Self-propelled assembly of nanoparticles with self-catalytic regulation for tumour-specific imaging and therapy.

Targeted assembly of nanoparticles in biological systems holds great promise for disease-specific imaging and therapy. However, the current manipulation of nanoparticle dynamics is primarily limited to organic pericyclic reactions, which necessitate the introduction of synthetic functional groups as bioorthogonal handles on the nanoparticles, leading to complex and laborious design processes. Here, we report the synthesis of tyrosine (Tyr)-modified peptides-capped iodine (I) doped CuS nanoparticles (CuS-I@P1 NPs) as self-catalytic building blocks that undergo self-propelled assembly inside tumour cells via Tyr-Tyr condensation reactions catalyzed by the nanoparticles themselves. Upon cellular internalization, the CuS-I@P1 NPs undergo furin-guided condensation reactions, leading to the formation of CuS-I nanoparticle assemblies through dityrosine bond. The tumour-specific furin-instructed intracellular assembly of CuS-I NPs exhibits activatable dual-modal imaging capability and enhanced photothermal effect, enabling highly efficient imaging and therapy of tumours. The robust nanoparticle self-catalysis-regulated in situ assembly, facilitated by natural handles, offers the advantages of convenient fabrication, high reaction specificity, and biocompatibility, representing a generalizable strategy for target-specific activatable biomedical imaging and therapy.

Orthogonally Sequential Activation of Self-Powered DNAzymes Cascade for Reliable Monitoring of mRNA in Living Cells.

Ratiometric imaging of tumor-related mRNA is significant, yet spatiotemporally resolved regulation on the ratiometric signals to avoid non-specific activation in the living cells remains challenging. Herein, orthogonally sequential activation of concatenated DNAzyme circuits is, first, developed for Spatio Temporally regulated Amplified and Ratiometric (STAR) imaging of TK1 mRNA inside living cells with enhanced reliability and accuracy. By virtue of the synthesized CuO/MnO2 nanosheets, orthogonally regulated self-powered DNAzyme circuits are operated precisely in living cells, sequentially activating two-layered DNAzyme cleavage reactions to achieve the two ratiometric signal readouts successively for reliable monitoring of low-abundance mRNA in living cells. It is found that the ratiometric signals can only be derived from mRNA over-expressed tumor cells, also irrespective of probes' delivery concentration. The presented approach could provide new insight into orthogonally regulated ratiometric systems for reliable imaging of specific biomarkers in living cells, benefiting disease precision diagnostics.

The electronic structure of the active center of Co3Se4 electrocatalyst was adjusted by Te doping for efficient oxygen evolution.

In order to enhance the energy efficiency of water electrolysis, it is imperative to devise electrocatalysts for oxygen evolution reaction that are both non-precious metal-based and highly efficient. Efficient catalyst design is generally based on electronic structural engineering. Considering the electronegativity disparity between selenium (Se) and tellurium (Te), the tunable bandgaps, and the conductive metallic nature of Te. We designed a material wherein Te atoms are uniformly doped onto the surface of Cobalt tetra selenide (Co3Se4) nanorods, leading to the synthesis of a defect-rich material. Experimental results demonstrate that Te doping in Co3Se4 increases active sites and optimizes the electronic structure of Co cations, enhancing the design of multi-defect structures. This promotes the generation of the Co(oxy) hydroxide (CoOOH) active phase, enhancing catalytic activity by maximizing the binding strength between Co sites and oxygenated intermediates. Te-Co3Se4 nanorods exhibit good catalytic activity for oxygen evolution reactions, with an overpotential of 269 mV at a driving current density of 50 mA cm-2 and excellent stability in alkaline media (over 100 h). This discovery indicates the feasibility of strategically combining various imperfect structures, thereby unlocking the latent potential of diverse catalysts in electrocatalytic reactions.

Synergistically Regulating the Electronic Structure of CoS by Cation and Anion Dual-Doping for Efficient Overall Water Splitting.

Precisely regulating the electronic construction of the reactive center is an essential method to improve the electrocatalysis, but achieving efficient multifunctional characteristics remains a challenge. Herein, CoS sample dual-doped by Cu and F atoms, as bifunctional electrocatalyst, is designed and synthesized for water electrolysis. According to the experimental results, Cu atom doping can perform primary electronic adjustment and obtain bifunctional properties, and then the electronic structure is adjusted for the second time to achieve an optimal state by introducing F atom. Meanwhile, this dual-doping strategy will result in lattice distortion and expose more active sites. As expected, dual-doped Cu-F-CoS show the brilliant electrocatalytic activity, revealing ultralow overpotentials (59 mV for HER, 213 mV for OER) at 10 mA cm-2 in alkaline electrolyte. Besides, it also exhibits distinguished water electrolysis activity with cell voltage as low as 1.52 V at 10 mA cm-2 . Our work can provide an atomic-level perception for adjusting the electronic construction of reactive sites by means of dual-doping engineering and put forward a contributing path for the electrocatalysts with multifunctional designing.

Regulating the Active Sites of Metal-Phthalocyanine at the Molecular Level for Efficient Water Electrolysis: Double Deciphering of Electron-Withdrawing Groups and Bimetallic.

Implementing a molecular modulation strategy for metallic phthalocyanines (MPc) without losing the activity of the metal center and inducing a multifunction characteristic in electrocatalytic remains a challenge. Herein, a series of 2D CuCo bimetallic polymerized phthalocyanine modified with strong electron-withdrawing groups (CuCoPc-g, g = F, Cl, Br, NO2 ) for water oxidation in the alkaline electrolyte is designed and simply synthesized. The experimental results testify that the bimetallic design can perform electronic adjustment once and introduce the second active sites to get bifunctional characteristics, and then the electronic structure of the active center can be regulated by electron-withdrawing groups for a second time to achieve the optimal state. These electrons that transfer in the active center of inner metal can generate space-charged regions and the design of the polymer can stabilize active site region to maintain long-term electrolytic stability and high activity. This study precisely regulates the electronic structure of MPc at the molecular level and provides insight into the multifunctional design of polymeric macrocyclic electrocatalysts.

Deciphering the Space Charge Effect of the p-n Junction between Copper Sulfides and Molybdenum Selenides for Efficient Water Electrolysis in a Wide pH Range.

Space charge transfer is crucial for an efficient electrocatalytic process, especially for narrow-band-gap metal sulfides/selenides. Herein, we designed and synthesized a core-shell structure which is an ultrathin MoSe2 nanosheet coated CuS hollow nanoboxes (CuS@MoSe2) to form an open p-n junction structure. The space charge effect in the p-n junction region will greatly improve electron mass transfer and conduction, and also have abundant active interfaces. It was used as a bifunctional electrocatalyst for water oxidation at a wide pH range. It exhibits a low overpotential of 49 mV for the HER and 236 mV for the OER at a current density of 10 mA·cm-2 in acidic pH, 72 mV for the HER and 219 mV at 10 mA·cm-2 for the OER in alkaline pH, and 62 mV for the HER and 230 mV at 10 mA·cm-2 for the OER under neutral conditions. The experimental results and density functional theory calculations testify that the p-n junction in CuS@MoSe2 designed and synthesized has a strong space charge region with a synergistic effect. The built-in field can boost the electron transport during the electrocatalytic process and can stabilize the charged active center of the p-n junction. This will be beneficial to improve the electrocatalytic performance. This work provides the understanding of semiconductor heterojunction applications and regulating the electronic structure of active sites.

Iron Doped in the Subsurface of CuS Nanosheets by Interionic Redox: Highly Efficient Electrocatalysts toward the Oxygen Evolution Reaction.

Modifying the electronic structure of electrocatalysts by metal doping is favorable to their electrocatalytic activity. Herein, by a facile one-pot redox process of Fe(III) and Cu(I), Fe(II) was successfully doped into the subsurface of CuS nanosheets (NSs) for the first time to obtain a novel electrocatalyst (Fesub-CuS NSs) that possesses not only subtle lattice defects but also an atomic-level coupled nanointerface, greatly enhancing the oxygen evolution reaction (OER) performances. Meanwhile, Fe(II) and Fe(III) coexisting in Fesub-CuS nanosheets are favorable to OER through valence regulation. As expected, by simultaneously controlling the abovementioned three factors to optimize Fesub-CuS nanosheets, they display a lower overpotential of 252 mV at a current density of 20 mA cm-2 for OER, better than 389 mV for pristine CuS nanosheets. This discovery furnishes low-cost and efficient Cu-based electrocatalysts by metal doping. Density functional theory (DFT) calculations further verify that Fesub-CuS(100) is thermodynamically stable and is more active for OER. This research provides a strategy for the atomic-scale engineering of nanocatalysts and also sheds light on the design of novel and efficient electrocatalysts.