Understanding the formation of the intracellular protein corona of nanoparticles is essential for a wide range of bio- and nanomedical applications. The innermost layer of the protein corona, the hard corona, directly interacts with the nanoparticle surface, and by shielding the surface, it has a deterministic effect on the intracellular processing of the nanoparticle. Here, we combine a direct qualitative analysis of the hard corona composition of gold nanoparticles with a detailed structural characterization of the molecules in their interaction with the nanoparticle surface and relate both to the effects they have on the ultrastructure of living cells and the processing of the gold nanoparticles. https://www.selleckchem.com/products/ABT-869.html Cells from the cell lines HCT-116 and A549 were incubated with 30 nm citrate-stabilized gold nanoparticles and with their aggregates in different culture media. The combined results of mass spectrometry based proteomics, cryo soft X-ray nanotomography and surface-enhanced Raman scattering experiments together revealed different uptake mechanisms in the two cell lines and distinct levels of induced cellular stress when incubation conditions were varied. The data indicate that the different incubation conditions lead to changes in the nanoparticle processing via different protein-nanoparticle interfacial interactions. Specifically, they suggest that the protein-nanoparticle surface interactions depend mainly on the surface properties of the gold nanoparticles, that is, the ζ-potential and the resulting changes in the hydrophilicity of the nanoparticle surface, and are largely independent of the cell line, the uptake mechanism and intracellular processing, or the extent of the induced cellular stress.Understanding the mechanisms controlling the redox transformation of organic contaminants mediated by biochar is of great significance for application of biochar in remediation of contaminated soils and sediments. Here we investigated the mediation effect of a pine wood-derived biochar (P-char) in comparison with multiwalled carbon nanotubes (MCNTs) and graphite on the reductive dechlorination of hexachloroethane by sulfide. Upon normalization of the mediator's surface area, the reduction rate of hexachloroethane follows an order of P-char less then MCNTs less then graphite. Aqueous polysulfides and polysulfide free radicals were readily produced by reacting sulfide only with P-char, and the supernatant separated from the reaction system could account for 83.4% of the pseudo-kinetic rate constant of hexachloroethane mediated by P-char. In contrast, MCNTs and graphite had weak abilities to produce reactive sulfur species, and the supernatant exhibited very low reduction capability ( less then 20.7%) of hexachloroethane. Electron paramagnetic resonance (EPR) analysis demonstrated that the surface quinone moieties on P-char induced the formation of polysulfides and polysulfide free radicals from sulfide by serving as one-electron acceptors. Consistently, polysulfides prepared by reacting elemental sulfur with sulfide showed **** stronger reducing capability compared to sulfide. Thus, the mediation effect of P-char was dominantly attributed to the surface quinone-induced formation of reactive reducing sulfur species, whereas the mediation effect of MCNTs and graphite mainly stemmed from the enhanced electron transfer by the graphitized carbon. These results showed for the first time that surface quinone-induced formation of aqueous reactive sulfur species could control biochar-mediated reductive dechlorination of chloroorganic contaminants by sulfides.Although Ni phosphides are efficient for hydrogen evolution reactions, they are unfavorable for oxygen evolution reactions, so their application in alkaline water electrolysis is limited. It is a feasible method for creating a novel Ni phosphide/oxide heterogeneous interface to promote the oxygen evolution kinetics of Ni phosphide materials in an alkaline medium, yet it has been an unprecedented challenge for researchers. In this work, NiP3@CeO2 hybrid nanoparticles are firstly in situ grown on Ni foam (NiP3@CeO2/NF) via a novel controlled phosphating strategy. The NiP3@CeO2/NF catalysts display a fairly small overpotential of 200 mV to achieve a current density of 25 mA cm-2 for the oxygen evolution reaction (OER) under alkaline conditions, 110 mV smaller than that of NiO@CeO2/NF. It is noteworthy that the improved electrocatalytic performance of NiP3@CeO2/NF can be attributed to rapid electron transfer and the synergistic catalytic effect of the hybrid material. Density functional theory results demonstrate that NiP3 shows a stronger water adsorption energy than CeO2. The novel strategy of controlled phosphating to construct transition metal phosphide/oxide interfaces provides new ideas and methods for the development of efficient and practical water splitting catalysts.As robust functional polymers, polymer brush-based hybrid nanomaterials have potential application in the highly sensitive determination of tumor markers (TMs). Currently, there are plentiful reports on the polymerization methods of functional polymer brushes. Low ppm ATRP (activators (re)generated by electron transfer for atom transfer radical polymerization (A(R)GET ATRP), initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) and electrochemically mediated atom transfer radical polymerization (eATRP)) is a facile and robust methodology with the advantages of simplicity, eco-friendliness and wide applicability to prepare well-defined polymeric materials. In this work, a controlled polymer brush-type functional nanoprobe is successfully fabricated by functional AGET ATRP and used as a sandwich-type electrochemical immunosensor for precise detection of TMs (alpha-fetoprotein, AFP). Using graphene oxide (GO) as an excellent conductive matrix, a GO-based poly-heterozygosis pyridine nanomaterial (GO@PHPY) is obtained by surface-initiated AGET ATRP and photocatalytic modification. The nanoprobe is assembled using GO@PHPY and a detection antibody (Ab2) to detect AFP, in which Cu(ii) serves as a signal label to coordinate with the pyridyl group. Under optimized conditions, the electrochemical sensor exhibits a good detection effect on AFP, with a detection range of 0.1 pg mL-1 to 100 ng mL-1 and a low detection limit of 0.08 pg mL-1. It is worth noting that the detection platform can be applied to the detection of real human serum samples. Thus, it is a desirable platform for AFP detection in clinical diagnosis and practical applications. Meanwhile, this work proves that designing and constructing functional polymer brushes is one of the most effective methods for developing new materials for analytical scientific applications.
Understanding the formation of the intracellular protein corona of nanoparticles is essential for a wide range of bio- and nanomedical applications. The innermost layer of the protein corona, the hard corona, directly interacts with the nanoparticle surface, and by shielding the surface, it has a deterministic effect on the intracellular processing of the nanoparticle. Here, we combine a direct qualitative analysis of the hard corona composition of gold nanoparticles with a detailed structural characterization of the molecules in their interaction with the nanoparticle surface and relate both to the effects they have on the ultrastructure of living cells and the processing of the gold nanoparticles. https://www.selleckchem.com/products/ABT-869.html Cells from the cell lines HCT-116 and A549 were incubated with 30 nm citrate-stabilized gold nanoparticles and with their aggregates in different culture media. The combined results of mass spectrometry based proteomics, cryo soft X-ray nanotomography and surface-enhanced Raman scattering experiments together revealed different uptake mechanisms in the two cell lines and distinct levels of induced cellular stress when incubation conditions were varied. The data indicate that the different incubation conditions lead to changes in the nanoparticle processing via different protein-nanoparticle interfacial interactions. Specifically, they suggest that the protein-nanoparticle surface interactions depend mainly on the surface properties of the gold nanoparticles, that is, the ζ-potential and the resulting changes in the hydrophilicity of the nanoparticle surface, and are largely independent of the cell line, the uptake mechanism and intracellular processing, or the extent of the induced cellular stress.Understanding the mechanisms controlling the redox transformation of organic contaminants mediated by biochar is of great significance for application of biochar in remediation of contaminated soils and sediments. Here we investigated the mediation effect of a pine wood-derived biochar (P-char) in comparison with multiwalled carbon nanotubes (MCNTs) and graphite on the reductive dechlorination of hexachloroethane by sulfide. Upon normalization of the mediator's surface area, the reduction rate of hexachloroethane follows an order of P-char less then MCNTs less then graphite. Aqueous polysulfides and polysulfide free radicals were readily produced by reacting sulfide only with P-char, and the supernatant separated from the reaction system could account for 83.4% of the pseudo-kinetic rate constant of hexachloroethane mediated by P-char. In contrast, MCNTs and graphite had weak abilities to produce reactive sulfur species, and the supernatant exhibited very low reduction capability ( less then 20.7%) of hexachloroethane. Electron paramagnetic resonance (EPR) analysis demonstrated that the surface quinone moieties on P-char induced the formation of polysulfides and polysulfide free radicals from sulfide by serving as one-electron acceptors. Consistently, polysulfides prepared by reacting elemental sulfur with sulfide showed much stronger reducing capability compared to sulfide. Thus, the mediation effect of P-char was dominantly attributed to the surface quinone-induced formation of reactive reducing sulfur species, whereas the mediation effect of MCNTs and graphite mainly stemmed from the enhanced electron transfer by the graphitized carbon. These results showed for the first time that surface quinone-induced formation of aqueous reactive sulfur species could control biochar-mediated reductive dechlorination of chloroorganic contaminants by sulfides.Although Ni phosphides are efficient for hydrogen evolution reactions, they are unfavorable for oxygen evolution reactions, so their application in alkaline water electrolysis is limited. It is a feasible method for creating a novel Ni phosphide/oxide heterogeneous interface to promote the oxygen evolution kinetics of Ni phosphide materials in an alkaline medium, yet it has been an unprecedented challenge for researchers. In this work, NiP3@CeO2 hybrid nanoparticles are firstly in situ grown on Ni foam (NiP3@CeO2/NF) via a novel controlled phosphating strategy. The NiP3@CeO2/NF catalysts display a fairly small overpotential of 200 mV to achieve a current density of 25 mA cm-2 for the oxygen evolution reaction (OER) under alkaline conditions, 110 mV smaller than that of NiO@CeO2/NF. It is noteworthy that the improved electrocatalytic performance of NiP3@CeO2/NF can be attributed to rapid electron transfer and the synergistic catalytic effect of the hybrid material. Density functional theory results demonstrate that NiP3 shows a stronger water adsorption energy than CeO2. The novel strategy of controlled phosphating to construct transition metal phosphide/oxide interfaces provides new ideas and methods for the development of efficient and practical water splitting catalysts.As robust functional polymers, polymer brush-based hybrid nanomaterials have potential application in the highly sensitive determination of tumor markers (TMs). Currently, there are plentiful reports on the polymerization methods of functional polymer brushes. Low ppm ATRP (activators (re)generated by electron transfer for atom transfer radical polymerization (A(R)GET ATRP), initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) and electrochemically mediated atom transfer radical polymerization (eATRP)) is a facile and robust methodology with the advantages of simplicity, eco-friendliness and wide applicability to prepare well-defined polymeric materials. In this work, a controlled polymer brush-type functional nanoprobe is successfully fabricated by functional AGET ATRP and used as a sandwich-type electrochemical immunosensor for precise detection of TMs (alpha-fetoprotein, AFP). Using graphene oxide (GO) as an excellent conductive matrix, a GO-based poly-heterozygosis pyridine nanomaterial (GO@PHPY) is obtained by surface-initiated AGET ATRP and photocatalytic modification. The nanoprobe is assembled using GO@PHPY and a detection antibody (Ab2) to detect AFP, in which Cu(ii) serves as a signal label to coordinate with the pyridyl group. Under optimized conditions, the electrochemical sensor exhibits a good detection effect on AFP, with a detection range of 0.1 pg mL-1 to 100 ng mL-1 and a low detection limit of 0.08 pg mL-1. It is worth noting that the detection platform can be applied to the detection of real human serum samples. Thus, it is a desirable platform for AFP detection in clinical diagnosis and practical applications. Meanwhile, this work proves that designing and constructing functional polymer brushes is one of the most effective methods for developing new materials for analytical scientific applications.
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