Hydrogen-bonded interpolymer complexes. Formation, structure and applications

Noncovalent interactions play key roles in many natural processes leading to the self-assembly of molecules with the formation of supramolecular structures. One of the most important forces responsible for self-assembly is hydrogen bonding, which also plays an important role in the self-assembly of synthetic polymers in aqueous solutions. Proton-accepting polymers can associate with proton-donating polymers via hydrogen bonding in aqueous solutions and form polymer-polymer or interpolymer complexes. There has been an increased interest among researchers in hydrogen-bonded interpolymer complexes since the first pioneering papers were published in the early 1960s. Several hundred research papers have been published on various aspects of complex formation reactions in solutions and interfaces, properties of interpolymer complexes and their potential applications. This book focuses on the latest developments in the area of interpolymer complexation via hydrogen bonding. It represents a collection of original and review articles written by recognized experts from Germany, Greece, Kazakhstan, Poland, Romania, Russia, UK, Ukraine, and the USA. It highlights many important applications of interpolymer complexes, including the stabilization of colloidal systems, pharmaceuticals, and nanomaterials.

The application of ichnofabrics towards bridging the dichotomy between siliciclastic and carbonate shelf facies: examples from the Upper Jurassic Fulmar Formation (UK) and the Jubaila Formation (Saudi Arabia)

An initial study of the ichnofabrics of the Upper Jurassic (Kimmeridgian) Jubaila Formation of Saudi Arabia shows that the ichnofabrics are closely matched to the relatively well-described ichnofabrics of the contemporary Fulmar Formation of the UK Continental Shelf (North Sea), in respect of the lower shoreface/offshore transition facies to offshore facies. The ichnology and ichnofabrics of the Lower Jubaila Formation show that deposition took place on an open-marine platform on the Arabian craton subject to periodic storm activity, but under a persisting equilibrium between sediment accumulation and subsidence. This is consistent with the moderately deep-marine foraminiferal assemblages and the presence of calcareous nannofossils. Cyclicity is absent, though storm beds may be grouped, in contrast with the genetic sequences present in the rift and halokinetic scenario of the North Sea. In contrast with the siliciclastic setting hardgrotinds (with Gastrochaenolites), more common firmground omission surfaces, and micritic mudstones with Chondrites and Zoophycos are notable features of the carbonate facies. In siliciclastic successions (parasequences) the latter ichnotaxa are generally regarded as having been deposited in rather deeper water, but in the carbonate Jubaila Formation are interpreted as being associated with local areas of lower turbulence. Likewise, the hardgrounds and firmgrounds, which have not been traced laterally, are tentatively regarded to be of local significance.

Potato glycoalkaloids: formation and strategies for mitigation

With the increasing production and consumption of potato and its products, glycoalkaloid (GA) formation and toxicity are likely to become an important focus for food safety researchers and public health agencies. Not only the presence of GA, particularly in the form of a-solanine and a-chaconine, but also the changes occurring as a result of various post-harvest handling practices and storage, are critical issues influencing the quality of stored potatoes. Studies on various factors (pre-harvest, during harvest anal post-harvest) affecting GA have been carried out from time to time, but it is difficult to compare the results of one study with another due to wide variation in the parameters chosen. This review aims to develop a clear understanding of these issues. Published information on the types of GA, their effects on health, their typical concentrations in potatoes, their formation mechanisms, and how their levels can be controlled by following appropriate post harvest practices and storage regimes are critically analysed. The levels of GA in potato can be controlled effectively by adopting appropriate post-harvest practices. Further studies are necessary, however, to investigate best practices, which either check completely or retard substantially their formation. (C) 2008 Society of Chemical Industry.

Influence of the Photorhabdus luminescens phosphomannose isomerase gene, manA, on mannose utilization, exopolysaccharide structure, and biofilm formation

Extracellular polysaccharide (EPS) is produced by diverse bacterial pathogens and fulfills assorted roles, including providing a structural matrix for biofilm formation and more specific functions in virulence, such as protection against immune defenses. We report here the first investigation of some of the genes important for biofilm formation in Photorhabdus luminescens and demonstrate the key role of the phosphomannose isomerase gene, manA, in the structure of functional EPS. Phenotypic analyses of a manA-deficient mutant showed the importance of EPS in motility, insect virulence, and biofilm formation on abiotic surfaces as well as the requirement of this gene for the use of mannose as the sole carbon source. Conversely, this defect had no apparent impact on symbiosis with the heterorhabditid nematode vector. A more detailed analysis of biofilm formation revealed that the manA mutant was able to attach to surfaces with the same efficiency as that of the wild-type strain but could not develop the more extended biofilm matrix structures. A compositional analysis of P. luminescens EPS reveals how the manA mutation has a major effect on the formation of a complete, branched EPS.

Layers of nocturnal insect migrants at high-altitude: the influence of atmospheric conditions on their formation

1 Radar studies of nocturnal insect migration have often found that the migrants tend to form well-defined horizontal layers at a particular altitude. 2 In previous short-term studies, nocturnal layers were usually observed to occur at the same altitude as certain meteorological features, most notably at the altitudes of temperature inversions or nocturnal wind jets. 3 Statistical analyses are presented of four years’ data that compared the presence, sharpness and duration of nocturnal layer profiles (observed using continuously-operating entomological radar) with meteorological variables at typical layer altitudes over the UK. 4 Analysis of these large datasets demonstrated that temperature was the foremost meteorological factor persistently associated with the presence and formation of longer-lasting and sharper layers of migrating insects over southern UK.

Pb-210-Ra-226 and Ra-228-Th-232 systematics in young arc lavas: implications for magma degassing and ascent rates

New data show that island arc rocks have (Pb-210/Ra-226)(o) ratios which range from as low as 0.24 up to 2.88. In contrast, (Ra-22S/Th-232) appears always within error of I suggesting that the large Ra-226-excesses observed in arc rocks were generated more than 30 years ago. This places a maximum estimate on melt ascent velocities of around 4000 m/year and provides further confidence that the Ra-226 excesses reflect deep (source) processes rather than shallow level alteration or seawater contamination. Conversely, partial melting must have occurred more than 30 years prior to eruption. The Pb-210 deficits are most readily explained by protracted magma degassing. Using published numerical models, the data suggest that degassing occurred continuously for periods up to several decades just prior to eruption but no link with eruption periodicity was found. Longer periods are required if degassing is discontinuous, less than 100% efficient or if magma is recharged or stored after degassing. The long durations suggest much of this degassing occurs at depth with implications for the formation of hydrothermal and copper-porphyry systems. A suite of lavas erupted in 1985-1986 from Sangeang Api volcano in the Sunda arc are characterised by deficits of Pb-210 relative to Ra-226 from which 6-8 years of continuous Rn-222 degassing would be inferred from recent numerical models. These data also form a linear (Pb-210)/Pb-(Ra-226)/Pb array which might be interpreted as a 71-year isochron. However, the array passes through the origin suggesting displacement downwards from the equiline in response to degassing and so the slope of the array is inferred not to have any age significance. Simple modelling shows that the range of (Ra-226)/Pb ratios requires thousands of years to develop consistent with differentiation occurring in response to cooling at the base of the crust. Thus, degassing post-dated, and was not responsible for magma differentiation. The formation, migration and extraction of gas bubbles must be extremely efficient in mafic magma whereas the higher viscosity of more siliceous magmas retards the process and can lead to Pb-210 excesses. A possible negative correlation between (Pb-210/Ra-226)(o) and SO2 emission rate requires further testing but may have implications for future eruptions. (C) 2004 Elsevier B.V. All rights reserved.

Pb-210-Ra-226 and Ra-228-Th-232 systematics in young arc lavas: implications for magma degassing and ascent rates

New data show that island arc rocks have (Pb-210/Ra-226)(o) ratios which range from as low as 0.24 up to 2.88. In contrast, (Ra-22S/Th-232) appears always within error of I suggesting that the large Ra-226-excesses observed in arc rocks were generated more than 30 years ago. This places a maximum estimate on melt ascent velocities of around 4000 m/year and provides further confidence that the Ra-226 excesses reflect deep (source) processes rather than shallow level alteration or seawater contamination. Conversely, partial melting must have occurred more than 30 years prior to eruption. The Pb-210 deficits are most readily explained by protracted magma degassing. Using published numerical models, the data suggest that degassing occurred continuously for periods up to several decades just prior to eruption but no link with eruption periodicity was found. Longer periods are required if degassing is discontinuous, less than 100% efficient or if magma is recharged or stored after degassing. The long durations suggest much of this degassing occurs at depth with implications for the formation of hydrothermal and copper-porphyry systems. A suite of lavas erupted in 1985-1986 from Sangeang Api volcano in the Sunda arc are characterised by deficits of Pb-210 relative to Ra-226 from which 6-8 years of continuous Rn-222 degassing would be inferred from recent numerical models. These data also form a linear (Pb-210)/Pb-(Ra-226)/Pb array which might be interpreted as a 71-year isochron. However, the array passes through the origin suggesting displacement downwards from the equiline in response to degassing and so the slope of the array is inferred not to have any age significance. Simple modelling shows that the range of (Ra-226)/Pb ratios requires thousands of years to develop consistent with differentiation occurring in response to cooling at the base of the crust. Thus, degassing post-dated, and was not responsible for magma differentiation. The formation, migration and extraction of gas bubbles must be extremely efficient in mafic magma whereas the higher viscosity of more siliceous magmas retards the process and can lead to Pb-210 excesses. A possible negative correlation between (Pb-210/Ra-226)(o) and SO2 emission rate requires further testing but may have implications for future eruptions. (C) 2004 Elsevier B.V. All rights reserved.

Environmental factors and vegetation composition, Lefka Ori Massif, Crete, S. Aegean

Aim The aim of this study was to explore the environmental factors that determine the spatial distribution of oro-mediterranean and alti-mediterranean plant communities in Crete. Location The paper provides a quantitative analysis of vegetation-environment relationships for two study areas within the Lefka Ori massif Crete, a proposed Natura 2000 site. Methods Eleven environmental variables were recorded: altitude, slope, aspect, percentage of bare rock, percentage of unvegetated ground, soil depth, pH, organic matter content and percentages of sand, silt and clay content. Classification of the vegetation was based on twinspan, while detrended correspondence analysis (DCA) and canonical correspondence analysis (CCA) were used to identify environmental gradients linked to community distribution. Results One hundred and twenty-five species were recorded from 120 plots located within the two study areas. Forty-seven of the recorded species are endemic, belonging to 35 families. Hemicryptophytes and chamaephytes were the most frequent, suggesting a typical oro-mediterranean life form spectrum. The samples were classified into five main community types and one transitional. The main gradients, identified by CCA, were altitude and surface cover type in the North-west site, while in the Central site the gradients were soil formation-development and surface cover type. Main conclusions The use of classification in combination with ordination techniques resulted in a good discrimination between plant communities and a greater understanding of controlling environmental factors. The methodology adopted can be employed for improving baseline information on plant community ecology and distribution in Mediterranean mountain zones.

Comparison between observations and models of the Mozambique Channel transport: Seasonal cycle and eddy frequencies

A time series of the observed transport through an array of moorings across the Mozambique Channel is compared with that of six model runs with ocean general circulation models. In the observations, the seasonal cycle cannot be distinguished from red noise, while this cycle is dominant in the transport of the numerical models. It is found, however, that the seasonal cycles of the observations and numerical models are similar in strength and phase. These cycles have an amplitude of 5 Sv and a maximum in September, and can be explained by the yearly variation of the wind forcing. The seasonal cycle in the models is dominant because the spectral density at other frequencies is underrepresented. Main deviations from the observations are found at depths shallower than 1500 m and in the 5/y–6/y frequency range. Nevertheless, the structure of eddies in the models is close to the observed eddy structure. The discrepancy is found to be related to the formation mechanism and the formation position of the eddies. In the observations, eddies are frequently formed from an overshooting current near the mooring section, as proposed by Ridderinkhof and de Ruijter (2003) and Harlander et al. (2009). This causes an alternation of events at the mooring section, varying between a strong southward current, and the formation and passing of an eddy. This results in a large variation of transport in the frequency range of 5/y–6/y. In the models, the eddies are formed further north and propagate through the section. No alternation similar to the observations is observed, resulting in a more constant transport.

Simulating the formation of secondary organic aerosol from the photooxidation of aromatic hydrocarbons

The formation and composition of secondary organic aerosol (SOA) from the photooxidation of benzene, p-xylene, and 1,3,5-trimethylbenzene has been simulated using the Master Chemical Mechanism version 3.1 (MCM v3.1) coupled to a representation of the transfer of organic material from the gas to particle phase. The combined mechanism was tested against data obtained from a series of experiments conducted at the European Photoreactor (EUPHORE) outdoor smog chamber in Valencia, Spain. Simulated aerosol mass concentrations compared reasonably well with the measured SOA data only after absorptive partitioning coefficients were increased by a factor of between 5 and 30. The requirement of such scaling was interpreted in terms of the occurrence of unaccounted-for association reactions in the condensed organic phase leading to the production of relatively more nonvolatile species. Comparisons were made between the relative aerosol forming efficiencies of benzene, toluene, p-xylene, and 1,3,5-trimethylbenzene, and differences in the OH-initiated degradation mechanisms of these aromatic hydrocarbons. A strong, nonlinear relationship was observed between measured (reference) yields of SOA and (proportional) yields of unsaturated dicarbonyl aldehyde species resulting from ring-fragmenting pathways. This observation, and the results of the simulations, is strongly suggestive of the involvement of reactive aldehyde species in association reactions occurring in the aerosol phase, thus promoting SOA formation and growth. The effect of NO, concentrations on SOA formation efficiencies (and formation mechanisms) is discussed.

Heat-inactivated peroxidases and the role of calcium abstraction as a cause of their enhanced lipid oxidation activity: potential effects on the flavour quality of heat-processed vegetables

Cationic swede and anionic turnip peroxidases were partially purified by ion-exchange and gel-filtration chromatography, respectively. Heat treatment of these enzymes and of a commercial high purity horseradish peroxidase (HRP) caused a loss of enzyme activity and a corresponding increase in linoleic acid hydroperoxide formation activity. The hydroperoxide levels in model systems increased only in the early stages of the oxidation reaction and then declined as degradation became more significant. The presence of a dialysed blend of cooked swede markedly lowered the hydroperoxide level formed. Analysis of volatile compounds formed showed that hexanal predominated in a buffer system and in a blend of cooked turnip. In dialysed blends of cooked swede, hexanol was the primary volatile compound generated. After inactivation under mild conditions in the presence of EDTA, the peroxidases showed hydroperoxide formation activity and patterns of volatile compounds from linoleic acid that were similar to those found on heat-inactivation. This suggested that calcium abstraction from the peroxidases was critical for the enhancement of lipid oxidation activity. (C) 2002 Elsevier Science Ltd. All rights reserved.