The liver and spleen are major biological barriers to translating nanomedicines because they sequester the majority of administered nanomaterials and prevent delivery to diseased tissue. Here we ...examined the blood clearance mechanism of administered hard nanomaterials in relation to blood flow dynamics, organ microarchitecture and cellular phenotype. We found that nanomaterial velocity reduces 1,000-fold as they enter and traverse the liver, leading to 7.5 times more nanomaterial interaction with hepatic cells relative to peripheral cells. In the liver, Kupffer cells (84.8 ± 6.4%), hepatic B cells (81.5 ± 9.3%) and liver sinusoidal endothelial cells (64.6 ± 13.7%) interacted with administered PEGylated quantum dots, but splenic macrophages took up less material (25.4 ± 10.1%) due to differences in phenotype. The uptake patterns were similar for two other nanomaterial types and five different surface chemistries. Potential new strategies to overcome off-target nanomaterial accumulation may involve manipulating intra-organ flow dynamics and modulating the cellular phenotype to alter hepatic cell interactions.
•Cr doped diamond like carbon (Cr-DLC) nanocomposite coatings were deposited by using a combined system.•The stress of the Cr-DLC coatings dramatically decreases from 0.98GPa to 0.49GPa as the Cr ...contents increases from 0at% to 9.7at%.•The results showed that Cr-DLC coating with low Cr concentration was a effective protective coating.
Cr doped diamond like carbon (Cr-DLC) coatings were deposited by using a combined system consisting of middle frequency (MF) magnetron sputtering and ion plating. The structure and properties of the undoped and Cr-doped DLC coatings were analyzed by various testing, such as Raman, XPS, hardness and temperature-dependent frictional wear testing. The results showed that Cr-DLC coatings with low Cr concentration was a effective protective coating containing Cr–C nanometer grains, whose mechanical properties were obviously improved, such as, residual stress and cohesive strength, and still kept good wear resistance at the ambient temperature of 400°C.
We disclose a novel radical strategy for the fluorination of alkyl bromides via the merger of silyl radical-mediated halogen-atom abstraction and benzophenone photosensitization. Selectivity for ...halogen-atom abstraction from alkyl bromides is observed in the presence of an electrophilic fluorinating reagent containing a weak N–F bond despite the predicted favorability for Si–F bond formation. To probe this surprising selectivity, preliminary mechanistic and computational studies were conducted, revealing that a radical chain mechanism is operative in which kinetic selectivity for Si–Br abstraction dominates due to a combination of polar effects and halogen-atom polarizability in the transition state. This transition-metal-free fluorination protocol tolerates a broad range of functional groups, including alcohols, ketones, and aldehydes, which demonstrates the complementary nature of this strategy to existing fluorination technologies. This system has been extended to the generation of gem-difluorinated motifs which are commonly found in medicinal agents and agrochemicals.
Solar flares and coronal mass ejections are the most powerful explosions in the Sun. They are major sources of potentially destructive space weather conditions. However, the possible causes of their ...initiation remain controversial. Using high-resolution data observed by the New Solar Telescope of Big Bear Solar Observaotry, supplemented by Solar Dynamics Observatory observations, we present unusual observations of a small-scale emerging flux rope near a large sunspot, whose eruption produced an M-class flare and a coronal mass ejection. The presence of the small-scale flux rope was indicated by static nonlinear force-free field extrapolation as well as data-driven magnetohydrodynamics modeling of the dynamic evolution of the coronal three-dimensional magnetic field. During the emergence of the flux rope, rotation of satellite sunspots at the footpoints of the flux rope was observed. Meanwhile, the Lorentz force, magnetic energy, vertical current, and transverse fields were increasing during this phase. The free energy from the magnetic flux emergence and twisting magnetic fields is sufficient to power the M-class flare. These observations present, for the first time, the complete process, from the emergence of the small-scale flux rope, to the production of solar eruptions.
Heavy metals removal from aqueous phase by adsorption technique has recently attracted a considerable interest. Although various adsorbing materials have been developed, introducing more functional ...groups is considered as the most efficient way to promote the adsorption capacity of the selected adsorbent. However, this approach is usually limited in costly modification precursor and unguaranteed loading efficacy. In this study, waste corn straw was converted to adsorbent precursor by hydrothermal carbonization. The obtained hydrochar (HC) was chemically activated before being modified by polyethyleneimine (PEI). Multiple analysis methods including Scanning Electron Microscopy, Fourier Transform Infrared analysis, and X-ray Photoelectron Spectroscopy analysis verified the alkali activated hydrochar (alkali-HC) was more efficacy to enhance PEI grafting than acid activation. Based on this, the modified HC materials obtained a better adsorption performance. The sorption process of Cu(II) and Zn(II) on the acid-PEI-HC, alkali-PEI-HC, and pristine HC fitted the pseudo second order kinetic and Freundlich model well, and was dominated by chemisorption. Among these adsorbents, the adsorption capacity of alkali-PEI-HC to metal ions was the maximum, which was 207.6 mg/g to Zn(II) and 56.1 mg/g to Cu(II) at 298 K. Regeneration tests showed a result of no less than 60% of its removal capacity was achieved after five cycles. Therefore, alkali-PEI-HC performed as a promising composite sorbent for metal ions. In addition, the study described here has provided a new basis for the utilization of hydrochar (1.08 kWh kg−1) derived from agricultural resources as a promising adsorbent precursor.
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•Desired hydrochars after acid/alkali activation and PEI loading were synthesized.•Higher Cu(II) and Zn(II) adsorption ability was obtained by alkali-PEI-HC.•Energy of straws converted into hydrochar precursor was consumed as 1.08 kWh kg−1.
A significant challenge to delivering therapeutic doses of nanoparticles to targeted disease sites is the fact that most nanoparticles become trapped in the liver. Liver-resident macrophages, or ...Kupffer cells, are key cells in the hepatic sequestration of nanoparticles. However, the precise role that the macrophage phenotype plays in nanoparticle uptake is unknown. Here, we show that the human macrophage phenotype modulates hard nanoparticle uptake. Using gold nanoparticles, we examined uptake by human monocyte-derived macrophages that had been driven to a “regulatory” M2 phenotype or an “inflammatory” M1 phenotype and found that M2-type macrophages preferentially take up nanoparticles, with a clear hierarchy among the subtypes (M2c > M2 > M2a > M2b > M1). We also found that stimuli such as LPS/IFN-γ rather than with more “regulatory” stimuli such as TGF-β/IL-10 reduce per cell macrophage nanoparticle uptake by an average of 40%. Primary human Kupffer cells were found to display heterogeneous expression of M1 and M2 markers, and Kupffer cells expressing higher levels of M2 markers (CD163) take up significantly more nanoparticles than Kupffer cells expressing lower levels of surface CD163. Our results demonstrate that hepatic inflammatory microenvironments should be considered when studying liver sequestration of nanoparticles, and that modifying the hepatic microenvironment might offer a tool for enhancing or decreasing this sequestration. Our findings also suggest that models examining the nanoparticle/macrophage interaction should include studies with primary tissue macrophages.
Uranium (U) is a toxic and radioactive element. Excessive amounts of aqueous U(VI) generated from U mining, processing and nuclear industry may result in severe and irreversible damage to the ...environment. Herein, Ficus microcarpa aerial root (FMAR), a biowaste material, was used to adsorb U(VI) from aqueous solutions for the first time. Potassium permanganate (KMnO4)-modified FMAR biochar was synthesised, characterised and compared with raw (unmodified) biochar with respect to U(VI) adsorption. The results showed that the adsorption capability of the modified FMAR biochar was evidently higher than that of the raw biochar. Multiple characterisation techniques confirmed that the discrepancy was mainly due to the increased content of O−H and formation of irregular sheet-like nanostructure with the ultrafine MnO2 nanoparticles on the biochar surfaces after KMnO4 modification. The abundance of O−H and nanoscale MnO2 notably enhanced the adsorption of U(VI) by means of coordination and Lewis acid-base interaction. The results indicate that KMnO4-modified FMAR biochar has a good potential to serve as an environment-friendly adsorbent for the removal of U(VI) from solution.
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•A novel biochar was synthesised from Ficus microcarpa aerial root (FMAR) biowaste.•Ultrafine MnO2 particles covered modified biochar after KMnO4 modification.•The increased OH and generated MnO2 enhanced the adsorption ability.•FMAR biochar serves as an environment-friendly adsorbent to remove U(VI).
Gravitational‐wave high‐energy Electromagnetic Counterpart All‐sky Monitor (GECAM) is a space‐borne instrument dedicated to monitoring high‐energy transients, including Terrestrial Gamma‐ray Flashes ...(TGFs) and Terrestrial Electron Beams (TEBs). We implemented a TGF/TEB search algorithm for GECAM, with which 147 bright TGFs, 2 typical TEBs and 2 special TEB‐like events are identified during an effective observation time of ∼9 months. We show that, with gamma‐ray and charged particle detectors, GECAM can effectively identify and distinguish TGFs and TEBs, and measure their temporal and spectral properties in detail. A very high TGF‐lightning association rate of ∼80% is obtained between GECAM and GLD360 in east Asia region.
Plain Language Summary
Terrestrial gamma‐ray flashes (TGFs) and Terrestrial Electron Beams (TEBs) represent the most energetic radioactive phenomena in the atmosphere of the Earth. They reflect a natural particle accelerator that can boost electrons up to at least several tens of mega electron volts and produce gamma‐ray radiation. With novel detection technologies, Gravitational‐wave high‐energy Electromagnetic Counterpart All‐sky Monitor (GECAM) is a new powerful instrument to observe TGFs and TEBs, as well as study their properties. For example, it is difficult for most space‐borne high‐energy instruments to distinguish between TGFs and TEBs. However, we show here that, with the joint observation of gamma‐ray and charged particle detectors, GECAM can effectively identify TGFs and TEBs. GECAM can also reveal their fine features in the light curves and spectra.
Key Points
During 9‐month observation, Gravitational‐wave high‐energy Electromagnetic Counterpart All‐sky Monitor (GECAM) has detected 147 bright Terrestrial Gamma‐ray Flashes (TGFs), 2 typical Terrestrial Electron Beams (TEBs), and 2 special TEB‐like events
With novel detector design, GECAM can effectively classify TGFs and TEBs, and reveal their fine temporal features
We obtained a very high TGF‐lightning association rate (∼80%) between GECAM and GLD360 in east Asia region
A series of CuCo2O4 composite spinels with an interconnected meso-macroporous nanosheet morphology were synthesized using the hydrothermal method and subsequent calcination treatment to activate ...peroxymonosulfate (PMS) for benzophenone-4 (BP-4) degradation. As-prepared CuCo2O4 composite spinels, especially CuCo-H3 prepared by adding cetyltrimethylammonium bromide, showed superior reactivity for PMS activation. In a typical reaction, BP-4 (10.0 mg/L) was almost completely degraded in 15 min by the activation of PMS (200.0 mg/L) using CuCo-H3 (100.0 mg/L), with only 9.2 μg/L cobalt leaching detected. Even after being used six times, the performance was not influenced by the lower leaching of ions and surface-absorbed intermediates. The possible interface mechanism of PMS activation by CuCo-H3 was proposed, wherein a unique interconnected meso-macroporous nanosheet structure, strong interactions between copper and cobalt, and cycling of Co(II)/Co(III) and Cu(I)/Cu(II) effectively facilitated PMS activation to generate SO4 •– and •OH, which contributed to BP-4 degradation. Furthermore, combined with intermediates detected by liquid chromatography quadrupole time-of-flight mass spectrometry and density functional theory calculation results, the degradation pathway of BP-4 involving hydroxylation and C–C bond cleavage was proposed.
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