Ecotoxicological Assessment of Microplastics and Cellulose Particles in the Galápagos Islands and Galápagos Penguin Food Web.

Microplastic pollution threatens some of the world's most iconic locations for marine biodiversity, including the remote Galápagos Islands, Ecuador. Using the Galápagos penguin (Spheniscus mendiculus) as a sentinel species, the present study assessed microplastics and suspected anthropogenic cellulose concentrations in surface seawater and zooplankton near Santa Cruz and Galápagos penguin colonies (Floreana, Isabela, Santiago), as well as in penguin potential prey (anchovies, mullets, milkfish) and penguin scat. On average, 0.40 ± 0.32 microplastics L-1 were found in surface seawater (<10 µm; n = 63 L), while 0.003, 0.27, and 5.12 microplastics individual-1 were found in zooplankton (n = 3372), anchovies (n = 11), and mullets (n = 6), respectively. The highest concentration (27 microplastics individual-1) was observed in a single milkfish. Calculations based on microplastics per gram of prey, in a potential diet composition scenario, suggest that the Galápagos penguin may consume 2881 to 9602 microplastics daily from prey. Despite this, no microplastics or cellulose were identified in 3.40 g of guano collected from two penguins. Our study confirms microplastic exposure in the pelagic food web and endangered penguin species within the UNESCO World Heritage site Galápagos Islands, which can be used to inform regional and international policies to mitigate plastic pollution and conserve biodiversity in the global ocean. Environ Toxicol Chem 2024;43:1442-1457. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Electrophoretic Deposition Interferometric Scattering Mass Photometry.

Interferometric scattering microscopy (iSCAT) has rapidly developed as a quantitative tool for the label-free detection of single macromolecules and nanoparticles. In practice, this measurement records the interferometric scattering signal of individual nanoparticles in solution as they land and stick on a coverslip, exhibiting an intensity that varies linearly with particle volume and an adsorption rate that reflects the solution-phase transport kinetics of the system. Together, such measurements provide a multidimensional gauge of the particle size and concentration in solution over time. However, the landing kinetics of particles in solution also manifest a measurement frequency limitation imposed by the slow long-range mobility of particle diffusion to the measurement interface. Here we introduce an effective means to overcome the inherent diffusion-controlled sampling limitation of spontaneous mass photometry. We term this methodology electrophoretic deposition interferometric scattering microscopy (EPD-iSCAT). This approach uses a coverslip supporting a conductive thin film of indium tin oxide (ITO). Charging this ITO film to a potential of around +1 V electrophoretically draws charged nanoparticles from solution and binds them in the focal plane of the microscope. Regulating this potential offers a direct means of controlling particle deposition. Thus, we find for a 0.1 nM solution of 50 nm polystyrene nanoparticles that the application of +1 V to an EPD-iSCAT coverslip assembly drives an electrophoretic deposition rate constant of 1.7 s-1 µm-2 nM-1. Removal of the potential causes deposition to cease. This user control of EPD-iSCAT affords a means to apply single-molecule mass photometry to monitor long-term changes in solution, owing to slow kinetic processes. In contrast with conventional coverslips chemically derivatized with charged thin films, EPD-iSCAT maintains a deposition rate that varies linearly with the bulk concentration.

Nanostructured Graphene Oxide Composite Membranes with Ultrapermeability and Mechanical Robustness.

Graphene oxide (GO) membranes have great potential for separation applications due to their low-friction water permeation combined with unique molecular sieving ability. However, the practical use of deposited GO membranes is limited by the inferior mechanical robustness of the membrane composite structure derived from conventional deposition methods. Here, we report a nanostructured GO membrane that possesses great permeability and mechanical robustness. This composite membrane consists of an ultrathin selective GO nanofilm (as low as 32 nm thick) and a postsynthesized macroporous support layer that exhibits excellent stability in water and under practical permeability testing. By utilizing thin-film lift off (T-FLO) to fabricate membranes with precise optimizations in both selective and support layers, unprecedented water permeability (47 L·m-2·hr-1·bar-1) and high retention (>98% of solutes with hydrated radii larger than 4.9 Å) were obtained.

Laser-Assisted Lattice Recovery of Graphene by Carbon Nanodot Incorporation.

Producing highly oriented graphene is a major challenge that constrains graphene from fulfilling its full potential in technological applications. The exciting properties of graphene are impeded in practical bulk materials due to lattice imperfections that hinder charge mobility. A simple method to improve the structural integrity of graphene by utilizing laser irradiation on a composite of carbon nanodots (CNDs) and 3D graphene is presented. The CNDs attach themselves to defect sites in the graphene sheets and, upon laser-assisted reduction, patch defects in the carbon lattice. Spectroscopic experiments reveal graphitic structural recovery of up to 43% and electrical conductivity four times larger than the original graphene. The composites are tested as electrodes in electrochemical capacitors and demonstrate extremely fast RC time constant as low as 0.57 ms. Due to their low defect concentrations, the reduced graphene oxide-carbon nanodot (rGO-CND) composites frequency response is sufficiently fast to operate as AC line filters, potentially replacing today's electrolytic capacitors. Using this methodology, demonstrated is a novel line filter with one of the fastest capacitive responses ever reported, and an aerial capacitance of 68.8 mF cm-2 . This result emphasizes the decisive role of structural integrity for optimizing graphene in electronic applications.

Patching laser-reduced graphene oxide with carbon nanodots.

Three-dimensional graphenes are versatile materials for a range of electronic applications and considered among the most promising candidates for electrodes in future electric double layer capacitors (EDLCs) as they are expected to outperform commercially used activated carbon. Parameters such as electrical conductivity and active surface area are critical to the final device performance. By adding carbon nanodots to graphene oxide in the starting material for our standard laser-assisted reduction process, the structural integrity (i.e. lower defect density) of the final 3D-graphene is improved. As a result, the active surface area in the hybrid starting materials was increased by 130% and the electrical conductivity enhanced by nearly an order of magnitude compared to pure laser-reduced graphene oxide. These improved material parameters lead to enhanced device performance of the EDLC electrodes. The frequency response, i.e. the minimum phase angle and the relaxation time, were significantly improved from -82.2° and 128 ms to -84.3° and 7.6 ms, respectively. For the same devices the specific gravimetric device capacitance was increased from 110 to a maximum value of 214 F g-1 at a scan rate of 10 mV s-1.

High-Throughput Continuous Production of Shear-Exfoliated 2D Layered Materials using Compressible Flows.

2D nanomaterials are finding numerous applications in next-generation electronics, consumer goods, energy generation and storage, and healthcare. The rapid rise of utility and applications for 2D nanomaterials necessitates developing means for their mass production. This study details a new compressible flow exfoliation method for producing 2D nanomaterials using a multiphase flow of 2D layered materials suspended in a high-pressure gas undergoing expansion. The expanded gas-solid mixture is sprayed in a suitable solvent, where a significant portion (up to 10% yield) of the initial hexagonal boron nitride material is found to be exfoliated with a mean thickness of 4.2 nm. The exfoliation is attributed to the high shear rates (γ˙ > 105 s-1 ) generated by supersonic flow of compressible gases inside narrow orifices and converging-diverging channels. This method has significant advantages over current 2D material exfoliation methods, such as chemical intercalation and exfoliation, as well as liquid phase shear exfoliation, with the most obvious benefit being the fast, continuous nature of the process. Other advantages include environmentally friendly processing, reduced occurrence of defects, and the versatility to be applied to any 2D layered material using any gaseous medium. Scaling this process to industrial production has a strong possibility of reducing the cost of creating 2D nanomaterials.

A Simple Route to Porous Graphene from Carbon Nanodots for Supercapacitor Applications.

A facile method to convert biomolecule-based carbon nanodots (CNDs) into high-surface-area 3D-graphene networks with excellent electrochemical properties is presented. Initially, CNDs are synthesized by microwave-assisted thermolysis of citric acid and urea according to previously published protocols. Next, the CNDs are annealed up to 400 °C in a tube furnace in an oxygen-free environment. Finally, films of the thermolyzed CNDs are converted into open porous 3D turbostratic graphene (3D-ts-graphene) networks by irradiation with an infrared laser. Based upon characterizations using scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, and Raman spectroscopy, a feasible reaction mechanism for both the thermolysis of the CNDs and the subsequent laser conversion into 3D-ts-graphene is presented. The 3D-ts-graphene networks show excellent morphological properties, such as a hierarchical porous structure and a high surface area, as well as promising electrochemical properties. For example, nearly ideal capacitive behavior with a volumetric capacitance of 27.5 mF L-1 is achieved at a current density of 560 A L-1 , which corresponds to an energy density of 24.1 mWh L-1 at a power density of 711 W L-1 . Remarkable is the extremely fast charge-discharge cycling rate with a time constant of 3.44 ms.

Characterization of Aniline Tetramer by MALDI TOF Mass Spectrometry upon Oxidative and Reductive Cycling.

By combining electrochemical experiments with mass spectrometric analysis, it is found that using short chain oligomers to improve the cycling stability of conducting polymers in supercapacitors is still problematic. Cycling tests via cyclic voltammetry over a potential window of 0 to 1.0 V or 0 to 1.2 V in a two-electrode device configuration resulted in solid-state electropolymerization and chain scission. Electropolymerization of the aniline tetramer to generate long chain oligomers is shown to be possible despite the suggested decrease in reactivity and increase in intermediate stability with longer oligomers. Because aniline oligomers are more stable towards reductive cycling when compared to oxidative cycling, future conducting polymer/oligomer-based pseudocapacitors should consider using an asymmetric electrode configuration.

Laser-scribed graphene presents an opportunity to print a new generation of disposable electrochemical sensors.

Graphene application within electrochemical sensing has been widely reported, but mainly as a composite, which adds summative effects to an underlying electrode. In this work we report the use of laser-scribed graphene as a distinct electrode patterned on a non-conducting flexible substrate. The laser-scribed graphene electrode compared favourably to established carbon macroelectrodes when evaluating both inner sphere and outer sphere redox probes, providing promise of extensive utility as an electrochemical sensor. The laser-scribed graphene electrode demonstrated the fastest heterogeneous electron transfer rate of all the electrodes evaluated with a k(0) of 0.02373 cm s(-1) for potassium ferricyanide, which exceeds commercially available edge plane pyrolytic graphite at 0.00260 cm s(-1), basal plane pyrolytic graphite at 0.00033 cm s(-1) and the very slow and effectively irreversible electrochemistry observed using single layer graphene. Finally and most significantly, a proof of principle system was fabricated using the laser-scribed graphene as working electrode, counter electrode and underlying base for the Ag/AgCl reference electrode, all in situ on the same planar flexible substrate, removing the requirement of macroscale external electrodes. The planar three electrode format operated with the same optimal electrode characteristics. Furthermore, the fabrication is inexpensive, scalable and compatible with a disposable biosensor format, considerably widening the potential applications in electrochemical bio-sensing for laser-scribed graphene.

Selected AB4(2-/-) (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn4(2-/-).

CAl(4)(2-/-) (D(4h), (1)A(1g)) is a cluster ion that has been established to be planar, aromatic, and contain a tetracoordinate planar C atom. Valence isoelectronic substitution of C with Si and Ge in this cluster leads to a radical change of structure toward distorted pentagonal species. We find that this structural change goes together with the cluster acquiring partial covalency of bonding between Si/Ge and Al(4), facilitated by hybridization of the atomic orbitals (AOs). Counter intuitively, for the AAl(4)(2-/-) (A = C, Si, Ge) clusters, hybridization in the dopant atom is strengthened from C, to Si, and to Ge, even though typically AOs are more likely to hybridize if they are closer in energy (i.e. in earlier elements in the Periodic Table). The trend is explained by the better overlap of the hybrids of the heavier dopants with the orbitals of Al(4). From the thus understood trend, it is inferred that covalency in such clusters can be switched off, by varying the relative sizes of the AOs of the main element and the dopant. Using this mechanism, we then successfully killed covalency in Si, and predicted a new aromatic cluster ion containing a tetracoordinate square planar Si, SiIn(4)(2-/-).