Unveiling the Dynamic Electrocatalytic Activity of Online Synthesized Bimetallic Nanocatalysts via Electrochemiluminescence Microscopy.

Effective bimetallic nanoelectrocatalysis demands precise control of composition, structure, and understanding catalytic mechanisms. To address these challenges, we employ a two-in-one approach, integrating online synthesis with real-time imaging of bimetallic Au@Metal core-shell nanoparticles (Au@M NPs) via electrochemiluminescence microscopy (ECLM). Within 120 s, online electrodeposition and in situ catalytic activity screening alternate. ECLM captures transient faradaic processes during potential switches, visualizes electrochemical processes in real-time, and tracks catalytic activity dynamics at the single-particle level. Analysis using ECL photon flux density eliminates size effects and yields quantitative electrocatalytic activity results. Notably, a nonlinear activity trend corresponding to the shell metal to Au surface atomic ratio is discerned, quantifying the optimal surface component ratio of Au@M NPs. This approach offers a comprehensive understanding of catalytic behavior during the deposition process with high spatiotemporal resolution, which is crucial for tailoring efficient bimetallic nanocatalysts for diverse applications.

Photoinduced Electrogenerated Chemiluminescence Imaging of Plasmonic Photoelectrochemistry at Single Nanocatalysts.

In this study, we proposed a novel imaging technique, photoinduced electrogenerated chemiluminescence microscopy (PECLM), to monitor redox reactions driven by hot carriers on single gold nanoparticles (AuNPs) on TiO2. Under laser irradiation, plasmon-generated hot carriers were separated by an electric field, leaving hot holes on the surface of AuNPs to drive ECL reactions. PECL intensity was highly sensitive to the number of hot carriers. Through quantitative image analysis, we found that PECL density on individual AuNPs decreased significantly with an increase in particle diameter, indicating that particle size has a significant impact on photoelectrochemical conversion efficiency. For the first time, we verified the feasibility of PECLM in mapping the catalytic activity of single photocatalysts. PECLM opens a new prospect for the in situ imaging of photocatalysis in a high-throughput way, which not only facilitates the optimization of plasmonic photocatalysts but also contributes to the dynamic study of photocatalytic processes on micro/nanointerfaces.

Cascade Reaction Regulated Electrochemiluminescence via Dual-Atomic-Site Catalysts.

Single-atom catalysts (SACs), a novel kind of electrocatalysts with full metal utilization, have been developed as unique signal amplifiers in several sensing platforms. Herein, based on theoretical prediction of the oxygen reduction reaction (ORR) mechanism on different atom sites, we constructed dual-atomic-site catalysts (DACs), Fe/Mn-N-C, to catalyze luminol-dissolved oxygen electrochemiluminescence (ECL). Computational simulation indicated that the weak adsorption of OH* on a single Fe site was overcome by introducing Mn as the secondary metallic active site, resulting in a synergic dual-site cascade mechanism. The superior catalytic activity of Fe/Mn-N-C DACs for the ORR was proven by the highly efficient cathodic luminol ECL, surpassing the performance of single-site catalysts (SACs), Fe-N-C and Mn-N-C. Furthermore, the ECL system, enhanced by a cascade reaction, exhibited remarkable sensitivity to ascorbic acid, with a detection limit of 0.02 nM. This research opens up opportunities for enhancing both the ECL efficiency and sensing performance by employing a rational atomic-scale design for DACs.

Intraoperative Cavity Local Delivery System with NETs-Specific Drug Release for Post-Breast Cancer Surgery Recurrence Correction.

Postoperative breast cancer recurrence is tricky due to the limited therapeutic options. Transforming growth factors-ß (TGF-ß) is vital in promoting postoperative tumor recurrence. However, conventional blocking strategies fail to satisfy both bio-safety and sufficient relapse correction. Neutrophil extracellular traps (NETs) are essential for the spatiotemporal dynamics of TGF-ß at tumor-resection sites, whose unique mechanism for local TGF-ß amplification could remarkably increase the risk of relapse after surgery. Herein, the principle of NETs formation is ingeniously utilized to construct a surgical residual cavity hydrogel that mimics NETs formation. The hydrogel is prepared based on the electrostatic interaction between histidine (His) and sodium alginate (Alg). Then, arginine deiminase 4 (PAD4) protein is released during NETs formation. Simultaneously, the electrical property of His in hydrogel changes automatically, which further lead to promising localized release of anti-TGF-ß. The hydrogel system can realize specific and selective drug release at targeted NETs site over a prolonged period while exhibiting excellent biocompatibility. Superior breast cancer recurrence inhibition is achieved by suppressing TGF-ß and related indicators, impeding epithelial-mesenchymal transition (EMT) progression, and rectifying the locally exacerbated immunosuppressive environment within NETs. The novel NETs local microenvironment drug release functional hydrogel will provide inspiration for postoperative recurrence correction strategies.

[Effects of simulated weightlessness on rats mandible, lumbar vertebra and femur].

OBJECTIVE: To observe the effect of weightlessness simulation on rats mandible, lumbar vertebra and femur. METHOD: Twenty five Wistar rats were randomly arranged into control group (n=10) and tail-suspension group (n=15 rats). The experiment lasted for 28 d. Then the mandible, lumbar vertebra and femur were excised and the histological structure of condylar process of mandible, molar and premolar area of mandible body, first lumbar, head, middle segment and condyle of femur were examined. RESULT: After tail-suspension there was no distinct change in bone density and bone mass of condylar process. But the degree of interlacement of trabecular bone increased. The bone substance of mandible was very dense in both control and experimental groups. There was no stimulated difference of bone structure and bone mass between the two groups. There was no marked change in the thickness of periodontal membrane. The bone lamella in premolar area of experimental group arranged regularly. And its maturity was higher than that in molar area. The line of bone hyperplasia in molar area of experimental group arranged disorderly and irregularly, which means that much bone remodeling occurred. The component of trabecular bone decreased in femur and lumbar vertebra and the thickness was uneven. The interlacement and connection among trabecular bones was poor. CONCLUSION: Four weeks of stimulated weightlessness can lead to osteoporosis in acantha and femur [correction of feurar] but has no distinct effect on mandible.

The enhanced longevity and liver targetability of Paclitaxel by hybrid liposomes encapsulating Paclitaxel-conjugated gold nanoparticles.

Organic and inorganic drug delivery systems both demonstrate their own advantages and challenges in practical applications. Combining these two drug delivery strategies in one system is expected to solve their current issues and achieve desirable functions. In this paper, gold nanoparticles (GNPs) and liposomes have been chosen as the model systems to construct a hybrid system and investigate its performance for the tumor therapy of Paclitaxel (PTX). The thiol-terminated polyethylene glycol (PEG400)-PTX derivative has been covalently modified on the surface of GNPs, followed by the encapsulation of PTX-conjugated GNPs (PTX-PEG400@GNPs) in liposomes. The hybrid liposomes solve the solubility and stability problems of gold conjugates and show high drug loading capacity. In vitro PTX release from the hybrid system maintains the similar sustained behavior demonstrated in its conjugates. Under the protection of a biocompatible liposome shell, encapsulated PTX shows enhanced circulation longevity and liver targetability compared to Taxol(®) and PTX-PEG400@GNPs suspension in the pharmacokinetic and biodistribution studies. These indicate that encapsulating drug-conjugated inorganic nanoparticles inside organic carriers maintains the superiority of both vehicles and improves the performance of hybrid systems. Although these attributes of hybrid liposomes lead to a better therapeutic capacity in a murine liver cancer model than that of the comparison groups, it shows no significant difference from Taxol(®) and conjugate suspension. This result could be due to the delayed and sustained drug release from the system. However, it indicates the promising potential for these hybrid liposomes will allow further construction of a compound preparation with improved performance that is based on their enhanced longevity and liver targetability of Paclitaxel.

Glutathione-mediated drug release from Tiopronin-conjugated gold nanoparticles for acute liver injury therapy.

Tiopronin-conjugated gold nanoparticles (TPN@GNPs), with glutathione (GSH)-responsive drug release property, were developed for acute liver injury therapy. The TPN@GNPs were prepared using a one-pot synthesis method and characterized by UV-vis and transmission electronic microscopy methods. The TPN@GNPs displayed typical surface plasmon resonance of nanogold with a narrow size distribution (ca. 2 nm). The in vitro drug release profiles of the conjugates indicated that TPN@GNPs were able to release TPN in a sustained fashion for 4 h at a simulated intracellular level of GSH. pH values or ionic strengths of the release media had no obvious influence on TPN release from the surface of nanoparticles. The pharmacokinetic studies in rats showed that the TPN@GNPs had longer MRT (7.71 h) than TPN (3.96 h), indicating sustained release pattern of TPN@GNPs in vivo. The sustained release of TPN at the relative high GSH concentration could ameliorate the instability of TPN and enable the drug release in the target cells. Although the IC50 value of TPN@GNPs with TPN/AuCl4(-) of 3:1 (mol/mol) showed slight increase in comparison with that of the free TPN in HepG2 cells (1.26±1.07 vs. 1.73±1.16 mg/mL), the TPN@GNPs displayed better effects over TPN in the treatment of acute liver injury in vivo. In a liver injury mice model induced by CCl4, the histological analysis showed both the TPN@GNPs and free TPN group could repair the liver injury. In addition, the biochemical parameters showed TPN@GNPs could reduced the aminotransferase to a lower level compared with TPN, which might be due to the sustained drug release and passive liver targeting properties of TPN@GNPs. It demonstrated that gold nanoparticle-based drug delivery system allowed smart functions and superior properties by taking advantages of the unique small size effects and surface chemical properties.