Synthetic mimetics of the endogenous gastrointestinal nanomineral: Silent constructs that trap macromolecules for intracellular delivery.

Amorphous magnesium-substituted calcium phosphate (AMCP) nanoparticles (75-150nm) form constitutively in large numbers in the mammalian gut. Collective evidence indicates that they trap and deliver luminal macromolecules to mucosal antigen presenting cells (APCs) and facilitate gut immune homeostasis. Here, we report on a synthetic mimetic of the endogenous AMCP and show that it has marked capacity to trap macromolecules during formation.

Seasonal variation and sources of dissolved trace metals in Maó Harbour, Minorca Island.

The environmental conditions of semi-enclosed coastal water-bodies are directly related to the catchment, human activities, and oceanographic setting in which they are located. As a result of low tidal forcing, and generally weak currents, waters in Mediterranean harbours are poorly renewed, leading to quality deterioration. Here, we characterise the seasonal variation of trace metals (i.

Influence of temperature on toxicity of single pharmaceuticals and mixtures, in the crustacean A. desmarestii.

Lethal and sublethal responses of the shrimp Atyaephyra desmarestii exposed to three pharmaceutical compounds, Diclofenac (DF), Ibuprofen (IB) and Carbamazepine (CBZ), individually and in mixtures, were evaluated under two temperature scenarios. LC50 (96h) values were obtained individually at 20° and 25°C. At 25°C, mortality in binary and ternary mixtures is higher than at 20°C.

Daily rhythms of digestive enzyme activity and gene expression in gilthead seabream (Sparus aurata) during ontogeny.

In order to identify daily changes in digestive physiology in developing gilthead seabream larvae, the enzyme activity (trypsin, lipases and α-amylase) and gene expression (trypsinogen-try, chymotrypsinogen-ctrb, bile salt-activated lipase-cel1b, phospholipase A2-pla2 and α-amylase-amy2a) were measured during a 24h cycle in larvae reared under a 12h light/12h dark photoperiod. Larvae were sampled at 10, 18, 30 and 60days post-hatch. In each sampling day, larvae were sampled every 3h during a complete 24h cycle.

Chemically Induced Cryptic Sesquiterpenoids and Expression of Sesquiterpene Cyclases in Botrytis cinerea Revealed New Sporogenic (+)-4-Epieremophil-9-en-11-ols.

The sequencing of the genomes of the B05.10 and T4 strains of the fungus Botrytis cinerea revealed an abundance of novel biosynthetic gene clusters, the majority of which were unexpected on the basis of the previous analyses of the fermentation of these and closely related species. By systematic alteration of easy accessible cultivation parameters, using chemical induction with copper sulfate, we have found a cryptic sesquiterpenoid family with new structures related to eremophil-9-ene, which had the basic structure of the sesquiterpene (+)-5-epiaristolochene ((+)-4-epieremophil-9-ene).

Toxicity of seabird guano to sea urchin embryos and interaction with Cu and Pb.

Guano is an important source of marine-derived nutrients to seabird nesting areas. Seabirds usually present high levels of metals and other contaminants because the bioaccumulation processes and biotic depositions can increase the concentration of pollutants in the receiving environments. The objectives of this study were to investigate: the toxicity of seabird guano and the joint toxicity of guano, Cu and Pb by using the sea urchin embryo-larval bioassay.

Cloning and molecular ontogeny of digestive enzymes in fed and food-deprived developing gilthead seabream (Sparus aurata) larvae.

We have determined the expression pattern of key pancreatic enzymes precursors (trypsinogen, try; chymotrypsinogen, ctrb; phospholipase A2, pla2; bile salt-activated lipase, cel; and α-amylase, amy2a) during the larval stage of gilthead seabream (Sparus aurata) up to 60days after hatching (dph). Previously, complete sequences of try, cel, and amy2a were cloned and phylogenetically analyzed. One new isoform was found for cel transcript (cel1b).

Are sunscreens a new environmental risk associated with coastal tourism?

The world coastal-zone population and coastal tourism are expected to grow during this century. Associated with that, there will be an increase in the use of sunscreens and cosmetics with UV-filters in their formulation, which will make coastal regions worldwide susceptible to the impact of these cosmetics. Recent investigations indicate that organic and inorganic UV-filters, as well as many other components that are constituents of the sunscreens, reach the marine environment--directly as a consequence of water recreational activities and/or indirectly from wastewater treatment plants (WWTP) effluents.

Citrate gold nanoparticle exposure in the marine bivalve Ruditapes philippinarum: uptake, elimination and oxidative stress response.

Gold nanoparticles (AuNPs) are considered an important nano-sized component of the twenty-first century. Due to their unique physical and chemical properties, they are being used and developed for a wide range of promising applications in medicine, biology and chemistry. Notwithstanding their useful aspects, in recent years concern has been raised over their ability to enter cells, organelles and nuclei and provoke oxidative stress.

Titanium carbenoid-mediated cyclopropanation of allylic alcohols: selectivity and mechanism.

A new method for the chemo- and stereoselective conversion of allylic alcohols into the corresponding cyclopropane derivatives has been developed. The cyclopropanation reaction was carried out with an unprecedented titanium carbenoid generated in situ from Nugent's reagent, manganese and methylene diiodide. The reaction involving the participation of an allylic hydroxyl group, proceeded with conservation of the alkene geometry and in a high diastereomeric excess.

Reactivity indices for natural bond orbitals: a new methodology.

A new reactivity index has been defined; this parameter is focused on a molecule's natural bond orbitals (NBOs) and derives in a natural way from Fukui functions. NBOs have the advantage of being very localized, allowing the reaction site of an electrophile or nucleophile to be determined within a very precise molecular region. Finally, the indices for a representative set of organic molecules were calculated and their usefulness tested on some protonation reactions.

An endogenous nanomineral chaperones luminal antigen and peptidoglycan to intestinal immune cells.

In humans and other mammals it is known that calcium and phosphate ions are secreted from the distal small intestine into the lumen. However, why this secretion occurs is unclear. Here, we show that the process leads to the formation of amorphous magnesium-substituted calcium phosphate nanoparticles that trap soluble macromolecules, such as bacterial peptidoglycan and orally fed protein antigens, in the lumen and transport them to immune cells of the intestinal tissue.

Importance of subcellular metal partitioning and kinetics to predicting sublethal effects of copper in two deposit-feeding organisms.

The role of subcellular partitioning of copper on the sublethal effects to two deposit-feeding organisms (41-day growth in the bivalve Tellina deltoidalis and 11-day reproduction in the amphipod Melita plumulosa) was assessed for copper-spiked sediments with different geochemical properties. Large differences in bioaccumulation and detoxification strategies were observed. The bivalve accumulated copper faster than the amphipod, and can be considered a relatively strong net bioaccumulator.

The asymmetric total synthesis of cinbotolide: a revision of the original structure.

The structure 3,4-dihydroxy-2,4,6,8-tetramethyldec-8-enolide (1) was assigned to a metabolite of Botrytis cinerea, but the spectra of several synthetic analogues had significant differences from that of 1. Examination of the constituents of a B. cinerea mutant that overproduces polyketides gave sufficient quantities of 1, now named cinbotolide, for chemical transformations.

Introducing "UCA-FUKUI" software: reactivity-index calculations.

A new software (UCA-FUKUI) has been developed to facilitate the theoretical study of chemical reactivity. This program can calculate global parameters like hardness, softness, philicities, and Fukui condensed functions, and also local parameters from the condensed functions. To facilitate access to the program we have developed a very easy-to-use interface.

Trace element contamination in the Guadalquivir River Estuary ten years after the Aznalcóllar mine spill.

Sediments, clams Scrobicularia plana and worms Hediste diversicolor from the Guadalquivir estuary were collected ten years after the Aznalcóllar mine spill and analyzed for metals. Significant seasonal and spatial effects were detected for most elements, so data from different sampling periods and locations were treated separately. Overall, the most polluted sites were found upstream, although Zn and Cu tended to accumulate at the estuary mouth.

Cathodic pseudopolarography: a new tool for the identification and quantification of cysteine, cystine and other low molecular weight thiols in seawater.

Thiols are compounds of paramount importance in the cellular metabolism due to their double detoxifying role as radical scavengers and trace metal ligands. However, we have scarce information about their extracellular cycling as limited data are available about their concentration, stability and speciation in the aquatic medium. In natural waters, they form part of the pool of reduced sulfur substance (RSS) whose presence has been documented by voltammetric and chromatographic methods.

Are the shells of Scrobicularia plana useful for monitoring trace metal pollution events?

The rupture of a mine dam in Aznalcóllar (SW Spain) in April 1998 entailed the contamination of Guadalquivir River and its estuary. To study the ability of bivalve shells to monitor the temporal changes on metal composition in the area, two year old Scrobicularia plana were obtained from two different locations of the estuary (Pantalan highly influenced and Pantoca less influenced) during the year 2000 and 2007. Co, Hg, Mo, Ni and Zn content was measured in shell and soft tissue of S.

Towards an integrated environmental risk assessment of emissions from ships' propulsion systems.

Large ships, particularly container ships, tankers, bulk carriers and cruise ships are significant individual contributors to air pollution. The European Environment Agency recognizes that air pollution in Europe is a local, regional and transborder problem caused by the emission of specific pollutants, which either directly or through chemical reactions lead to negative impacts, such as damage to human health and ecosystems. In the Marine Strategy Framework Directive 2008/56/EC of the European Parliament emissions from ships are mentioned explicitly in the list of pressures and impacts that should be reduced or minimized to maintain or obtain a good ecological status.

Pain exacerbates chronic mild stress-induced changes in noradrenergic transmission in rats.

Depression can influence pain and vice versa, yet the biological mechanisms underlying how one influences the pathophysiology of the other remains unclear. Dysregulation of locus coeruleus-noradrenergic transmission is implicated in both conditions, although it is not known whether this effect is exacerbated in cases of co-morbid depression and chronic pain. We studied locus coeruleus activity using immunofluorescence and electrophysiological approaches in rats subjected to unpredictable chronic mild stress (CMS, an experimental model of depression) and/or chronic constriction injury (CCI, a model of chronic neuropathic pain) for 2 weeks.

Tolerance of polar phytoplankton communities to metals.

Large amounts of pollutants reach polar regions, particularly the Arctic, impacting their communities. In this study we analyzed the toxic levels of Hg, Cd and Pb to natural phytoplankton communities of the Arctic and Southern Oceans, and compared their sensitivities with those observed on phytoplankton natural communities from temperate areas. Mercury was the most toxic metal for both Arctic and Antarctic communities, while both Cd and Pb were toxic only for the Antarctic phytoplankton.

Is Atyaephyra desmarestii a useful candidate for lethal and sub-lethal toxicity tests on pharmaceutical compounds?

Single and mixture toxicity tests on three pharmaceutical compounds, Diclofenac (DF), Ibuprofen (IB) and Carbamazepine (CBZ), were carried out with the freshwater shrimp Atyaephyra desmarestii. Lethal and sublethal responses were analyzed for single compounds. Lethal concentrations (LC50) obtained for each individual compound, after 96 h of exposure, were 6.

Simple strategy for producing superhydrophobic nanocomposite coatings in situ on a building substrate.

Numerous superhydrophobic materials have been developed in recent years by using a combination of two strategies: reducing the surface free energy and roughening the surface. Most of these procedures have the serious drawback of involving tedious multistage processes, which prevent their large-scale application, such as on the external stone and similar material surfaces of buildings exposed to the weather. This paper describes an innovative synthesis route for producing superhydrophobic surface coatings.

Demonstrating the appropriateness of developing sediment quality guidelines based on sediment geochemical properties.

The pool of bioavailable metals in sediments is typically much smaller than the total metal concentration and is strongly influenced by metal-binding with acid-volatile sulfide (AVS), particulate organic carbon (OC), and iron and manganese oxide solid phases. We have investigated how the properties of relatively oxidized sediments influence the exposure and effects of copper on the survival and growth rate of the deposit-feeding benthic bivalve Tellina deltoidalis. Growth rate was a much more sensitive end point than survival.