Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products.

Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure-selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N2, reaching a current density of 20 mA cmgeo -2 at 1.04 V - 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in-situ spectroscopies and scattering experiments reveal a unique in situ generated Cu(2-x)+-OO-• active sites in CuCo, which initiates nucleophilic substitution of NH2 from the amide, leading to N-N coupling between *NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high-valence Ni3+ and Ni4+, which facilitates N-H activation. This process, in conjunction with the excessive accumulation of OH- ions on Jahn-Teller (JT) distorted Co sites, leads to the generation of NO2 - as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.

Intracellular Delivery of Therapeutic Protein via Ultrathin Layered Double Hydroxide Nanosheets.

The therapeutic application of biofunctional proteins relies on their intracellular delivery, which is hindered by poor cellular uptake and transport from endosomes to cytoplasm. Herein, we constructed a two-dimensional (2D) ultrathin layered double hydroxide (LDH) nanosheet for the intracellular delivery of a cell-impermeable protein, gelonin, towards efficient and specific cancer treatment. The LDH nanosheet was synthesized via a facile method without using exfoliation agents and showed a high loading capacity of proteins (up to 182%). Using 2D and 3D 4T1 breast cancer cell models, LDH-gelonin demonstrated significantly higher cellular uptake efficiency, favorable endosome escape ability, and deep tumor penetration performance, leading to a higher anticancer efficiency, in comparison to free gelonin. This work provides a promising strategy and a generalized nanoplatform to efficiently deliver biofunctional proteins to unlock their therapeutic potential for cancer treatment.

Label-free electrochemical immunosensor for highly sensitive COVID-19 spike protein detection.

The ongoing coronavirus pandemic responsible for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has rapidly increased the rate of global death and infections due to variant mutations (such as Delta and Omicron). While specifically developed and approved vaccines can limit the spread of disease in a population and severity of resulting symptoms, none have been demonstrated to effectively prevent infection altogether. Thus, reliable early diagnosis of COVID-19 is critical to identify positive cases to help contain the outbreak. Herein we report a label-free electrochemical immunosensor for rapid diagnosis of COVID-19 by using nitrogen-doped holey graphene (N-HRGO) as a nanocarrier decorated with thionine (TH) molecules as electrochemical indicators. With the spike protein located on the surface of the COVID-19 particles as the model target, the as-prepared electrochemical immunosensor could detect the presence of the COVID-19 spike protein over a wide linear range (1 pg mL-1-10 ng mL-1) with a low detection limit (0.3 pg mL-1). In addition, the developed electrochemical immunosensor exhibited an excellent selectivity (with insignificant current changes towards interfering proteins comparing with COVID-19 spike protein), a good reproducibility and long-term storage stability. Importantly, the electrochemical immunosensor thus developed could successfully and reliably detect the spike protein of COVID-19 in saliva and human serum complex samples. Thus, the as-prepared label-free electrochemical immunosensor can achieve rapid and sensitive detection of the COVID-19 spike protein, as a promising clinical diagnosis tool in monitoring the progression of COVID-19.

Understanding of catalytic ROS generation from defect-rich graphene quantum-dots for therapeutic effects in tumor microenvironment.

Owing to their low cost, high catalytic efficiency and biocompatibility, carbon-based metal-free catalysts (C-MFCs) have attracted intense interest for various applications, ranging from energy through environmental to biomedical technologies. While considerable effort and progress have been made in mechanistic understanding of C-MFCs for non-biomedical applications, their catalytic mechanism for therapeutic effects has rarely been investigated. In this study, defect-rich graphene quantum dots (GQDs) were developed as C-MFCs for efficient ROS generation, specifically in the H2O2-rich tumor microenvironment to cause multi-level damages of subcellular components (even in nuclei). While a desirable anti-cancer performance was achieved, the catalytic performance was found to strongly depend on the defect density. It is for the first time that the defect-induced catalytic generation of ROS by C-MFCs in the tumor microenvironment was demonstrated and the associated catalytic mechanism was elucidated. This work opens a new avenue for the development of safe and efficient catalytic nanomedicine.