results by measurements on another Z9TDF formulation. The accuracy of the method is discussed.Mention of a commercial or proprietary product in this paper does not constitute an endorsement by the USDA.     

The hydrocarbon fraction of virgin olive oil and changes resulting from refining

In numerous Spanish virgin olive oils, 6,10-dimethyl-1-undecene, various sesquiterpenes, the series ofn-alkanes from C14 to C35, n-8-heptadecene and squalene are the only less volatile components detected by gas chromatography in the hydrocarbon fraction. In oils from olives of the Arbequine variety, a series ofn-9-alkenes has also been found. In refined oils, notable features are the absence of the most volatile compounds and the appearance of other hydrocarbons produced during the refining process. Among these,n-alkanes, alkadienes (mainlyn-hexacosadiene), stigmasta-3,5-diene, isomerization products of squalene, isoprenoidal polyolefins coming from hydroxy derivatives of squalene and steroidal hydrocarbons derived from 24-methylene cycloartanol were identified. Physical refining produces larger amounts of degradation products and greater losses ofn-alkanes than chemical processing. Squalene is the major hydrocarbon component in all oils, both virgin and refined. The ranges of concentration for the different hydrocarbons found in Spanish virgin olive oils are presented.     

A variable gap penalty function and feature weights for protein 3-D structure comparisons

We have developed a variable gap penalty function for use inthe comparison program COMPARER which aligns protein sequenceson the basis of their 3-D structures. For deletions and insertions,components are a function of structural features of individualamino acid residues (e.g. secondary structure and accessibility).We have also obtained relative weights for different featuresused in the comparison by examining the equivalent residuesin weight matrices and in alignments for pairs of 3-D structureswhere the equivalences are relatively unambiguous. We have usedthe new parameters and the varible gap penalty function in COMPARERto align protein structures in the Brookhaven Data Bank. Thevariable gap penalty function is useful especially in avoidinggaps in secondary structure elements and the new feature weightsgive improved alignments. The alignments for both azurins andplastocyanins and N- and C-terminal lobes for aspartic proteinasesare discussed     

Swelling and mechanical properties of cellulose hydrogels. I. Preparation,characterization, and swelling behavior

Cellulose hydrogels have been synthesized by reacting solutions of cellulose xanthate with different amounts of epichlorohydrin (0–24% w/w on cellulose) after which the cellulose was regenerated. The weight fraction of crystalline cellulose, determined by density measurements, decreases with the extent of chemical crosslinking and was estimated to vary between 30 and 42% for dry gels. The degree of equilibrium swelling in water of the prepared hydrogels varied between 3.05 and 6.33 g water/g dry gel (g/g). The degree of swelling decreases with increasing chemical crosslinking. As a result of the irreversible changes occurring during drying, the degree of swelling in water can be reduced down to 0.74 g/g. According to density gradient column measurements, the partial specific volume of water is 0.865 cm³/g at water contents below 0.13 g/g. It is suggested that water having this partial specific volume is the specific hydration water. At higher water contents, the partial specific volume of gel water equals the specific volume of bulk water. It is implicit in the interpretation of the density data in terms of a two state model of gel water that the crystallinity of cellulose is independent of the water content. Depending on the degree of swelling, heat treatment resulted in either an irreversible increase or decrease of the degree of swelling.     

Development of Habitat Suitability Criteria and In‐Stream Habitat Assessment for the Benthic Cyanobacteria Phormidium

Global demand for freshwater has led to unprecedented levels of water abstraction from riverine systems. This has resulted in large alterations in natural river flows. The deleterious impacts of reduced flows on fish and macroinvertebrate abundances have been thoroughly investigated; in contrast, there is a limited understanding of the potential for changes in the abundance of nuisance benthic algal/cyanobacterial blooms. In New Zealand, Phormidium sp. blooms are common in numerous rivers during summer low flows. In this study, an in‐stream habitat assessment is used to examine the relationship between Phormidium habitat availability and reducing flows. Over 650 observations of Phormidium mats, from seven sites (Hutt River, lower North Island, New Zealand), were used to construct habitat suitability curves for depth, velocity and substrate. Preference curves were fitted using both the ‘forage ratio’ and ‘quantile regression’ methods. Phormidium growth, observed at all seven sites, increased significantly from upstream (uppermost site, 5.2% mat cover) to downstream (63.5%). The habitat suitability curves revealed Phormidium had a large tolerance to velocity, depth and substrate type. Consequently, decreases in flow had only negligible effects on available Phormidium habitat. During periods of stable flow, Phormidium abundance positively correlated with increased nitrogen concentrations, potentially explaining the large variation in Phormidium cover from upstream to downstream. Quantile regression generated habitat suitability criteria were a more accurate predictor of available Phormidium habitat than the forage ratio criteria. Copyright © 2013 John Wiley & Sons, Ltd.