Dissociation of deprotonated microcystin variants by collision-induced dissociation following electrospray ionization

Microcystins (MC) are a family of hepatotoxic cyclic heptapeptides produced by a number of different cyanobacterial species. Considering the recent advances in the characterization of deprotonated peptides by mass spectrometry, the fragmentation behavior of four structurally related microcystin compounds was investigated using collision-induced dissociation (CID) experiments on an orbitrap mass spectrometer. It is demonstrated in this study that significant structural information can be obtained from the CID spectra of deprotonated microcystins. A predominant ring-opening reaction at the isoMeAsp residue, as well as two major complementary fragmentation pathways, was observed, reducing the complexity of the product ion spectra in comparison with spectra observed from protonated species. This proposed fragmentation behavior was applied to characterize [Leu(1)]MC-LR from a cyanobacterial cell extract. In conclusion, CID spectra of microcystins in the negative ion mode provide rich structurally informative mass spectra which greatly enhance confidence in structural assignments, in particular when combined with complementary positive ion CID spectra.     

IKNO,a user facility for coherent terahertz and UV synchrotron radiation

IKNO (Innovation and KNOwledge) is a proposal for a multi‐user facility based on an electron storage ring optimized for the generation of coherent synchrotron radiation (CSR) in the terahertz frequency range, and of broadband incoherent synchrotron radiation ranging from the IR to the VUV. IKNO can be operated in an ultra‐stable CSR mode with photon flux in the terahertz frequency region up to nine orders of magnitude higher than in existing third‐generation light sources. Simultaneously to the CSR operation, broadband incoherent synchrotron radiation up to VUV frequencies is available at the beamline ports. The main characteristics of the IKNO storage and its performance in terms of CSR and incoherent synchrotron radiation are described in this paper. The proposed location for the infrastructure facility is Sardinia, Italy.     

Fine structure of Mytella falcata (Bivalvia) gill filaments

Bivalve filter feeders are sessile animals that live in constant contact with water and its pollutants. Their gill is an organ highly exposed to these conditions due to its large surface and its involvement in gas exchanges and feeding. The bivalve Mytella falcata is found in estuaries of Latin America, on the Atlantic as well as the Pacific Coast. It is commonly consumed, and sometimes is the only source of protein of low-income communities. In this study, gill filaments of M. falcata were characterized using histology, histochemistry and transmission electron microscopy for future comparative studies among animals exposed to environmental pollutants. Gill filaments may be divided into abfrontal, intermediate and frontal zones. Filaments are interconnected by ciliary discs. In the center of filaments, haemocytes circulate through a haemolymph vessel internally lined by an endothelium and supported by an acellular connective tissue rich in polysaccharides and collagen. The abfrontal zone contains cuboidal cells, while the intermediate zone consists of a simple squamous epithelium. The frontal zone is composed of five columnar cell types: one absorptive, mainly characterized by the presence of pinocytic vesicles in the apical region of the cell; one secretory, rarely observed; and three ciliated with abundant mitochondria. All cells lining the filament exhibit numerous microvilli and seem to absorb substances from the environment. PAS staining was observed in mucous cells in the frontal and abfrontal zones. Bromophenol blue allowed the distinction of haemocytes and detection of a glycoprotein secretion in the secretory cells of the frontal region. The characteristics of M. falcata gill filaments observed in this study were very similar to those of other bivalves, especially other Mytilidae, and are suitable for histopathological studies on the effect of water-soluble pollutants.     

Ultramorphological characteristics of Chrysomya megacephala (Diptera, Calliphoridae) eggs and its eclosion

Chrysomya blowflies are originally from Africa and Australasia and were introduced in the American Continent, probably as a sheep parasite, in the 1970s. These flies are extremely important for medical-sanitary purposes and are useful to forensic entomology being used as an indicative of decomposition time in human corpses. The morphology of the larval and pupal stages of some species has been already studied by different authors demonstrating that it is possible to identify them in premature stages. In this study, Chrysomya megacephala egg ultramorphology was analyzed to describe its structure, generating data for further comparison between different species and genera. The blowflies were collected in Rio Claro city, SP, Brazil. Flies were attracted by fish carcasses and maintained in net cages; small portions of minced meat were placed in plastic pots for egg laying. Eggs were collected, fixed in alcoholic Bouin, prepared according to SEM routine and observed under Philips scanning electron microscope. C. megacephala eggs are oval with one flat face and another convex, measuring approximately 0.52 (+/-0.03) mm of length and 0.12 (+/-0.02) mm of width. The micropyle is circular in shape, with two perforations enclosed by countless small projections and is located in one of the extremities in the interface between the flat and convex faces. On the convex surface hexagonal imprints were observed, this surface is impermeable to water and gases. The flat surface has numerous round projections with different sizes, creating a permeable surface with a thinner chorion from which the larvae hatches. The larvae presents itself all wrinkled and with numerous cuticular projections with a thorn shape facing the posterior region. The cuticle projections with a thorn shape from C. megacephala larvae are probably a vestige of the thorns found in larvae of parasite Diptera.     

Raman evidence of the interaction between multiwalled carbon nanotubes and nanostructured TiO2

Nanocomposites of carbon nanotubes and titanium dioxide (TiO₂) have attracted much attention due to their photocatalytic properties. Although many examples in the literature have visualized these nanocomposites by electron microscopic images, spectroscopic characterization is still lacking with regard to the interaction between the carbon nanotube and TiO₂. In this work, we show evidence of the attachment of nanostructured TiO₂ to multiwalled carbon nanotubes (MWNTs) by Raman spectroscopy. The nanostructured TiO₂ was characterized by both full‐width at half‐maximum (FWHM) and the Raman shift of the TiO₂ band at ca 144 cm⁻¹, whereas the average diameter of the crystallite was estimated as approximately 7 nm. Comparison of the Raman spectra of the MWNTs and MWNTs/TiO₂ shows a clear inversion of the relative intensities of the G and D bands, suggesting a substantial chemical modification of the outermost tubes due to the attachment of nanostructured TiO₂. To complement the nanocomposite characterization, scanning electronic microscopy and X‐ray diffraction were performed. Copyright © 2011 John Wiley & Sons, Ltd.     

Closed-Loop Recycling of Vinylogous Urethane Vitrimers

Devising energy-efficient strategies for the depolymerization of plastics and the recovery of their structural components in high yield and purity is key to a circular plastics economy. Here, we report a case study in which we demonstrate that vinylogous urethane ( VU ) vitrimers synthesized from bis-polyethylene glycol acetoacetates ( aPEG ) and tris(2-aminoethyl)amine can be degraded by water at moderate temperature with almost quantitative recovery (≈98 %) of aPEG . The rate of depolymerization can be controlled by the temperature, amount of water, molecular weight of aPEG , and composition of the starting material. These last two parameters also allow one to tailor the mechanical properties of the final materials, and this was used to access soft, tough, and brittle vitrimers, respectively. The straightforward preparation and depolymerization of the aPEG -based VU vitrimers are interesting elements for the design of polymer materials with enhanced closed-loop recycling characteristics.     

Toughness of epoxies modified by preformed acrylic rubber particles

A bisphenol-A diglycidyl ether resin, cured with isophorone-diamine at 60°C, was modified by means of preformed core-shell acrylic rubber particles. Blends with rubber contents up to 30 phr by wt were tested. The fracture toughness depended linearly on the amount of rubber and significant improvement was found. No deterioration of temperature resistance was also observed. The viscosity of resin/modifier mixtures was controlled by means of antifoaming agents. A comparison with liquid acrylonitrile-butadiene copolymers showed that core-shell particles are efficacious tougheners. The effect of a bimodal particle size distribution was considered. In the size range investigated (0.2+5μm) no synergic effect was observed.     

Multi-Layer Pipes for Hydrocarbons Conveyance

The replacement of metals with plastics in piping systems is a well established practice in a vast range of public and industrial applications. However, difficulties still exist, mainly related to the limited chemical resistance of the polymers commonly used in pipe manufacturing to some conveyed fluids. This prevents using plastic pipes in important applications such as the transport of liquid hydrocarbons, particularly in oil fields. The use of chemically resistant polymers, such as fluorinated polyolefins, is precluded by high cost and poor mechanical properties. Co-extrusion of multi-layer pipes carrying an internal chemically resistant liner can be a viable alternative capable to extend the use of plastic pipes to refining and chemical industries. An experimental PE/PA multi-layer pipe has been developed whose resistance to diffusion and mechanical properties have been tested. Tests in real oil fields confirm the good performance of the new pipes.