Epoxy/Polycaprolactone Systems with Triple-Shape Memory Effect: Electrospun Nanoweb with and without Graphene Versus Co-Continuous Morphology

Triple-shape memory epoxy (EP)/polycaprolactone (PCL) systems (PCL content: 23 wt %) with different structures (PCL nanoweb embedded in EP matrix and EP/PCL with co-continuous phase structure) were produced. To set the two temporary shapes, the glass transition temperature (Tg) of the EP and the melting temperature (Tm) of PCL served during the shape memory cycle. An attempt was made to reinforce the PCL nanoweb by graphene nanoplatelets prior to infiltrating the nanoweb with EP through vacuum assisted resin transfer molding. Morphology was analyzed by scanning electron microscopy and Raman spectrometry. Triple-shape memory characteristics were determined by dynamic mechanical analysis in tension mode. Graphene was supposed to act also as spacer between the nanofibers, improving the quality of impregnation with EP. The EP phase related shape memory properties were similar for all systems, while those belonging to PCL phase depended on the structure. Shape fixity of PCL was better without than with graphene reinforcement. The best shape memory performance was shown by the EP/PCL with co-continuous structure. Based on Raman spectrometry results, the characteristic dimension of the related co-continuous network was below 900 nm

Effects of UV-B radiation on the structural and physiological diversity of bacterioneuston and bacterioplankton

The effects of UV radiation (UVR) on estuarine bacterioneuston and bacterioplankton were assessed in microcosm experiments. Bacterial abundance and DNA synthesis were more affected in bacterioplankton. Protein synthesis was more inhibited in bacterioneuston. Community analysis indicated that UVR has the potential to select resistant bacteria (e.g., Gammaproteobacteria), particularly abundant in bacterioneuston

Ecotoxicological effects of chemical contaminants adsorbed to microplastics in the clam Scrobicularia plana

Although microplastics (MPs) are distributed globally in the marine environment, a great deal of unknowns relating to their ecotoxicological effects on the marine biota remains. Due to their lipophilic nature, microplastics have the potential to adsorb persistent organic pollutants present in contaminated regions, which may increase their detrimental impact once assimilated by organisms. This study investigates the ecotoxicological effects of exposure to low-density polyethylene (LDPE) microplastics (11-13 beta m), with and without adsorbed contaminants (benzo[a]pyrene- BaP and perfluorooctane sulfonic acid-PFOS), in the peppery furrow shell clam, Scrobicularia plana. Environmentally relevant concentrations of contaminants (BaP-16.87 +/- 0.22 mu g g(-1) and PFOS-70.22 +/- 12.41 mu g g(-1)) were adsorbed to microplastics to evaluate the potential role of plastic particles as a source of chemical contamination once ingested. S. plana were exposed to microplastics, at a concentration of 1 mg L-1, in a water-sediment exposure setup for 14 days. Clams were sampled at the beginning of the experiment (day 0) and after 3, 7, and 14 days. BaP accumulation, in whole clam tissues, was analyzed. A multi-biomarker assessment was conducted in the gills, digestive gland, and haemolymph of clams to clarify the effects of exposure. This included the quantification of antioxidant (superoxide dismutase, catalase, glutathione peroxidase) and biotransformation (glutathione-Stransferases) enzyme activities, oxidative damage (lipid peroxidation levels), genotoxicity (single and double strand DNA breaks), and neurotoxicity (acetylcholinesterase activity). Results suggest a potential mechanical injury of gills caused by ingestion of microplastics that may also affect the analyzed biomarkers. The digestive gland seems less affected by mechanical damage caused by virgin microplastic exposure, with the MPs-adsorbed BaP and PFOS exerting a negative influence over the assessed biomarkers in this tissue.JPI Oceans FCT JPIOCEANS/0005/2015 JPI Oceans (BELSPO) JPI Oceans (FWO) JPI Oceans (FORMAS) JPI Oceans (SwAM) FCT UID/MAR/00350/2013info:eu-repo/semantics/publishedVersio

Impact of polystyrene microplastics on Daphnia magna mortality and reproduction in relation to food availability

Microplastics (MPs) in the environment continue to be a growing area of concern in terms of acute and chronic impacts on aquatic life. Whilst increasing numbers of studies are providing important insights into microparticle behaviour and impacts in the marine environment, a paucity of information exists regarding the freshwater environment. This study focusses on the uptake, retention and the impact of 2µm polystyrene MPs in the freshwater cladoceran Daphnia magna in relation to food intake (algae Chlorella vulgaris), with MP size chosen to approximately match the cell size of the algae. Daphnia were exposed to varied concentrations of MPs and algae. When exposed to a single concentration of MPs Daphnia almost immediately ingested them in large quantities. However, the presence of algae, even at low concentrations, had a significant negative impact on MP uptake that was not in proportion to relative availability. As MP concentrations increased, intake did not if algae were present, even at higher concentrations of MPs. This suggests that Daphnia are selectively avoiding ingesting plastics. Adult Daphnia exposed to MPs for 21 days showed mortality after 7 days of exposure in all treatments compared to the control. However significant differences were all related to algal concentration rather than to MP concentration. This suggests that where ample food is present, MPs have little effect on adults. There was also no impact on their reproduction. The neonate toxicity test confirmed previous results that mortality and reproduction was linked to availability of food rather than MP concentrations. This would make sense in light of our suggestion that Daphnia are selectively avoiding ingesting microplastics

Microplastics in Seawater: Recommendations from the Marine Strategy Framework Directive Implementation Process

Microplastic litter is a pervasive pollutant present in marine systems across the globe. The legacy of microplastics pollution in the marine environment today may remain for years to come due to the persistence of these materials. Microplastics are emerging contaminants of potential concern and as yet there are few recognized approaches for monitoring. In 2008, the EU Marine Strategy Framework Directive (MSFD, 2008/56/EC) included microplastics as an aspect to be measured. Here we outline the approach as discussed by the European Union expert group on marine litter, the technical Subgroup on Marine litter (TSG-ML), with a focus on the implementation of monitoring microplastics in seawater in European seas. It is concluded that harmonization and coherence is needed to achieve reliable monitoring

Isolation of microplastics in biota-rich seawater samples and marine organisms.

notes: PMCID: PMC3970126types: Journal Article; Research Support, Non-U.S. Gov'tThis is an open access article that is freely available in ORE or from the publisher's web site. Please cite the published version.Microplastic litter is a pervasive pollutant present in aquatic systems across the globe. A range of marine organisms have the capacity to ingest microplastics, resulting in adverse health effects. Developing methods to accurately quantify microplastics in productive marine waters, and those internalized by marine organisms, is of growing importance. Here we investigate the efficacy of using acid, alkaline and enzymatic digestion techniques in mineralizing biological material from marine surface trawls to reveal any microplastics present. Our optimized enzymatic protocol can digest >97% (by weight) of the material present in plankton-rich seawater samples without destroying any microplastic debris present. In applying the method to replicate marine samples from the western English Channel, we identified 0.27 microplastics m(-3). The protocol was further used to extract microplastics ingested by marine zooplankton under laboratory conditions. Our findings illustrate that enzymatic digestion can aid the detection of microplastic debris within seawater samples and marine biota.Natural Environment Research Council (NERC

Pharmacokinetic and Pharmacodynamic Challenges of Antibody-Directed Enzyme Prodrug Therapy (ADEPT)

Antibody-Directed Enzyme Prodrug Therapy (ADEPT) is an experimental cancer treatment. First, an antibody-enzyme is targeted to the tumour. After clearance from healthy tissue, a prodrug is administered and activated by the enzyme. MFE-CP, an anti-carcinoembryonic antibody fragment fused to the enzyme carboxypeptidase G2, has been used for ADEPT in combination with a nitrogen mustard prodrug. Clinical trials are encouraging but highlight major challenges of sub-optimal MFE-CP pharmacokinetics and drug resistance. This thesis explores means to address these challenges. MFE-CP, manufactured in P. pastoris, clears rapidly from the circulation due to yeast mannosylation. This leads to excellent tumour:blood ratios but decreased opportunity for tumour uptake. MFE-CP was therefore mutated in an attempt to reduce glycosylation. Initially, N-linked glycosylated asparagine residues were mutated to glutamine. The enzyme remained active but cleared rapidly in vivo. O-linked residue mutations were then explored. Changes that would least impede enzyme function were predicted using bioinformatics and a series of mutated constructs generated. The T55V mutation generated a functional enzyme that also cleared rapidly in vivo. The DNA damage response was investigated as a mechanism of drug resistance. Using the comet assay, DNA interstrand cross-links were shown to form rapidly in carcinoma cells and xenografts in response to ADEPT, but these were unhooked over 48 hours. The γ-H2AX and RAD51 response indicated unhooking was due to DNA damage repair. Cell cycle studies showed that ADEPT treatment also led to G2/M arrest. G2/M arrest allowed DNA repair to occur and it was hypothesised that ADEPT could be made more effective by blocking arrest and driving entry into mitosis. To test this hypothesis, Chk1 inhibitors, UCN-01 and PF-477736, were investigated. Results demonstrated an enhanced anticancer effect with the ADEPT and PF-477736 combination, whereby increased cell death was observed at 48 hours post treatment. The approach has potential for clinical translation

Sub-micron sized saccharide fibres via electrospinning

In this work, the production of continuous submicron diameter saccharide fibres is shown to be possible using the electrospinning process. The mechanism for the formation of electrospun polymer fibres is usually attributed to the physical entanglement of long molecular chains. The ability to electrospin continuous fibre from a low molecular weight saccharides was an unexpected phenomenon. The formation of sub-micron diameter “sugar syrup” fibres was observed in situ using high speed video. The trajectory of the electrospun saccharide fibre was observed to follow that typical of electrospun polymers. Based on initial food grade glucose syrup tests, various solutions based on combinations of syrup components, i.e. mono-, di- and tri-saccharides, were investigated to map out materials and electrospinning conditions that would lead to the formation of fibre. This work demonstrated that sucrose exhibits the highest propensity for fibre formation during electrospinning amongst the various types of saccharide solutions studied. The possibility of electrospinning low molecular weight saccharides into sub-micron fibres has implications for the electrospinability of supramolecular polymers and other biomaterial

Preformulation Studies of Furosemide-Loaded Electrospun Nanofibrous Systems for Buccal Administration

Furosemide loaded electrospun fibers were prepared for buccal administration, with the aim of improving the oral bioavailability of the poorly soluble and permeable crystalline drug, which can be achieved by the increased solubility and by the circumvention of the intensive first pass metabolism. The water soluble hydroxypropyl cellulose (HPC) was chosen as a mucoadhesive polymer. In order to improve the electrospinnability of HPC, poly (vinylpyrrolidone) (PVP) was used. During the experiments, the total polymer concentration was kept constant at 15% (w/w), and only the ratio of the two polymers (HPC-PVP = 5:5, 6:4, 7:3, 8:2, 9:1) was changed. A combination of rheological measurements with scanning electron microscopic morphological images of electrospun samples was applied for the determination of the optimum composition of the gels for fiber formation. The crystalline–amorphous transition of furosemide was tracked by Fourier transform infrared spectroscopy. A correlation was found between the rheological properties of the polymer solutions and their electrospinnability, and the consequent morphology of the resultant samples. With decreasing HPC ratio of the system, a transition from the spray-dried droplets to the randomly oriented fibrous structures was observed. The results enable the determination of the polymer ratio for the formation of applicable quality of electrospun fibers

Assessment of microplastic-sorbed contaminant bioavailability through analysis of biomarker gene expression in larval zebrafish

publisher: Elsevier articletitle: Assessment of microplastic-sorbed contaminant bioavailability through analysis of biomarker gene expression in larval zebrafish journaltitle: Marine Pollution Bulletin articlelink: http://dx.doi.org/10.1016/j.marpolbul.2016.12.055 content_type: article copyright: © 2016 The Authors. Published by Elsevier Ltd