The occurrence of microplastics (MPs) in saltwater bodies is relatively well studied, but nothing is known about their presence in most of the commercial salts that are widely consumed by humans across the globe. Here, we extracted MP-like particles larger than 149 μm from 17 salt brands originating from 8 different countries followed by the identification of their polymer composition using micro-Raman spectroscopy. Microplastics were absent in one brand while others contained between 1 to 10 MPs/Kg of salt. Out of the 72 extracted particles, 41.6% were plastic polymers, 23.6% were pigments, 5.50% were amorphous carbon, and 29.1% remained unidentified. The particle size (mean ± SD) was 515 ± 171 μm. The most common plastic polymers were polypropylene (40.0%) and polyethylene (33.3%). Fragments were the primary form of MPs (63.8%) followed by filaments (25.6%) and films (10.6%). According to our results, the low level of anthropogenic particles intake from the salts (maximum 37 particles per individual per annum) warrants negligible health impacts. However, to better understand the health risks associated with salt consumption, further development in extraction protocols are needed to isolate anthropogenic particles smaller than 149 μm.
Inspired by natural muscle, a key challenge in soft robotics is to develop self-contained electrically driven soft actuators with high strain density. Various characteristics of existing technologies, such as the high voltages required to trigger electroactive polymers ( > 1KV), low strain ( < 10%) of shape memory alloys and the need for external compressors and pressure-regulating components for hydraulic or pneumatic fluidicelastomer actuators, limit their practicality for untethered applications. Here we show a single self-contained soft robust composite material that combines the elastic properties of a polymeric matrix and the extreme volume change accompanying liquid-vapor transition. The material combines a high strain (up to 900%) and correspondingly high stress (up to 1.3 MPa) with low density (0.84 g cm(-3)). Along with its extremely low cost (about 3 cent per gram), simplicity of fabrication and environment-friendliness, these properties could enable new kinds of electrically driven entirely soft robots.The development of self-contained electrically driven soft actuators with high strain density is difficult. Here the authors show a single self-contained soft robust composite material that combines the elastic properties of a polymeric matrix and the extreme volume change accompanying liquid vapour transition.
Much physiological and behavioral evidence has been provided suggesting that insect Odorant Binding Proteins (OBPs) are indispensable for odorant recognition and thus appealing targets for structure-based discovery and design of novel host-seeking disruptors. Despite the fact that more than 60 putative OBP-encoding genes have been identified in the malaria vector Anopheles gambiae, the crystal structures of only six of them are known. It is therefore clear that OBP structure determination constitutes the bottle-neck for structure-based approaches to mosquito repellent/attractant discovery. Here, we describe the three dimensional structure of an Anopheles gambiae “Plus-C” group OBP, AgamOBP48, which exhibits the second highest expression levels in female antennae. This structure represents the first example of a 3D domain-swapped dimer in dipteran species. A combined binding site is formed at the dimer interface by equal contribution of each monomer. Structural comparisons with the monomeric AgamOBP47 revealed that the major structural difference between the two “Plus-C” proteins localizes in their N- and C-terminal regions and their concerted conformational change may account for monomer-swapped dimer conversion and, furthermore, the formation of novel binding pockets. Using a combination of gel filtration chromatography, differential scanning calorimetry and analytical ultracentrifugation, we demonstrate the AgamOBP48 dimerization in solution. Eventually, molecular modelling calculations were used to predict the binding mode of the most potent synthetic ligand of AgamOBP48 known so far, discovered by ligand- and structure-based virtual screening. The structure-aided identification of multiple OBP-binders represents a powerful tool to be employed in the effort to control the vector-borne diseases transmission.
Here we describe the synthesis and biological properties of two types of star-shaped polymer-doxorubicin conjugates: non-targeted conjugate prepared as long-circulating high-molecular-weight (HMW) polymer prodrugs with a dendrimer core and a targeted conjugate with the anti-CD20 monoclonal antibody (mAb) rituximab (RTX). The copolymers were linked to the dendrimer core or to the reduced mAb via one-point attachment forming a star-shaped structure with a central antibody or dendrimer surrounded by hydrophilic polymer chains. The anticancer drug doxorubicin (DOX) was attached to the N-(2-hydroxypropyl)methacrylamide (HPMA)-based copolymer chain in star polymer systems via a pH-labile hydrazone linkage. Such polymer-DOX conjugates were fairly stable in aqueous solutions at pH 7.4, and the drug was readily released in mildly acidic environments at pH 5-5.5 by hydrolysis of the hydrazone bonds. The cytotoxicity of the polymer conjugates was tested on several CD20-positive or negative human cell lines. Similar levels of in vitro cytotoxicity were observed for all tested polymer conjugates regardless of type or structure. In vivo experiments using primary cell-based murine xenograft models of human diffuse large B-cell lymphoma confirmed the superior anti-lymphoma efficacy of the polymer-bound DOX conjugate when compared with the original drug. Targeting with RTX did not further enhance the anti-lymphoma efficacy relative to the non-targeted star polymer conjugate. Two mechanisms could play roles in these findings: changes in the binding ability to the CD-20 receptor and a significant loss of the immunological properties of RTX in the polymer conjugates.
Understanding high-velocity microparticle impact is essential for many fields, from space exploration to medicine and biology. Investigations of microscale impact have hitherto been limited to post-mortem analysis of impacted specimens, which does not provide direct information on the impact dynamics. Here we report real-time multi-frame imaging studies of the impact of 7 μm diameter glass spheres traveling at 700-900 m/s on elastomer polymers. With a poly(urethane urea) (PUU) sample, we observe a hyperelastic impact phenomenon not seen on the macroscale: a microsphere undergoes a full conformal penetration into the specimen followed by a rebound which leaves the specimen unscathed. The results challenge the established interpretation of the behaviour of elastomers under high-velocity impact.
Plastics are synthetic polymers derived from fossil oil and largely resistant to biodegradation. Polyethylene (PE) and polypropylene (PP) represent ∼92% of total plastic production. PE is largely utilized in packaging, representing ∼40% of total demand for plastic products (www.plasticseurope.org) with over a trillion plastic bags used every year . Plastic production has increased exponentially in the past 50 years (Figure S1A in Supplemental Information, published with this article online). In the 27 EU countries plus Norway and Switzerland up to 38% of plastic is discarded in landfills, with the rest utilized for recycling (26%) and energy recovery (36%) via combustion (www.plasticseurope.org), carrying a heavy environmental impact. Therefore, new solutions for plastic degradation are urgently needed. We report the fast bio-degradation of PE by larvae of the wax moth Galleria mellonella, producing ethylene glycol.
We present a new 4D printing approach that can create high resolution (up to a few microns), multimaterial shape memory polymer (SMP) architectures. The approach is based on high resolution projection microstereolithography (PμSL) and uses a family of photo-curable methacrylate based copolymer networks. We designed the constituents and compositions to exhibit desired thermomechanical behavior (including rubbery modulus, glass transition temperature and failure strain which is more than 300% and larger than any existing printable materials) to enable controlled shape memory behavior. We used a high resolution, high contrast digital micro display to ensure high resolution of photo-curing methacrylate based SMPs that requires higher exposure energy than more common acrylate based polymers. An automated material exchange process enables the manufacture of 3D composite architectures from multiple photo-curable SMPs. In order to understand the behavior of the 3D composite microarchitectures, we carry out high fidelity computational simulations of their complex nonlinear, time-dependent behavior and study important design considerations including local deformation, shape fixity and free recovery rate. Simulations are in good agreement with experiments for a series of single and multimaterial components and can be used to facilitate the design of SMP 3D structures.
High thermal conductivity is critical for many applications of polymers (for example, packaging of light-emitting diodes), in which heat must be dissipated efficiently to maintain the functionality and reliability of a system. Whereas uniaxially extended chain morphology has been shown to significantly enhance thermal conductivity in individual polymer chains and fibers, bulk polymers with coiled and entangled chains have low thermal conductivities (0.1 to 0.4 W m(-1) K(-1)). We demonstrate that systematic ionization of a weak anionic polyelectrolyte, polyacrylic acid (PAA), resulting in extended and stiffened polymer chains with superior packing, can significantly enhance its thermal conductivity. Cross-plane thermal conductivity in spin-cast amorphous films steadily grows with PAA degree of ionization, reaching up to ~1.2 W m(-1) K(-1), which is on par with that of glass and about six times higher than that of most amorphous polymers, suggesting a new unexplored molecular engineering strategy to achieve high thermal conductivities in amorphous bulk polymers.
The widespread prevalence of commercial products made from microgels illustrates the immense practical value of harnessing the jamming transition; there are countless ways to use soft, solid materials that fluidize and become solid again with small variations in applied stress. The traditional routes of microgel synthesis produce materials that predominantly swell in aqueous solvents or, less often, in aggressive organic solvents, constraining ways that these exceptionally useful materials can be used. For example, aqueous microgels have been used as the foundation of three-dimensional (3D) bioprinting applications, yet the incompatibility of available microgels with nonpolar liquids, such as oils, limits their use in 3D printing with oil-based materials, such as silicone. We present a method to make micro-organogels swollen in mineral oil, using block copolymer self-assembly. The rheological properties of this micro-organogel material can be tuned, leveraging the jamming transition to facilitate its use in 3D printing of silicone structures. We find that the minimum printed feature size can be controlled by the yield stress of the micro-organogel medium, enabling the fabrication of numerous complex silicone structures, including branched perfusable networks and functional fluid pumps.
Biodegradable polymeric nanoparticles have the potential to be safer alternatives to viruses for gene delivery; however, their use has been limited by poor efficacy in vivo. In this work, we synthesize and characterize polymeric gene delivery nanoparticles and evaluate their efficacy for DNA delivery of herpes simplex virus type I thymidine kinase (HSVtk) combined with the prodrug ganciclovir (GCV) in a malignant glioma model. We investigated polymer structure for gene delivery in two rat glioma cell lines, 9L and F98, to discover nanoparticle formulations more effective than the leading commercial reagent Lipofectamine 2000. The lead polymer structure, poly(1,4-butanediol diacrylate-co-4-amino-1-butanol) end-modified with 1-(3-aminopropyl)-4-methylpiperazine, is a poly(beta-amino ester) (PBAE) and formed nanoparticles with HSVtk DNA that were 138 ± 4 nm in size and 13 ± 1 mV in zeta potential. These nanoparticles containing HSVtk DNA showed 100% cancer cell killing in vitro in the two glioma cell lines when combined with GCV exposure, while control nanoparticles encoding GFP maintained robust cell viability. For in vivo evaluation, tumor-bearing rats were treated with PBAE/HSVtk infusion via convection-enhanced delivery (CED) in combination with systemic administration of GCV. These treated animals showed a significant benefit in survival (p=0.0012 vs. control). Moreover, following a single CED infusion, labeled PBAE nanoparticles spread completely throughout the tumor. This study highlights a nanomedicine approach that is highly promising for the treatment of malignant glioma.