The development of carbon based hollow-structured nanospheres (HNSs) materials has stimulated growing interest due to their controllable structure, high specific surface area, large void space, enhanced mass transport, and good biocompatibility. The incorporation of functional nanomaterials into their core and/or shell opens new horizons in designing functionalized HNSs for a wider spectrum of promising applications. In this work, we report a new type of functionalized HNSs based on Pd nanoparticles (NPs) decorated double shell structured N-doped graphene quantum dots (NGQDs)@N-doped carbon (NC) HNSs, with ultrafine Pd NPs and "nanozyme" NGQDs as dual signal-amplifying nanoprobes, and explore their promising application as a highly efficient electrocatalyst in electrochemical sensing of a newly emerging biomarker, i.e., hydrogen peroxide (H2O2), for cancer detection. Due to the synergistic effect of the robust and conductive HNS supports and catalytically active Pd NPs and NGQD in facilitating electron transfer, the NGQD@NC@Pd HNS hybrid material exhibits high electrocatalytic activity toward the direct reduction of H2O2 and can promote the electrochemical reduction reaction of H2O2 at a favorable potential of 0 V, which effectively restrains the redox of most electroactive species in physiological samples and eliminates interference signals. The resultant electrochemical H2O2 biosensor based hybrid HNSs materials demonstrates attractive performance, including low detection limit down to nanomole level, short response time within 2 s, as well as high sensitivity, reproducibility, selectivity, and stability, and have been used in real-time tracking of trace amounts of H2O2 secreted from different living cancer cells in a normal state and treated with chemotherapy and radiotherapy.
A novel donor-acceptor-donor-acceptor (D-A1-D-A2) π-conjugated copolymer (PDBPyDT2FBT) has been prepared by Stille coupling reaction. It is found that PDBPyDT2FBT exhibits low LUMO energy level mainly because of multiple electron-deficient units and donor-acceptor interaction, which is favorable to obtain more efficient electron injection and transport in organic thin-film transistors (OTFTs). Moreover, introducing two electron-deficient moieties into the thiophene-containing copolymer increases the length of conjugated main chain and enhances the coplanarity of the backbone, which may be beneficial for promoting the molecular crystallinity and improving molecular ordering capability at low temperatures. High electron and hole mobilities up to 0.65 and 0.24 cm(2) V(-1) s(-1) were obtained at relatively low annealing temperatures of 100 and 80 °C, respectively, implying that PDBPyDT2FBT is a promising ambipolar polymer semiconductor applied in low-cost and large-area manufacturing of OTFTs.
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