Defect engineering to tailor structure-activity relationship in biodegradable nanozymes for tumor therapy by dual-channel death strategies.

Pursuing biodegradable nanozymes capable of equipping structure-activity relationship provides new perspectives for tumor-specific therapy. A rapidly degradable nanozymes can address biosecurity concerns. However, it may also reduce the functional stability required for sustaining therapeutic activity. Herein, the defect engineering strategy is employed to fabricate Pt-doping MoOx (PMO) redox nanozymes with rapidly degradable characteristics, and then the PLGA-assembled PMO (PLGA@PMO) by microfluidics chip can settle the conflict between sustaining therapeutic activity and rapid degradability. Density functional theory describes that Pt-doping enables PMO nanozymes to exhibit an excellent multienzyme-mimicking catalytic activity originating from synergistic catalysis center construction with the interaction of Pt substitution and oxygen vacancy defects. The peroxidase- (POD), oxidase- (OXD), glutathione peroxidase- (GSH-Px), and catalase- (CAT) mimicking activities can induce robust ROS output and endogenous glutathione depletion under tumor microenvironment (TME) response, thereby causing ferroptosis in tumor cells by the accumulation of lipid peroxide and inactivation of glutathione peroxidase 4. Due to the activated surface plasmon resonance effect, the PMO nanozymes can cause hyperthermia-induced apoptosis through 1064 nm laser irradiation, and augment multienzyme-mimicking catalytic activity. This work represents a potential biological application for the development of therapeutic strategy for dual-channel death via hyperthermia-augmented enzyme-mimicking nanocatalytic therapy.

Optimizing Porous Metal-Organic Layers for Stable Zinc Anodes.

Aqueous zinc-ion batteries (ZIBs) have been considered as alternative stationary energy storage systems, but the dendrite and corrosion issues of Zn anodes hinder their practical applications. Here we report a series of two-dimensional (2D) metal-organic frameworks (MOFs) with Zr12 clusters, which act as artificial solid electrolyte interphase (SEI) layers to prevent dendrites and corrosion of Zn anodes. The Zr12-based 2D MOF layers were formed by incubating 3D layer-pillared Zr-MOFs in ZnSO4 aqueous electrolytes, which replaced the pillar ligands with terminal SO42-. Furthermore, the pore sizes of Zr12-based 2D MOF layers were systematically tuned, leading to optimized Zn2+ conduction properties and protective performance for Zn anodes. In contrast to the traditional 2D-MOFs with Zr6 clusters, Zr12-based 2D MOF layers as artificial SEI significantly reduced the polarization and increased the stability of Zn anodes in MOF@Zn||MOF@Zn symmetric cells and MOF@Zn||MnO2 full cells. In situ experiments and DFT computations reveal that the enhanced cell performance is attributed to the unique Zr12-based layered structure with intrinsic pores to allow fast Zn2+ diffusion, surface Zr-SO4 zincophilic sites to induce uniform Zn deposition, and inhibited hydrogen evolution by 2D MOF Zr12 layers.

Local photothermal/photodynamic synergistic antibacterial therapy based on two-dimensional BP@CQDs triggered by single NIR light source.

Pathogenic bacteria-infected wound healing faces challenges even though many advanced antibiotics and antibacterial nanoagents have been developed. Herein, we established a two-dimensional antibacterial nanoplatform with synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) antibacterial capabilities mediated by a single 808 nm laser irradiation. The nanoplatform is constructed by combining black phosphorus (BP) obtained by liquid phase exfoliation and hydrothermally prepared tellurium-doped carbon quantum dots (CQDs) prepared by electrostatic interaction. As a result, the photothermal conversion of BP and hydroxyl radical (‧OH) production of CQDs under NIR laser makes the nanoplatform (BP@CQDs) possess an outstanding antibacterial performance against S. aureus and E. coli (as high as 92.7% and 98.4%, respectively), resulting in a faster wound closure ratio than another infected wound. Moreover, in vitro and in vivo researches showed that BP@CQDs have good hemocompatibility, cytocompatibility, and biocompatibility during the therapeutic process. This work demonstrates the broad application prospect of BP nanosheets in infectious microenvironments and develops a potential strategy for S. aureus-infected wound repair.

Antibacterial fluorescent nano-sized lanthanum-doped carbon quantum dot embedded polyvinyl alcohol for accelerated wound healing.

Bacteria is one of the main culprits that cause human diseases and pose long-term challenges to people's health. Rare earth elements have unique antibacterial advantages, but little research is available. In this paper, we reported an antibacterial composite film based on lanthanum-doped carbon quantum dot nanoparticles (La@N-P-CQDs) and polyvinyl alcohol (PVA) film for fluorescence of antibiotics and accelerating wound healing. PVA/La@N-P-CQDs composite film presented excellent hydrophilicity, biocompatibility, fluorescence intensity, and antibacterial effects. The antibacterial activity of La@N-P-CQDs was evaluated by employing antibacterial assay using Escherichia coli (E.coli)and Staphylococcus aureus (S.aureus) in vitro. La@N-P-CQDs showed enhanced antibacterial activity compared with N-P-CQDs. Moreover, the PVA/La@N-P-CQDs composite film with 0.5 mg/mL La@N-P-CQDs showed better antibacterial capability and wound healing performance than PVA and PVA/N-P-CQDs films in bacterial adhesion experiment. PVA/La@N-P-CQDs composite film could be used for wound dressing in vivo experiment and had no side effects on major organs in mice. The antibacterial composite film significantly promoted in vivo wound healing process because of its multifunctional properties. Therefore, it was an excellent candidate for wound dressing.

Dual enzyme-mimic nanozyme based on single-atom construction strategy for photothermal-augmented nanocatalytic therapy in the second near-infrared biowindow.

Nanozyme-based catalytic therapy, an emerging therapeutic pattern, has significantly incorporated in the advancement of tumor therapy by generating lethal reactive oxygen species. Nevertheless, most of the nanozymes have mono catalytic performances with H2O2 in the tumor microenvironment (TME), which lowers their therapeutic efficiency. Herein, we design a newly-developed single-atom Fe dispersed N-doped mesoporous carbon nanospheres (SAFe-NMCNs) nanozyme with high H2O2 affinity for photothermal-augmented nanocatalytic therapy. The SAFe-NMCNs nanozyme possesses dual enzyme-mimic catalytic activity which not only acts as a catalase-mimic role to achieve ultrasonic imaging in tumor site by O2 generation, but also exhibits the superior peroxidase-mimic catalytic performance to generate •OH for nanocatalytic therapy. Besides, the SAFe-NMCNs nanozyme with strong optical absorption in the second near-infrared (NIR-II) region shows excellent photothermal conversion performance. The peroxidase-mimic catalytic process of SAFe-NMCNs nanozyme is realized using density functional theory (DFT). Both in vitro and in vivo results indicate that the SAFe-NMCNs nanozyme can efficiently suppress tumor cells growth by a synergistic therapy effect with photothermal-augmented nanocatalytic therapy. The work developed a single-atom-coordinated nanozyme with dual-enzyme catalytic performance and achieve hyperthermia-augmented nanocatalytic therapy effect, can open a window for potential biological applications.

A ZIF-8 Host for Dendrite-Free Zinc Anodes and N,O Dual-doped Carbon Cathodes for High-Performance Zinc-Ion Hybrid Capacitors.

Zn is a promising anode for aqueous energy storage owing to it intrinsic superior properties such as large capacity, abundant reserves, low potential and safety. But, the growth of dendrites during charge and discharge leads to a decrease in reversibility. In addition, further development of zinc-ion hybrid capacitors (ZICs) is seriously challenging because of the lack of an exceptional cathode. Herein, we use ZIF-8 annealed at 500 °C (annealed ZIF-8) as a host material for stable and dendrite-free Zn anodes. Utilization of annealed ZIF-8 results in dendrite-free Zn deposition and stripping as a result of its porous construction, which contains trace Zn. Furthermore, we firstly proposed innovative N,O dual-doped carbon which was designed by the derived ZIF-8 (ZIF-8 derived C) as cathode for high-energy and power-density ZICs. The new ZIC assembled by Zn@annealed ZIF-8 anode and ZIF-8 derived C cathode provides a capacity of 135.5 mAh g-1 and an energy density of 108.4 Wh kg-1 with a power density of 800 W kg-1 at 1.0 A g-1 . In addition, it shows outstanding cycling stability of 91% capacity retention after 6000 cycles at 5.0 A g-1 . Moreover, the solid-state ZICs can drive LEDs and smart watches. This ZIC holds promise for the practical application of supercapacitors.

Facile Synthesis of the Cu, N-CDs@GO-CS Hydrogel with Enhanced Antibacterial Activity for Effective Treatment of Wound Infection.

Drug resistance and increasing dangers during antibiotic treatment have brought a new eternal task for the research of effective antibacterial agents or therapeutics. In this work, we used Cu, N-doped carbon dots (Cu, N-CDs) to modify graphene oxide (GO) nanosheets and then loaded to chitosan (CS) hydrogels via electrostatic interaction to form Cu, N-CDs@GO-CS hydrogel nanoplatforms to treat Staphylococcus aureus and Escherichia coli. The excellent antibacterial activity is from the combined effects of hyperthermia and reactive oxygen species generated under near-infrared (NIR) laser irradiation of the Cu, N-CDs@GO-CS hydrogel, which shows excellent antibacterial activity compared with the CS hydrogel or the Cu, N-CDs@GO-CS hydrogel without NIR laser irradiation. Moreover, the inherent antibacterial nature of the CS hydrogel or the Cu, N-CDs@GO-CS hydrogel was used to treat bacteria-infected wounds in mice, which also protected the wound area from second infection. In vivo experiments demonstrate favorable wound healing results and have no significant harmful side effects to the major organs in mice. Overall, this work demonstrates that the antibacterial Cu, N-CDs@GO-CS hydrogel offers significant prospect as an antibacterial reagent for wound healing.

Tumor Microenvironment-Activatable Cyclic Cascade Reaction to Reinforce Multimodal Combination Therapy by Destroying the Extracellular Matrix.

The optimal therapy effect of tumors is frequently restricted by the dense extracellular matrix (ECM) and anoxia. Herein, an intelligent BPNs-Arg-GOx@MnO2 (BAGM) nanozyme is innovatively designed as a multimodal synergistic therapeutic paradigm that possesses both nitric oxide (NO) self-supplying and ECM degradation properties to reinforce the therapy effect by a tumor microenvironment (TME)-activatable cyclic cascade catalytic reaction. This theranostic nanoplatform is constructed by using polyethyleneimine-modified black phosphorus nanosheets as a "fishnet" to attach l-Arginine (l-Arg) and glucose oxidase (GOx) and then depositing mini-sized MnO2 nanosheets (MNs) on the surface by a facile situ biomineralization method. As an intelligent "switch", the MNs can effectively trigger the cascade reaction by disintegrating intracellular H2O2 to release O2. Then, the conjugated GOx can utilize O2 production to catalyze intracellular glucose to generate H2O2, which not only starves the tumor cells but also promotes oxidation of l-Arg to NO. Thereafter, matrix metalloproteinases will be activated by NO production to degrade the dense ECM and transform matrix collagen into a loose state. In turn, a loose ECM can enhance the accumulation of the BAGM nanozyme and thereby reinforce synergistic photothermal therapy/starvation therapy/NO gas therapy. Both in vitro and in vivo results indicate that the TME-tunable BAGM therapeutic nanoplatform with cascade anticancer property and satisfactory biosecurity shows potential in nanomedicine.

Three-Dimensional PdPtCu Nanoalloys with a Controllable Composition and Spiny Surface for the Enhancement of Ethanol Electrocatalytic Properties.

Pt-based nanomaterials have been proven to be effective catalysts for direct alcohol fuel cells (DAFCs). Specifically, the ternary nanoalloys (NAs) composed of Pt with other noble metals and transition metals can not only reduce the component of Pt but also enhance the electrocatalytic property and durability for alcohol oxidation. Herein, ternary PdPtCu NAs were synthesized through the solvothermal method using ethylene glycol as the solvent and reducing agent. The morphology and composition of PdPtCu NAs can be effectively controlled via selecting suitable surfactants and adjusting the proportion of precursors. The three-dimensional (3D) PdPtCu NAs with spiny rambutan-like morphology were obtained using the triblock copolymer Pluronic F-127 (PF-127) as the surfactant and adding three precursors with an equal molar ratio. The unique structure of PdPtCu NAs and the synergistic effect between the components significantly improved the electrocatalytic activity toward ethanol oxidation. Compared with different atomic ratio binary or ternary nanomaterials, 3D PdPtCu NAs manifested the best electrocatalytic performance.

Facile Synthesis Of Composition-Controllable PtPdAuTe Nanowires As Superior Electrocatalysts For Direct Methanol Fuel Cells.

Multicomponent Pt-based nanowires (NWs) have attracted widespread attention as eletrocatalysts toward direct alcohol fuel cells because of their unique one-dimensional structure and high reaction dynamics. Quaternary PtPdAuTe NWs are designed via a facile template method, and NWs with a different composition are obtained by adjusting the feed ratio of metal precursors. The direct displacement reaction of metal precursors with Te NWs and the partial oxidation of Te lead to the formation of quaternary NWs. The rough surface and abundant reactive sites deriving from the rearrangement of metal atoms on the Te NWs surface endow the PtPdAuTe NWs with a superior electrocatalytic property and durability for methanol oxidation. The Pt20 Pd20 Au10 Te50 NWs display the largest mass activity and best stability among all catalysts. The preparation of PtPdAuTe NWs could provide a viable strategy for the preparation of other multicomponent NWs.

Facile Synthesis of PdCu Echinus-Like Nanocrystals as Robust Electrocatalysts for Methanol Oxidation Reaction.

Exploiting high-performance and inexpensive electrocatalysts for methanol electro-oxidation is conductive to promoting the commercial application of direct methanol fuel cells. Here, we present a facile synthesis of echinus-like PdCu nanocrystals (NCs) via a one-step and template-free method. The echinus-like PdCu NCs possess numerous straight and long branches which can provide abundant catalytic active sites. Owing to the novel nanoarchitecture and electronic effect of the PdCu alloy, the echinus-like PdCu NCs display high electrocatalytic performance toward methanol oxidation reaction in an alkaline medium. The mass activity of echinus-like PdCu NCs is 1202.1 mA mgPd -1 , which is 3.7 times that of Pd/C catalysts. In addition, the echinus-like structure, as a kind of three-dimensional self-supported nanoarchitecture, endows PdCu NCs with significantly enhanced stability and durability. Hence, the echinus-like PdCu NCs hold prospect of being employed as electrocatalysts for direct alcohol fuel cells.

Ag@Fe3O4@C nanoparticles for multi-modal imaging-guided chemo-photothermal synergistic targeting for cancer therapy.

Novel multifunctional core-shell nanoparticles (NPs) have attracted widespread attention due to their easy-to-modify surface properties and abundant functional groups. This study introduces a facile approach to synthesize Ag@ iron oxide (Fe3O4) @C NPs, and modify with amino-poly (ethylene glycol) (PEG)-carboxyl and folate (FA) on the exposed carbon surface to produce high contrast for excellent stability, good biocompatibility, cancer cell targeting, and synergistic treatment. The multi-armed PEG at the edge of Ag@Fe3O4@C NPs provides the materials an excellent capacity for doxorubicin (DOX) loading. The carbon layer could be used as a photothermal reagent due to its excellent near-infrared (NIR) absorbance capacity, and Fe3O4 was used as a reagent for magnetic resonance (MR) imaging. In vivo combination therapy with this agent was administered in a mouse tumor model, and a remarkable synergistic antitumor effect that is superior to that obtained by monotherapy was achieved. Concerning these features together, these unique multifunctional Ag@Fe3O4@C-PEG-FA/DOX NPs could be regarded as an attractive nanoplatforms for chemo-photothermal synergistic tumor therapy with dual-modal fluorescence and MR imaging-guided targeting.

Binding of calcium cations with three different types of oxygen-based functional groups of superplasticizers studied by atomistic simulations.

This work investigated interactions between calcium cations (Ca2+) and three common types of oxygen-based functional groups of concrete superplasticizers using density functional theory (DFT) calculations and all-atom molecular dynamics (MD) simulations. The three common types of oxygen-based functional groups were modeled as three hypothetical, low-molecular-weight organic molecules, each containing a methyl-terminated oxyethylene dimer and an adsorbing head of two oxygen-based functional groups, and are referred to as carboxylate, sulfonate, and phosphate groups, respectively, following the usual terminology in the field of concrete admixtures. Our DFT results show that the binding strength of the three groups with calcium cations follows (from high to low) phosphate>carboxylate>sulfonate, and both the electrophilic attack and the chemical reactivity of the three groups contribute significantly to the binding strength. The MD simulation results indicate that the adsorption of the three small molecules on the calcite (1 0 4) surface in aqueous solution shares a similar pattern in the sense that just two oxygen atoms of two adjacent anchor groups adsorb on the calcium atoms on the top layer of the crystal. The adsorption strength among the three types of functional groups follows the same order as the binding strength obtained from DFT calculations; both results corroborate a similar rule-of-thumb established by experiments. Furthermore, interactions of the three types of groups with water molecules suggest that strong hydrogen-bonding interactions exist in those systems. Graphical abstract Binding of calcium cations with three different types of oxygen-based functional groups of superplasticizersᅟ.

Ultrasmall black phosphorus quantum dots: synthesis, characterization, and application in cancer treatment.

Black phosphorus quantum dots (BPQDs) are gaining popularity for applications in various fields because of their unique advantages. For biomedical applications, good biosafety is a prerequisite for the use of BPQDs in vivo. However, currently, little information is available about their basic properties and biocompatibility, which are of great importance for potential biomedical applications. In this work, we prepared BPQDs by an improved solvothermal method and evaluated their fluorescence, biocompatibility, and photothermal therapy (PTT) effectiveness. First, the structures and functions of the BPQDs were investigated at the cellular and molecular levels. It was found that the fluorescence of the BPQDs is wavelength-dependent and that they absorb in the UV-vis range; also, their quantum yield reached 10.2%. In particular, we considered the morphology and lysis of human red blood cells, in vivo blood coagulation, and plasma recalcification profiles. We found that the BPQDs have excellent biocompatibility and hemocompatibility with blood components. Overall, concentrations of the BPQDs ≤0.5 mg mL-1 had few adverse effects on blood components. The resulting BPQDs can efficiently convert near-infrared (NIR) light into heat; thus, they are suitable as a novel nanotheranostic agent for PTT of cancer. Meanwhile, the results of serum biochemistry tests revealed that the indicators were at similar levels for mice exposed to BPQDs and for control mice. Furthermore, from biodistribution analysis of the BPQDs, no apparent pathological damage was observed in any organs, especially in the spleen and kidneys, during the 30 day period. Our research indicates that the BPQDs have bio-imaging capability and biocompatibility and highlights their great potential in the therapy of cancer.

Bioinspired carbon quantum dots for sensitive fluorescent detection of vitamin B12 in cell system.

Zwitterion-modification, as a bioinspired strategy, provides greatly promising platforms for biological detection and sensor applications. A green, low-cost and straight-forward method for synthesis of highly fluorescent biomimetic carbon quantum dots (BCQDs) has been developed via pyrolysis of cytidine diphosphate choline (CDPC) and ethylenediamine. The BCQDs with a strong emission at wavelength of 450 nm shows ultrasensitive sensing capability for vitamin B12 with high selectivity. Using the fluorometric assay, the detection limit (DL) for vitamin B12 was found to be as low as 81 nM. Meanwhile, the results of 3-(4,5)-dimethylthiahiazo(-z-y1)-3,5-di-phenytetrazoliumromide (MTT), hemolysis measuring and morphological characterization of Red blood cells (RBCs) confirms the excellent biocompatibility of BCQDs. The imaging experiments of human cervical cancer cells (HeLa) certify that BCQDs could be served as an effective fluorescent sensing probe for label-free sensitive and selective detection of vitamin B12 in biological samples on account of their low toxicity and good biocompatibility. The BCQDs, further, were successfully applied to probe vitamin B12 in living cells, which broaden its potential application in vivo system.

Bamboo-like Composites of V2O5/Polyindole and Activated Carbon Cloth as Electrodes for All-Solid-State Flexible Asymmetric Supercapacitors.

A bamboo-like nanomaterial composed of V2O5/polyindole (V2O5/PIn) decorated onto the activated carbon cloth was fabricated for supercapacitors. The PIn could effectively enhance the electronic conductivity and prevent the dissolution of vanadium. And the activation of carbon cloth with functional groups is conducive to anchoring the V2O5 and improving surface area, which results in an enhancement of electrochemical performance and leads to a high specific capacitance of 535.5 F/g. Moreover, an asymmetric flexible supercapacitor based on V2O5/PIn@activate carbon cloth and reduced graphene oxide (rGO)@activate carbon cloth exhibits a high energy density (38.7 W h/kg) at a power density of 900 W/kg and good cyclic stability (capacitance retention of 91.1% after 5000 cycles). And the prepared device is shown to power the light-emitting diode bulbs efficiently.

On-chip supercapacitors with ultrahigh volumetric performance based on electrochemically co-deposited CuO/polypyrrole nanosheet arrays.

We introduce a new method for fabricating unique on-chip supercapacitors based on CuO/polypyrrole core/shell nanosheet arrays by means of direct electrochemical co-deposition on interdigital-like electrodes. The prepared all-solid-state device demonstrates exceptionally high specific capacitance of 1275.5 F cm(-3) (∼40 times larger than that of CuO-only supercapacitors) and high-energy-density of 28.35 mWh cm(-3), which are both significantly greater than other solid-state supercapacitors. More importantly, the device maintains approximately 100% capacity retention at 2.5 A cm(-3) after 3000 cycles. The in situ co-deposition of CuO/polypyrrole nanosheets on interdigital substrate enables effective charge transport, electrode fabrication integrity, and device integration. Because of their high energy, power density, and stable cycling stability, these newly developed on-chip supercapacitors permit fast, reliable applications in portable and miniaturized electronic devices.

Facile Synthesis of Molecularly Imprinted Graphene Quantum Dots for the Determination of Dopamine with Affinity-Adjustable.

A facilely prepared fluorescence sensor was developed for dopamine (DA) determination based on polyindole/graphene quantum dots molecularly imprinted polymers (PIn/GQDs@MIPs). The proposed sensor exhibits a high sensitivity with a linear range of 5 × 10(-10) to 1.2 × 10(-6) M and the limit of detection as low as 1 × 10(-10) M in the determination of DA, which is probably due to the tailor-made imprinted cavities for binding DA thought hydrogen bonds between amine groups of DA and oxygen-containing groups of the novel composite. Furthermore, the prepared sensor can rebind DA in dual-type: a low affinity type (noncovalent interaction is off) and a high affinity type (noncovalent interaction is on), and the rebinding interaction can be adjusted by tuning the pH, which shows a unique potential for adjusting the binding interaction while keeping the specificity, allowing for wider applications.

Dopamine fluorescent sensors based on polypyrrole/graphene quantum dots core/shell hybrids.

A facilely prepared fluorescent sensor was developed for dopamine (DA) detection with high sensitivity and selectivity based on polypyrrole/graphene quantum dots (PPy/GQDs) core/shell hybrids. The composites exhibit strong fluorescence emission, which is dramatically enhanced as high as three times than pristine GQDs. The prepared sensor allows a highly sensitive determination of DA by fluorescent intensity decreasing with the addition of DA and presents a good linearity in range of 5-8000 nM with the detection limit of 10 pM (S/N = 3). Furthermore, the application of the proposed approach have been demonstrated in real samples and showed promise in diagnostic purposes.

Polypeptide-functionalized NaYF4:Yb(3+),Er(3+) nanoparticles: red-emission biomarkers for high quality bioimaging using a 915 nm laser.

We prepared poly-L-aspartic acid (PASP) functionalized NaYF4:Yb(3+),Er(3+) upconversion nanoparticles (UCNP-PASP). These nanoparticles can give red upconversion emission under excitation at 915 nm, whose wavelength of emission and excitation is located in the optical window of biological tissue. Dynamic laser scatting and zeta potentials of UCNP-PASP were used to study their stabilities in different aqueous solution. To understand the mechanism of the red emission of UCNP-PASP, photoluminescence spectra of samples were recorded before and after modification with PASP, poly acrylic acid (PAA), and poly(ether imide) (PEI) ligands under excitation at 915 and 980 nm, respectively. The cytotoxicity of the UCNP-PASP was also examined on a A549 cell and KB cell by 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl-tetrazolium bromide (MTT) assay. Moreover, the PASP-functionalized UCNP was employed as a potential biomarker for in vitro and in vivo experiments of upconversion luminescence imaging.