Nanomaterials with intrinsic enzyme-like activities (nanozymes), have been widely used as artificial enzymes in biomedicine. However, how to control their in vivo performance in a target cell is still challenging. Here we report a strategy to coordinate nanozymes to target tumor cells and selectively perform their activity to destruct tumors. We develop a nanozyme using nitrogen-doped porous carbon nanospheres which possess four enzyme-like activities (oxidase, peroxidase, catalase and superoxide dismutase) responsible for reactive oxygen species regulation. We then introduce ferritin to guide nitrogen-doped porous carbon nanospheres into lysosomes and boost reactive oxygen species generation in a tumor-specific manner, resulting in significant tumor regression in human tumor xenograft mice models. Together, our study provides evidence that nitrogen-doped porous carbon nanospheres are powerful nanozymes capable of regulating intracellular reactive oxygen species, and ferritinylation is a promising strategy to render nanozymes to target tumor cells for in vivo tumor catalytic therapy.
Composites of LDPE filled with different amounts of graphene nanoplatelets (GnP) were prepared in form of films by means of precoating technique and single screw melt-extrusion using two types of screws, compression and mixing. This manufacturing process imposes strong anisotropy on the sample's morphology, in which the nanoplatelets become oriented along the extrusion direction. Such orientation of GnP in LDPE matrix is confirmed by scanning electron microscopy observations and it yields unique electrical properties. As compared to pure LDPE, significant reductions of the through-plane conductivity are found for the composites at relatively low electric fields (<20 kV/mm) at low filler concentrations. Above the field level of 20 kV/mm, a crossover effect is observed that results in a strong field dependency of the conductivity where the non-linear behavior starts to dominate. Moreover, differential scanning calorimetry (DSC) results indicate a decrease in polymer crystallinity of the composite matrix with increasing filler content, whereas thermogravimetric (TG) analysis shows a slight increase in the material's thermal stability. Application of GnP also leads to improvement of mechanical properties, manifested by the increase of Young's modulus and tensile strength in both types of samples.
Nanozymes, as a new generation of artificial enzymes, offer great opportunities in biomedical engineering and disease treatment. Synergizing the multiple intrinsic functions of nanozymes can improve their performance in biological systems. Here, we report a novel nanozyme with yolk-shell structure fabricated by combining a single gold nanoparticle core with a porous hollow carbon shell nanospheres (Au@HCNs). Au@HCNs exhibited enzyme-like activities similar to horseradish peroxidase and oxidase under an acidic environment, showing the ability of ROS generation. More importantly, the ROS production of Au@HCNs was significantly improved upon 808 nm light irradiation by the photothermal effect, which is often used for tumor therapy. Cellular and animal studies further demonstrated that the efficient tumor destruction was achieved through the combination of light-enhanced ROS and photothermal therapy. These results implied that the intrinsic enzyme-like activity and photothermal conversion of nanozymes can be synergized for efficient tumor treatment, providing a proof-of-concept of tumor catalytic-photothermal therapy based on nanozymes.
The most common type of extruded power cable insulation is based on cross-linked polyethylene (XLPE), which cannot be recycled as a thermoplastic material. Hence, thermoplastic insulation materials currently receive considerable attention because they would allow recycling through re-melting. In particular blends of polyethylene (PE) and polypropylene (PP) would be a compelling alternative to XLPE, provided that the poor compatibility of the two polymers can be overcome. Here, we establish an alternative approach that exploits the in situ formation of a PE–PP-type copolymer through reactive compounding. Ternary blends of an ethylene-glycidyl methacrylate copolymer, a maleic anhydride-grafted polypropylene, and up to 70 wt % low-density polyethylene (LDPE) are compounded at 170 °C. Covalent bonds form through reaction between epoxy and carboxyl groups, leading to a PE–PP-type copolymer that shows good compatibility with LDPE. The in situ generated PE–PP copolymer arrests creep above the melting temperature of LDPE, mediated by a continuous network that is held together by PP crystallites. Recyclability is confirmed by reprocessing at 170 °C. Furthermore, the here investigated formulations feature a low direct-current electrical conductivity of ∼4 × 10–14 S m–1 at 70 °C and 30 kV mm–1, on a par with values measured for LDPE and XLPE. Evidently, in situ formation of a PE–PP-type copolymer through reactive compounding is a promising approach that may enable the design of thermoplastic insulation materials for power cables.
High‐voltage direct‐current power cables are vital for the efficient transport of electricity derived from renewable sources of energy. The most widely used material for high‐voltage power cable insulation – low‐density polyethylene (LDPE) – is usually crosslinked with peroxides, a process that releases unwanted by‐products. Hence, by‐product‐free crosslinking concepts that mitigate the associated increase in electrical conductivity are in high demand. Click chemistry‐type crosslinking of polyethylene copolymer mixtures that contain glycidyl methacrylate and acrylic acid co‐monomers is a promising alternative, provided that the curing reaction can be controlled. Here, we demonstrate that the rate of the curing reaction can be adjusted by tuning the number of epoxy and carboxyl groups. Both dilution of copolymer mixtures with neat LDPE and the selection of copolymers with a lower co‐monomer content have an equivalent effect on the curing speed. Ternary blends that contain 50 wt% of neat LDPE feature an extended extrusion window of up to 170 °C. Instead, at 200 °C rapid curing is possible, leading to thermosets with a low direct‐current electrical conductivity of about 10−16 S cm−1 at an electric field of 20 kV mm−1 and 70 °C. The conductivity of the blends explored here is comparable to or even lower than values measured for both ultraclean LDPE and a peroxide‐cured commercial crosslinked polyethylene grade. Hence, click chemistry curing represents a promising alternative to radical crosslinking with peroxides. © 2019 Society of Chemical Industry
Poly(3‐hexylthiophene) (P3HT) is found to be a highly effective conductivity‐reducing additive for low‐density polyethylene (LDPE), which introduces a new application area to the field of conjugated polymers. Additives that reduce the direct‐current (DC) electrical conductivity of an insulation material at high electric fields have gained a lot of research interest because they may facilitate the design of more efficient high‐voltage direct‐current power cables. An ultralow concentration of regio‐regular P3HT of 0.0005 wt% is found to reduce the DC conductivity of LDPE threefold, which translates into the highest efficiency reported for any conductivity‐reducing additive to date. The here‐established approach, i.e., the use of a conjugated polymer as a mere additive, may boost demand in absolute terms beyond the quantities needed for thin‐film electronics, which would turn organic semiconductors from a niche product into commodity chemicals.
To design reliable high voltage cables, clean materials with superior insulating properties capable of operating at high electric field levels at elevated temperatures are required. This study aims at the electrical characterization of a byproduct-free crosslinked copolymer blend, which is seen as a promising alternative to conventional peroxide crosslinked polyethylene currently used for high voltage direct current cable insulation. The characterization entails direct current (DC) conductivity, dielectric response and surface potential decay measurements at different temperatures and electric field levels. In order to quantify the insulating performance of the new material, the electrical properties of the copolymer blend are compared with those of two reference materials; i.e., low-density polyethylene (LDPE) and peroxide crosslinked polyethylene (XLPE). It is found that, for electric fields of 10–50 kV/mm and temperatures varying from 30 °C to 70 °C, the DC conductivity of the copolymer blend is in the range of 10−17–10−13 S/m, which is close to the conductivity of crosslinked polyethylene. Furthermore, the loss tangent of the copolymer blend is about three to four times lower than that of crosslinked polyethylene and its magnitude is on the level of 0.01 at 50 °C and 0.12 at 70 °C (measured at 0.1 mHz and 6.66 kV/mm). The apparent conductivity and trap density distributions deduced from surface potential decay measurements also confirmed that the new material has electrical properties at least as good as currently used insulation materials based on XLPE (not byproduct-free). Thus, the proposed byproduct-free crosslinked copolymer blend has a high potential as a prospective insulation medium for extruded high voltage DC cables.
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