Creation of an international laboratory network towards global microplastics monitoring harmonisation.

Infrastructure is often a limiting factor in microplastics research impacting the production of scientific outputs and monitoring data. International projects are therefore required to promote collaboration and development of national and regional scientific hubs. The Commonwealth Litter Programme and the Ocean Country Partnership Programme were developed to support Global South countries to take actions on plastics entering the oceans. An international laboratory network was developed to provide the infrastructure and in country capacity to conduct the collection and processing of microplastics in environmental samples. The laboratory network was also extended to include a network developed by the University of East Anglia, UK. All the laboratories were provided with similar equipment for the collection, processing and analysis of microplastics in environmental samples. Harmonised protocols and training were also provided in country during laboratory setup to ensure comparability of quality-controlled outputs between laboratories. Such large networks are needed to produce comparable baseline and monitoring assessments.

Unveiling the potential of cellulose, chitosan and polylactic acid as precursors for the production of green carbon nanofibers with controlled morphology and diameter.

Carbon nanofibers (CNFs) are very promising materials with application in many fields, such as sensors, filtration systems, and energy storage devices. This study aims to explore the use of eco-friendly biopolymers for CNF production, finding novel, suitable and sustainable precursors and thus prioritising environmentally conscious processes and ecological compatibility. Polymeric nanofibers (PNFs) using cellulose acetate, polylactic acid, and chitosan as precursors were successfully prepared via electrospinning. Rheological testing was performed to determine suitable solution concentrations for the production of PNFs with controlled diameter and appropriate morphology. Their dimensions and structure were found to be significantly influenced by the solution concentration and electrospinning flow rate. Subsequently, the electrospun green nanofibers were subject to stabilisation and carbonisation to convert them into CNFs. Thermal behaviour and chemical/structural changes of the nanofibers during stabilisation were investigated by means of thermogravimetric analysis and Fourier-transform infrared spectroscopy, while the final morphology of the fibers after stabilisation and carbonisation was examined through scanning electron microscopy to determine the optimal stabilisation parameters. The optimal fabrication parameters for cellulose and chitosan-based CNFs with excellent morphology and thermal stability were successfully established, providing valuable insight and methods for the sustainable and environmentally friendly synthesis of these promising materials.

Atmospheric microplastic transport and deposition to urban and pristine tropical locations in Southeast Asia.

Atmospheric microplastic transport is an important delivery pathway with the deposition of microplastics to ecologically important regions raising environmental concerns. Investigating atmospheric delivery pathways and their deposition rates in different ecosystems is necessary to understanding its global impact. In this study, atmospheric deposition was collected at three sites in Malaysia, two urban and one pristine, covering the Northeast and Southwest monsoons to quantify the role of this pathway in Southeast Asia. Air mass back trajectories showed long-range atmospheric transport of microplastics to all sites with atmospheric deposition varying from 114 to 689 MP/m2/day. For the east coast of Peninsular Malaysia, monsoonal season influenced microplastic transport and deposition rate with peak microplastic deposition during the Northeast monsoon due to higher wind speed. MP morphology combined with size fractionation and plastic type at the coastal sites indicated a role for long-range marine transport of MPs that subsequently provided a local marine source to the atmosphere at the coastal sites.

An Insight into the Growing Concerns of Styrene Monomer and Poly(Styrene) Fragment Migration into Food and Drink Simulants from Poly(Styrene) Packaging.

Poly(styrene) (PS) has been heavily utilised in disposable food packaging due to its insulating properties, optical translucency, and long-shelf life. Despite these desirable characteristics, (PS) poses toxicity concerns to human's health through styrene monomer leaching into foodstuffs. Environmental and marine hazards are another growing concerns due to improper and/or absence of recycling strategies and facilities. This preliminary work aims to investigate the effect of temperature, food composition and contact times on the migration of the styrene monomer from poly(styrene) food contact materials into food simulants. Poly(styrene) cups showed a relatively low level of styrene migration with the highest being 0.110 µg/mL, whereas food containers showed a much higher level of styrene leaching with up to 6 µg/mL. This could be due to an increase in the hydrophobicity of the simulants' characteristics from low to high fat content and the increase in the testing temperatures from 5 °C to 70 °C. ANOVA statistical analysis is used to compare the means of three or more groups of data, whereas t-test analysis is used to compare means of two groups. This was carried out on each individual sample to determine the significance of changing the temperature, simulant type, or both on the level of migration observed in the results. All significant values were tested at 95% confidence level p < 0.05, concluding that fat content and high temperatures were found to significantly increase the level of styrene migration. Nile Red staining method was used to demonstrate that particulate poly(styrene), as well as styrene monomer, migrated into tested food simulants from typical containers, which is becoming a cause for concern as evidence of microplastic ingestion increases.

PD1 blockade potentiates the therapeutic efficacy of photothermally-activated and MRI-guided low temperature-sensitive magnetoliposomes.

This study investigates the effect of PD1 blockade on the therapeutic efficacy of novel doxorubicin-loaded temperature-sensitive liposomes. Herein, we report photothermally-activated, low temperature-sensitive magnetoliposomes (mLTSL) for efficient drug delivery and magnetic resonance imaging (MRI). The mLTSL were prepared by embedding small nitrodopamine palmitate (NDPM)-coated iron oxide nanoparticles (IO NPs) in the lipid bilayer of low temperature-sensitive liposomes (LTSL), using lipid film hydration and extrusion. Doxorubicin (DOX)-loaded mLTSL were characterized using dynamic light scattering, differential scanning calorimetry, electron microscopy, spectrofluorimetry, and atomic absorption spectroscopy. Photothermal experiments using 808 nm laser irradiation were conducted. In vitro photothermal DOX release studies and cytotoxicity was assessed using flow cytometry and resazurin viability assay, respectively. In vivo DOX release and tumor accumulation of mLTSL(DOX) were assessed using fluorescence and MR imaging, respectively. Finally, the therapeutic efficacy of PD1 blockade in combination with photothermally-activated mLTSL(DOX) in CT26-tumor model was evaluated by monitoring tumor growth, cytokine release and immune cell infiltration in the tumor tissue. Interestingly, efficient photothermal heating was obtained by varying the IO NPs content and the laser power, where on-demand burst DOX release was achievable in vitro and in vivo. Moreover, our mLTSL exhibited promising MR imaging properties with high transverse r2 relaxivity (333 mM-1 s-1), resulting in superior MR imaging in vivo. Furthermore, mLTSL(DOX) therapeutic efficacy was potentiated in combination with anti-PD1 mAb, resulting in a significant reduction in CT26 tumor growth via immune cell activation. Our study highlights the potential of combining PD1 blockade with mLTSL(DOX), where the latter could facilitate chemo/photothermal therapy and MRI-guided drug delivery.

Inkjet Printing of Polyacrylic Acid-Coated Silver Nanoparticle Ink onto Paper with Sub-100 Micron Pixel Size.

Printed electronics (PE) technology shows huge promise for the realisation of low-cost and flexible electronics, with the ability to pattern heat- or pressure-sensitive materials. In future developments of the PE market, the ability to produce highly conductive, high-resolution patterns using low-cost and roll-to-roll processes, such as inkjet printing, is a critical technology component for the fabrication of printed electronics and displays. Here, we demonstrate inkjet printing of polyacrylic acid (PAA) capped silver nanoparticle dispersions onto paper for high-conductivity electronic interconnects. We characterise the resulting print quality, feature geometry and electrical performance of inkjet patterned features and demonstrate the high-resolution printing, sub-100 micron feature size, of silver nanoparticle materials onto flexible paper substrate. Printed onto photo-paper, these materials then undergo chemically triggered sintering on exposure to chloride contained in the paper. We investigated the effect of substrate temperature on the properties of printed silver material from room temperature to 50 °C. At room temperature, the resistivity of single layer printed features, of average thickness of 500 nm and width 85 µm, was found to be 2.17 × 10-7 Ω·m or 13 times resistivity of bulk silver (RBS). The resistivity initially decreased with an increase in material thickness, when achieved by overprinting successive layers or by decreasing print pitch, and a resistivity of around 10 times RBS was observed after overprinting two times at pitch 75 µm and with single pass print pitch of between 60 and 80 µm, resulting in line thickness up to 920 nm. On further increases in thickness the resistivity increased and reached 27 times RBS at print pitch of 15 µm. On moderate heating of the substrate to 50 °C, more compact silver nanoparticle films were formed, reducing thickness to 200 nm from a single pass print, and lower material resistivity approaching five times RBS was achieved.

Enhanced covalent p-phenylenediamine crosslinked graphene oxide membranes: Towards superior contaminant removal from wastewaters and improved membrane reusability.

The increasing depletion of freshwater necessitates the re-use and purification of wastewaters. Among the existing separation membrane materials, graphene oxide (GO) is a promising candidate, owing to its tunable physicochemical properties. However, the widening of GO membranes pore gap in aqueous environments is a major limitation. Crosslinking agents can be incorporated to alleviate this problem. This study describes a comparative analysis of uncrosslinked and p-Phenylenediamine (PPD) crosslinked GO membranes' water purification performance. Dip-coating and dip-assisted layer-by-layer methods were used to fabricate the uncrosslinked and crosslinked membranes respectively. The covalent interaction between GO and PPD was confirmed by Fourier Transform Infra-Red and X-ray Photoelectron Spectroscopy. The excellent membrane topographical continuity and intactness was assessed by means of Scanning Electron Microscopy, while water contact angle measurements were undertaken to evaluate and confirm membrane hydrophilicity. The improvement impact of the crosslinker was manifested on the enhancement of the stability and performance of the membranes during nanofiltration tests of aqueous solutions of methylene blue in a homemade nanofiltration cell operated at 1 bar.

Microplastic ingestion ubiquitous in marine turtles.

Despite concerns regarding the environmental impacts of microplastics, knowledge of the incidence and levels of synthetic particles in large marine vertebrates is lacking. Here, we utilize an optimized enzymatic digestion methodology, previously developed for zooplankton, to explore whether synthetic particles could be isolated from marine turtle ingesta. We report the presence of synthetic particles in every turtle subjected to investigation (n = 102) which included individuals from all seven species of marine turtle, sampled from three ocean basins (Atlantic [ATL]: n = 30, four species; Mediterranean (MED): n = 56, two species; Pacific (PAC): n = 16, five species). Most particles (n = 811) were fibres (ATL: 77.1% MED: 85.3% PAC: 64.8%) with blue and black being the dominant colours. In lesser quantities were fragments (ATL: 22.9%: MED: 14.7% PAC: 20.2%) and microbeads (4.8%; PAC only; to our knowledge the first isolation of microbeads from marine megavertebrates). Fourier transform infrared spectroscopy (FT-IR) of a subsample of particles (n = 169) showed a range of synthetic materials such as elastomers (MED: 61.2%; PAC: 3.4%), thermoplastics (ATL: 36.8%: MED: 20.7% PAC: 27.7%) and synthetic regenerated cellulosic fibres (SRCF; ATL: 63.2%: MED: 5.8% PAC: 68.9%). Synthetic particles being isolated from species occupying different trophic levels suggest the possibility of multiple ingestion pathways. These include exposure from polluted seawater and sediments and/or additional trophic transfer from contaminated prey/forage items. We assess the likelihood that microplastic ingestion presents a significant conservation problem at current levels compared to other anthropogenic threats.

Graphene Oxide in Lossy Mode Resonance-Based Optical Fiber Sensors for Ethanol Detection.

The influence of graphene oxide (GO) over the features of an optical fiber ethanol sensor based on lossy mode resonances (LMR) has been studied in this work. Four different sensors were built with this aim, each comprising a multimode optical fiber core fragment coated with a SnO2 thin film. Layer by layer (LbL) coatings made of 1, 2 and 4 bilayers of polyethyleneimine (PEI) and graphene oxide were deposited onto three of these devices and their behavior as aqueous ethanol sensors was characterized and compared with the sensor without GO. The sensors with GO showed much better performance with a maximum sensitivity enhancement of 176% with respect to the sensor without GO. To our knowledge, this is the first time that GO has been used to make an optical fiber sensor based on LMR.

A rapid-screening approach to detect and quantify microplastics based on fluorescent tagging with Nile Red.

A new approach is presented for analysis of microplastics in environmental samples, based on selective fluorescent staining using Nile Red (NR), followed by density-based extraction and filtration. The dye adsorbs onto plastic surfaces and renders them fluorescent when irradiated with blue light. Fluorescence emission is detected using simple photography through an orange filter. Image-analysis allows fluorescent particles to be identified and counted. Magnified images can be recorded and tiled to cover the whole filter area, allowing particles down to a few micrometres to be detected. The solvatochromic nature of Nile Red also offers the possibility of plastic categorisation based on surface polarity characteristics of identified particles. This article details the development of this staining method and its initial cross-validation by comparison with infrared (IR) microscopy. Microplastics of different sizes could be detected and counted in marine sediment samples. The fluorescence staining identified the same particles as those found by scanning a filter area with IR-microscopy.

Optical Fibre Sensors Using Graphene-Based Materials: A Review.

Graphene and its derivatives have become the most explored materials since Novoselov and Geim (Nobel Prize winners for Physics in 2010) achieved its isolation in 2004. The exceptional properties of graphene have attracted the attention of the scientific community from different research fields, generating high impact not only in scientific journals, but also in general-interest newspapers. Optical fibre sensing is one of the many fields that can benefit from the use of these new materials, combining the amazing morphological, chemical, optical and electrical features of graphene with the advantages that optical fibre offers over other sensing strategies. In this document, a review of the current state of the art for optical fibre sensors based on graphene materials is presented.

Magnetic hyperthermia controlled drug release in the GI tract: solving the problem of detection.

Drug delivery to the gastrointestinal (GI) tract is highly challenging due to the harsh environments any drug- delivery vehicle must experience before it releases it's drug payload. Effective targeted drug delivery systems often rely on external stimuli to effect release, therefore knowing the exact location of the capsule and when to apply an external stimulus is paramount. We present a drug delivery system for the GI tract based on coating standard gelatin drug capsules with a model eicosane- superparamagnetic iron oxide nanoparticle composite coating, which is activated using magnetic hyperthermia as an on-demand release mechanism to heat and melt the coating. We also show that the capsules can be readily detected via rapid X-ray computed tomography (CT) and magnetic resonance imaging (MRI), vital for progressing such a system towards clinical applications. This also offers the opportunity to image the dispersion of the drug payload post release. These imaging techniques also influenced capsule content and design and the delivered dosage form. The ability to easily change design demonstrates the versatility of this system, a vital advantage for modern, patient-specific medicine.

Molecularly Imprinted Polymer Coated Quantum Dots for Multiplexed Cell Targeting and Imaging.

Advanced tools for cell imaging are of great interest for the detection, localization, and quantification of molecular biomarkers of cancer or infection. We describe a novel photopolymerization method to coat quantum dots (QDs) with polymer shells, in particular, molecularly imprinted polymers (MIPs), by using the visible light emitted from QDs excited by UV light. Fluorescent core-shell particles specifically recognizing glucuronic acid (GlcA) or N-acetylneuraminic acid (NANA) were prepared. Simultaneous multiplexed labeling of human keratinocytes with green QDs conjugated with MIP-GlcA and red QDs conjugated with MIP-NANA was demonstrated by fluorescence imaging. The specificity of binding was verified with a non-imprinted control polymer and by enzymatic cleavage of the terminal GlcA and NANA moieties. The coating strategy is potentially a generic method for the functionalization of QDs to address a much wider range of biocompatibility and biorecognition issues.

A SPION-eicosane protective coating for water soluble capsules: Evidence for on-demand drug release triggered by magnetic hyperthermia.

An orally-administered system for targeted, on-demand drug delivery to the gastrointestinal (GI) tract is highly desirable due to the high instances of diseases of that organ system and harsh mechanical and physical conditions any such system has to endure. To that end, we present an iron oxide nanoparticle/wax composite capsule coating using magnetic hyperthermia as a release trigger. The coating is synthesised using a simple dip-coating process from pharmaceutically approved materials using a gelatin drug capsule as a template. We show that the coating is impervious to chemical conditions within the GI tract and is completely melted within two minutes when exposed to an RF magnetic field under biologically-relevant conditions. The overall simplicity of action, durability and non-toxic and inexpensive nature of our system demonstrated herein are key for successful drug delivery systems.

On-demand, magnetic hyperthermia-triggered drug delivery: optimisation for the GI tract.

An orally-administered vehicle for targeted, on-demand drug delivery to the gastrointestinal (GI) tract is highly desirable due to the high incidence of diseases of that organ system and harsh mechanical and physical conditions any such drug delivery vehicle has to endure. To that end, we present an iron oxide nanoparticle/wax composite capsule coating that protects the capsule contents from the highly variable chemical conditions of the GI tract. It can be triggered using magnetic hyperthermia initiated from an external AC magnetic field. The coating is produced from pharmaceutically approved materials and is applied using a simple dip-coating process using a gelatin drug capsule as a template. We show that the coating is impervious to chemical conditions found within the GI tract, but is completely melted within two minutes of magnetically-induced heating under biologically-relevant conditions of temperature, pH, buffer and external field strength, allowing the delivery and dispersal of the capsule contents. The overall simplicity of action, durability and non-toxic and inexpensive nature of our drug delivery vehicle demonstrated herein are key for successful drug delivery systems for the kinds of focal therapy being sought for modern precision medicine.

Copper-doped CdSe/ZnS quantum dots: controllable photoactivated copper(I) cation storage and release vectors for catalysis.

The first photoactivated doped quantum dot vector for metal-ion release has been developed. A facile method for doping copper(I) cations within ZnS quantum dot shells was achieved through the use of metal-dithiocarbamates, with Cu(+) ions elucidated by X-ray photoelectron spectroscopy. Photoexcitation of the quantum dots has been shown to release Cu(+) ions, which was employed as an effective catalyst for the Huisgen [3+2] cycloaddition reaction. The relationship between the extent of doping, catalytic activity, and the fluorescence quenching was also explored.

Holographic molecularly imprinted polymers for label-free chemical sensing.

Holographic molecularly imprinted polymer films for the use in chemical sensors are obtained in one step through photopolymerization with interfering laser beams. This results in hierarchical structuring at four length scales: micrometer-scale patterning of millimeter- to centimeter- size polymer objects with holographic optical properties, exhibiting nanometer-scale porosity and specific molecular recognition properties at the molecular scale through self-assembly. Specific binding of the target analyte testosterone is measured by diffraction analysis.

Synthesis and characterization of carbon nanotubes covalently functionalized with amphiphilic polymer coated superparamagnetic nanocrystals.

Herein, we report the synthesis of three covalently linked superparamagnetic nanocrystal-multi-walled carbon nanotube (MWCNT) composites. A generic strategy for amphiphilic polymer coating of nanocrystals and further functionalization for amide bond formation with the MWCNTs is discussed. This approach can in principle allow attachment of any colloidal nanocrystal to the MWCNTs. The materials were characterized at each stage of the syntheses using DLS, zeta-potential measurements, FT-IR, TEM, and XPS techniques. The practicality of this linkage is demonstrated by the reversible magnetic immobilization of these materials on an electrode during non-aqueous electrochemistry.

The relationship between redox enzyme activity and electrochemical potential-cellular and mechanistic implications from protein film electrochemistry.

In protein film electrochemistry a redox protein of interest is studied as an electroactive film adsorbed on an electrode surface. For redox enzymes this configuration allows quantification of the relationship between catalytic activity and electrochemical potential. Considered as a function of enzyme environment, i.e., pH, substrate concentration etc., the activity-potential relationship provides a fingerprint of activity unique to a given enzyme. Here we consider the nature of the activity-potential relationship in terms of both its cellular impact and its origin in the structure and catalytic mechanism of the enzyme. We propose that the activity-potential relationship of a redox enzyme is tuned to facilitate cellular function and highlight opportunities to test this hypothesis through computational, structural, biochemical and cellular studies.