Selective oxidation of 5-hydroxymethylfurfural using monometallic and bimetallic supported nanoparticles

This work deals with the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) using metal supported catalysts. Catalysts were prepared from the immobilisation of preformed monometallic (Au, Pd) and bimetallic (AuCu, AuPd) nanoparticles on commercial oxides (TiO2, CeO2). Au-TiO2 catalyst was found to be very active for HMF oxidation; however, this system deactivated very fast. For this reason, we prepared bimetallic gold-copper nanoparticles and an increase in the catalytic activity was observed together with an increase in catalyst stability. In order to optimise the interaction of the metal active phase with the support, Au and AuCu nanoparticles were supported onto CeO2. Au-CeO2 catalyst was found to be more active than the bimetallic one, leading to the conclusion that in this case the most important feature is the interaction between gold and the support. Catalyst pre-treatments (calcination and washing) were carried out to maximise the contact between the metal and the oxide and an increase in the FDCA production could be observed. The presence of ceria defective sites was crucial for FDCA formation. Mesoporous cerium oxide was synthesised with the hard template method and was used as support for Au nanoparticles to promote the catalytic activity. In order to study the role of active phase in HMF oxidation, PdAu nanoparticles were supported onto TiO2. Au and Pd monometallic catalysts were very active in the formation of HMFCA (5-hydroxymethyl-2-furan carboxylic acid), but Pd was not able to convert it, leading to a low FDCA yield. The calcination of PdAu catalysts led to Pd segregation on the particles surface, which changed the reaction pathway and included an important contribution of the Cannizzaro reaction. PVP protected PdAu nanoparticles, synthesised with different morphologies (core-shell and alloyed structure), confirmed the presence of a different reaction mechanism when the metal surface composition changes.

Spawning coordination of mates in a shell brooding cichlid

Aim. External fertilisation requires synchronisation of gamete release between the two sexes. Adequate synchronisation is essential in aquatic media because sperm is very short-lived in water. In the cichlid Lamprologus callipterus, fertilisation of the eggs takes place inside an empty snail shell, where females stay inside the shell and males have to ejaculate into the shell opening. This spawning pattern makes the coordination of gamete release difficult. Methods. This study examined the synchronisation of males and females during egg laying. Results. The results showed that the male initiates each spawning sequence and that sperm release and egg laying are very well synchronised. 68% of all sperm releases occurred at exactly the same time when the female laid an egg, and 99% of ejaculations occurred within ±5 seconds from egg deposition. On average 95 eggs are laid one by one with intervals of several minutes between subsequent eggs, leading to a total spawning duration in excess of six hours. Conclusions. We discuss this exceptional spawning pattern and how it might reflect a conflict between the sexes, with males attempting to induce egg laying and females extending the egg laying period to raise the chance for parasitic males to participate in spawning.

Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

Morphological descriptions from the recent bivalve of the genus Calyptogena (Vesicomyidae)

The genus Calyptogena (Bivalvia: Vesicomyidae) comprises highly specialized bivalves living in symbiosis with sulphur-oxidizing bacteria in reducing habitats. In this study, the genus is revised using shell and anatomical features. The work is based on type material, as well as on the extensive collection of vesicomyids obtained during twelve expeditions to the Pacific and Indian Oceans. Nine Recent species are ascribed to the genus Calyptogena, four of which are new: C. pacifica Dall, 1891, C. fausta Okutani, Fujikura & Hashimoto, 1993, C. rectimargo Scarlato, 1981, C. valdiviae (Thiele & Jaeckel, 1931), C. gallardoi Sellanes & Krylova, 2005, C. goffrediae n. sp., C. starobogatovi n. sp., C. makranensis n. sp. and C. costaricana n. sp. The characteristic features of Calyptogena are: shell up to 90 mm in length, elongate-elliptical or elongate; presence of escutcheon; presence of broad posterior ramus (3b) of right subumbonal cardinal tooth as well as right posterior nymphal ridge; absence of pallial sinus as a result of attachment of intersiphonal septal retractor immediately adjacent to ventral surface of posterior adductor; absence of processes on inner vulva of inhalant siphon; presence of inner demibranch only, with descending and ascending lamellae with interlamellar septa not divided into separate tubes. The most closely related taxa to Calyptogena are probably the genus Isorropodon Sturany, 1896, and the group of species represented by 'Calyptogena' phaseoliformis Métivier, Okutani & Ohta, 1986. These groups have several characters in common, namely absence of pallial sinus, presence of single inner pair of demibranchs and absence of processes on inner vulva of inhalant siphon. The worldwide distribution of the genus Calyptogena suggests that methane seeps at continental margins are the major dispersal routes and that speciation was promoted by geographical isolation. Recent species diversity and fossil records indicate that the genus originated in the Pacific Ocean. Sufficient data to discuss the distribution at species level exist only for C. pacifica, which has a remarkably narrow bathymetric range. Published studies on the physiology of C. pacifica suggest that adaptation to a specific geochemical environment has led to coexisting vesicomyid genera. The bacteria-containing gill of C. pacifica and other Calyptogena species is one of the most specialized in the family Vesicomyidae and may reflect these ecological adaptations.

Seawater carbonate chemistry and biological processes of Mytilus edulis during experiments, 2010

Marine organisms are exposed to increasingly acidic oceans, as a result of equilibration of surface ocean water with rising atmospheric CO2 concentrations. In this study, we examined the physiological response of Mytilus edulis from the Baltic Sea, grown for 2 months at 4 seawater pCO2 levels (39, 113, 243 and 405 Pa/385, 1,120, 2,400 and 4,000 µatm). Shell and somatic growth, calcification, oxygen consumption and excretion rates were measured in order to test the hypothesis whether exposure to elevated seawater pCO2 is causally related to metabolic depression. During the experimental period, mussel shell mass and shell-free dry mass (SFDM) increased at least by a factor of two and three, respectively. However, shell length and shell mass growth decreased linearly with increasing pCO2 by 6-20 and 10-34%, while SFDM growth was not significantly affected by hypercapnia. We observed a parabolic change in routine metabolic rates with increasing pCO2 and the highest rates (+60%) at 243 Pa. excretion rose linearly with increasing pCO2. Decreased O:N ratios at the highest seawater pCO2 indicate enhanced protein metabolism which may contribute to intracellular pH regulation. We suggest that reduced shell growth under severe acidification is not caused by (global) metabolic depression but is potentially due to synergistic effects of increased cellular energy demand and nitrogen loss.

Seawater carbonate chemistry and biological processes of oysters Crassostrea virginica during experiments, 2010

Estuarine organisms are exposed to periodic strong fluctuations in seawater pH driven by biological carbon dioxide (CO2) production, which may in the future be further exacerbated by the ocean acidification associated with the global rise in CO2. Calcium carbonate-producing marine species such as mollusks are expected to be vulnerable to acidification of estuarine waters, since elevated CO2 concentration and lower pH lead to a decrease in the degree of saturation of water with respect to calcium carbonate, potentially affecting biomineralization. Our study demonstrates that the increase in CO2 partial pressure (pCO2) in seawater and associated decrease in pH within the environmentally relevant range for estuaries have negative effects on physiology, rates of shell deposition and mechanical properties of the shells of eastern oysters Crassostrea virginica (Gmelin). High CO2 levels (pH ~7.5, pCO2 ~3500 µatm) caused significant increases in juvenile mortality rates and inhibited both shell and soft-body growth compared to the control conditions (pH ~8.2, pCO2 ~380 µatm). Furthermore, elevated CO2 concentrations resulted in higher standard metabolic rates in oyster juveniles, likely due to the higher energy cost of homeostasis. The high CO2 conditions also led to changes in the ultrastructure and mechanical properties of shells, including increased thickness of the calcite laths within the hypostracum and reduced hardness and fracture toughness of the shells, indicating that elevated CO2 levels have negative effects on the biomineralization process. These data strongly suggest that the rise in CO2 can impact physiology and biomineralization in marine calcifiers such as eastern oysters, threatening their survival and potentially leading to profound ecological and economic impacts in estuarine ecosystems.

pH and calcium change in the microenvironment of a benthic foraminifer (Ammonia sp.) and its size during experiments

Calcareous foraminifera are well known for their CaCO3 shells. Yet, CaCO3 precipitation acidifies the calcifying fluid. Calcification without pH regulation would therefore rapidly create a negative feedback for CaCO3 precipitation. In unicellular organisms, like foraminifera, an effective mechanism to counteract this acidification could be the externalization of H+ from the site of calcification. In this study we show that a benthic symbiont-free foraminifer Ammonia sp. actively decreases pH within its extracellular microenvironment only while precipitating calcite. During chamber formation events the strongest pH decreases occurred in the vicinity of a newly forming chamber (range of gradient about 100 µm) with a recorded minimum of 6.31 (< 10 µm from the shell) and a maximum duration of 7 h. The acidification was actively regulated by the foraminifera and correlated with shell diameters, indicating that the amount of protons removed during calcification is directly related to the volume of calcite precipitated. The here presented findings imply that H+ expulsion as a result of calcification may be a wider strategy for maintaining pH homeostasis in unicellular calcifying organisms.

Limited effects of increased CO2 and temperature on metal and radionuclide bioaccumulation in a sessile invertebrate, the oyster Crassostrea gigas

This study investigated the combined effects of reduced pH and increased temperature on the capacities of the Pacific cupped oyster Crassostrea gigas to bioconcentrate radionuclide and metals. Oysters were exposed to dissolved radiotracers (110mAg, 241Am, 109Cd,57Co,54Mn, and 65Zn) at three pH (7.5, 7.8, 8.1) and two temperatures (21 and 24°C) under controlled laboratory conditions. Although calcifying organisms are recognized as particularly vulnerable to ocean acidification, the oyster did not accumulate differently the studied metals when exposed under the different pH conditions. However, temperature alone or in combination with pH somewhat altered the bioaccumulation of the studied elements. At pH 7.5, Cd was accumulated with an uptake rate constant twofold higher at 24°C than 21°C. Bioaccumulation of Mn was significantly affected by an interactive effect between seawater pH and temperature, with a decreased uptake rate at pH 7.5 when temperature increased (27 ± 1 vs. 17 ± 1 /day at 21 and 24°C, respectively). Retention of Co and Mn tended also to decrease at the same pH with decreasing temperature. Neither pH nor temperature affected strongly the elements distribution between shell and soft tissues. Significant effects of pH were found on the bioaccessibility of Mn, Zn, and 241Am during experimental in vitro simulation of human digestion.

Topological invariance and spatial scaling of surface roughness in two highly eroded zones of Mexico: a comparative study

The Fractal Image Informatics toolbox (Oleschko et al., 2008 a; Torres-Argüelles et al., 2010) was applied to extract, classify and model the topological structure and dynamics of surface roughness in two highly eroded catchments of Mexico. Both areas are affected by gully erosion (Sidorchuk, 2005) and characterized by avalanche-like matter transport. Five contrasting morphological patterns were distinguished across the slope of the bare eroded surface of Faeozem (Queretaro State) while only one (apparently independent on the slope) roughness pattern was documented for Andosol (Michoacan State). We called these patterns ?the roughness clusters? and compared them in terms of metrizability, continuity, compactness, topological connectedness (global and local) and invariance, separability, and degree of ramification (Weyl, 1937). All mentioned topological measurands were correlated with the variance, skewness and kurtosis of the gray-level distribution of digital images. The morphology0 spatial dynamics of roughness clusters was measured and mapped with high precision in terms of fractal descriptors. The Hurst exponent was especially suitable to distinguish between the structure of ?turtle shell? and ?ramification? patterns (sediment producing zone A of the slope); as well as ?honeycomb? (sediment transport zone B) and ?dinosaur steps? and ?corals? (sediment deposition zone C) roughness clusters. Some other structural attributes of studied patterns were also statistically different and correlated with the variance, skewness and kurtosis of gray distribution of multiscale digital images. The scale invariance of classified roughness patterns was documented inside the range of five image resolutions. We conjectured that the geometrization of erosion patterns in terms of roughness clustering might benefit the most semi-quantitative models developed for erosion and sediment yield assessments (de Vente and Poesen, 2005).

MIA - a free and open source software for gray scale medical image analysis

Background Gray scale images make the bulk of data in bio-medical image analysis, and hence, the main focus of many image processing tasks lies in the processing of these monochrome images. With ever improving acquisition devices, spatial and temporal image resolution increases, and data sets become very large. Various image processing frameworks exists that make the development of new algorithms easy by using high level programming languages or visual programming. These frameworks are also accessable to researchers that have no background or little in software development because they take care of otherwise complex tasks. Specifically, the management of working memory is taken care of automatically, usually at the price of requiring more it. As a result, processing large data sets with these tools becomes increasingly difficult on work station class computers. One alternative to using these high level processing tools is the development of new algorithms in a languages like C++, that gives the developer full control over how memory is handled, but the resulting workflow for the prototyping of new algorithms is rather time intensive, and also not appropriate for a researcher with little or no knowledge in software development. Another alternative is in using command line tools that run image processing tasks, use the hard disk to store intermediate results, and provide automation by using shell scripts. Although not as convenient as, e.g. visual programming, this approach is still accessable to researchers without a background in computer science. However, only few tools exist that provide this kind of processing interface, they are usually quite task specific, and don’t provide an clear approach when one wants to shape a new command line tool from a prototype shell script. Results The proposed framework, MIA, provides a combination of command line tools, plug-ins, and libraries that make it possible to run image processing tasks interactively in a command shell and to prototype by using the according shell scripting language. Since the hard disk becomes the temporal storage memory management is usually a non-issue in the prototyping phase. By using string-based descriptions for filters, optimizers, and the likes, the transition from shell scripts to full fledged programs implemented in C++ is also made easy. In addition, its design based on atomic plug-ins and single tasks command line tools makes it easy to extend MIA, usually without the requirement to touch or recompile existing code. Conclusion In this article, we describe the general design of MIA, a general purpouse framework for gray scale image processing. We demonstrated the applicability of the software with example applications from three different research scenarios, namely motion compensation in myocardial perfusion imaging, the processing of high resolution image data that arises in virtual anthropology, and retrospective analysis of treatment outcome in orthognathic surgery. With MIA prototyping algorithms by using shell scripts that combine small, single-task command line tools is a viable alternative to the use of high level languages, an approach that is especially useful when large data sets need to be processed.

Raman spectroscopy in Group IV nanowires and nanowire axial heterostructures

The control of the SiGe NW composition is fundamental for the fabrication of high quality heterostructures. Raman spectroscopy has been used to analyse the composition of SiGe alloys. We present a study of the Raman spectrum of SiGe nanowires and SiGe/Si heterostructures. The inhomogeneity of the Ge composition deduced from the Raman spectrum is explained by the existence of a Ge-rich outer shell and by the interaction of the NW with the electromagnetic field associated with the laser beam.

A large displacement structural analysis of a pipeline subjected to gravity and buoyancy forces

A nonlinear analysis of an elastic tube subjected to gravity forces and buoyancy pressure is carried out. An update lagrangian formulation is used. The structural analysis efficiency in terms of computer time and accuracy, has been improved when load stiffness matrices have been introduced. In this way the follower forces characteristics such as their intensity and direction changes can be well represented. A sensitivity study of different involved variables on the final deformed pipeline shape is carried out.

Book Review: Elastic Beams and Frames, by J. D. Renton

The book represents a very interesting example of the possibility to combine in a single publication basic theory of structures and quite advanced topics on the same subject. The author fulfills this objective in a reasonable size book, less than 400 pages divided into 15 chapters averaging 20 pages each plus 9 short appendices. A diskette is also included in the book. This diskette contains training as well practical executable programs on different aspects of structural analysis, such as cross-sections properties,general-purpose computer programs for the static, dynamic and stability analysis of simple bar structures, etc. The book figures are didactic and have been carefully drawn.

Numerical methods in Nonlinear Analysis of shell structures

The design of shell and spatial structures represents an important challenge even with the use of the modern computer technology.If we concentrate in the concrete shell structures many problems must be faced,such as the conceptual and structural disposition, optimal shape design, analysis, construction methods, details etc. and all these problems are interconnected among them. As an example the shape optimization requires the use of several disciplines like structural analysis, sensitivity analysis, optimization strategies and geometrical design concepts. Similar comments can be applied to other space structures such as steel trusses with single or double shape and tension structures. In relation to the analysis the Finite Element Method appears to be the most extended and versatile technique used in the practice. In the application of this method several issues arise. First the derivation of the pertinent shell theory or alternatively the degenerated 3-D solid approach should be chosen. According to the previous election the suitable FE model has to be adopted i.e. the displacement,stress or mixed formulated element. The good behavior of the shell structures under dead loads that are carried out towards the supports by mainly compressive stresses is impaired by the high imperfection sensitivity usually exhibited by these structures. This last effect is important particularly if large deformation and material nonlinearities of the shell may interact unfavorably, as can be the case for thin reinforced shells. In this respect the study of the stability of the shell represents a compulsory step in the analysis. Therefore there are currently very active fields of research such as the different descriptions of consistent nonlinear shell models given by Simo, Fox and Rifai, Mantzenmiller and Buchter and Ramm among others, the consistent formulation of efficient tangent stiffness as the one presented by Ortiz and Schweizerhof and Wringgers, with application to concrete shells exhibiting creep behavior given by Scordelis and coworkers; and finally the development of numerical techniques needed to trace the nonlinear response of the structure. The objective of this paper is concentrated in the last research aspect i.e. in the presentation of a state-of-the-art on the existing solution techniques for nonlinear analysis of structures. In this presentation the following excellent reviews on this subject will be mainly used.

The folded plate model in structural analysis. Elastic, plastic and dynamic formulations for nonprismatic structures

A specific numerical procedure for the analysis of arbitrary nonprismatic folded plate structures is presented. An elastic model is studied and compared with a harmonic solution for a prismatic structure. An extension to the plastic analysis is developed, and the influence of the structural geometry and loading pattern is analyzed. Nonprismatic practical cases, with arbitrary geometry and loading are shown, as well in the elastic range as in the plastic one. Finally, a dynamic formulation is outlined