Coordination-induced and tunable layered rare-earth hydroxide-complex intercalated nanohybrid phosphorescent photosensitizer and therapy.

Hydrotalcite intercalated nanohybrid has served as a vital phosphorescent photosensitizer owing to remarkable 1O2 quantum yield and high cell mortality performance. However, it is rather difficult for potential large or complex guest phosphors to directly intercalate into the hydrotalcite gallery. Hence, it is necessary to regulate the interlayer microenvironment of hydrotalcites firstly for outstanding photosensitive properties. Herein, two isomers, 5,5'BDA and 4,4'BDA, with distinctive dual coordinative features were selected to modify the layer microenvironment of the LGdH gallery and induce the introduction of prospective Gd(HPhN)3 phosphorescent complexes into hydrotalcite through two different coordination effects successively. A LGdH-BDA-Gd(HPhN)3 intercalated nanohybrid phosphorescent photosensitizer was successfully obtained. The results indicated that the more efficient improvement was observed from 5,5'BDA due to offering a more spacious and stable space. Specifically, LGdH-5,5'BDA-Gd(HPhN)3 showed significantly better room temperature phosphorescence properties than LGdH-4,4'BDA-Gd(HPhN)3, whose lifetime was nearly 15 times longer than the latter. Additionally, the LGdH-5,5'BDA-Gd(HPhN)3 system displayed superior singlet oxygen generation in vitro under 460 nm irradiation (the quantum yield Φ = 0.48) and outstanding photodynamic therapy performance in tumor cells. LGdH presented more remarkable enhancement performance on the RTP properties of the luminescent molecules. This work provides a novel platform for designing a high-performance hydrotalcite intercalated nanohybrid phosphorescent photosensitizer through coordination induction to regulate the layer microenvironment.

Framework Nucleic Acid-Enabled Programming of Electrochemical Catalytic Properties of Artificial Enzymes.

The creation and engineering of artificial enzymes remain a challenge, especially the arrangement of enzymes into geometric patterns with nanometer precision. In this work, we fabricated a series of novel DNA-tetrahedron-scaffolded-DNAzymes (Tetrazymes) and evaluated the catalytic activity of these Tetrazymes by electrochemistry. Tetrazymes were constructed by precisely positioning G-quadruplex on different sites of a DNA tetrahedral framework, with hemin employed as the co-catalyst. Immobilization of Tetrazymes on a gold electrode surface revealed horseradish peroxidase (HPR)-mimicking bioelectrocatalytic property. Cyclic voltammogram and amperometry were employed to evaluate the capability of Tetrazymes of different configurations to electrocatalyze the reduction of hydrogen peroxide (H2O2). These artificial Tetrazymes displayed 6- to 14-fold higher enzymatic activity than G-quadruplex/hemin (G4-hemin) without the DNA tetrahedron scaffold, demonstrating application potential in developing novel G-quadruplex-based electrochemical sensors.

Real-Time in Situ Monitoring of Nitrogen Dynamics in Wastewater Treatment Processes using Wireless, Solid-State, and Ion-Selective Membrane Sensors.

Real-time, in situ accurate monitoring of nitrogen contaminants in wastewater over a long-term period is critical for swift feedback control, enhanced nitrogen removal efficiency, and reduced energy consumption of wastewater treatment processes. Existing nitrogen sensors suffer from high cost, low stability, and short life times, posing hurdles for their mass deployment to capture a complete picture within heterogeneous systems. Tackling this challenge, this study presents solid-state ion-selective membrane (S-ISM) nitrogen sensors for ammonium (NH4+) and nitrate (NO3-) in wastewater that were coupled to a wireless data transmission gateway for real-time remote data access. Lab-scale test and continuous-flow field tests using real municipal wastewater indicated that the S-ISM nitrogen sensors possessed excellent accuracy and precision, high selectivity, and multiday stability. Importantly, autocorrections of the sensor readings on the cloud minimized temperature influences and assured accurate nitrogen concentration readings in remote-sensing applications. It was estimated that real-time, in situ monitoring using wireless S-ISM nitrogen sensors could save 25% of electric energy under normal operational conditions and reduce 22% of nitrogen discharge under shock conditions.

Disposable self-support paper-based multi-anode microbial fuel cell (PMMFC) integrated with power management system (PMS) as the real time "shock" biosensor for wastewater.

A paper-based multi-anode microbial fuel cell (PMMFC) integrated with power management system (PMS) was developed as a disposable self-support real-time "shock" biosensor for wastewater. PMMFCs were examined at three types of shocks (chromium, hypochlorite and acetate) in a batch-mode chamber, and exhibited various responses to shock types and concentrations. The power output of PMMFC sensor was four times as the carbon cloth (CC)-based MFCs, indicating the advantage of paper-based anode for bacterial adhesion. The power output was more sensitive than the voltage output under shocks, and thus preventing the false signals. The simulation of power harvest using PMS indicated that PMMFC could accomplish more frequent data transmission than single-anode MFCs (PSMFC) and CC anode MFCs (CCMMFC), making the self-support wastewater monitor and data transmission possible. Compared with traditional MFC sensors, PMMFCs integrated with PMS exhibit the distinct advantages of tight paper-packed structure, short acclimation period, high power output, and high sensitivity to a wide range of shocks, posing a great potential as "disposable self-support shock sensor" for real time in situ monitoring of wastewater quality.