Cation exchange (CE) is a burgeoning method for controlled crystal synthesis; however, its applications in bioanalysis are still in their infancy. Herein, we explored the transformation of ZnIn2S4 in properties after the CE reaction with Cu2+ ions; furthermore, the discrepancy was employed to design a dual-readout detection system of photothermal and polarity-switchable photoelectrochemical (PEC) immunoassays to realize reliable detection of carcinoembryonic antigen (CEA). In the presence of CEA, the CuO nanoparticles (CuO NPs) employed as dual-signal response probes would bond to the microplates and be acidolyzed by HCl to release Cu2+, which could replace Zn2+ and In3+ via the CE reaction. After the CE reaction is completed, the photocurrent would switch from a weak anodic photocurrent to a cathode one by using a 635 nm laser as a signal amplifier, while the photothermal signal would be enhanced with 808 nm laser illumination. On the basis of the polarity-switchable PEC strategy, CEA could be accurately detected from 0.1 to 50 ng mL-1 with a limit of detection (LOD) of 48 pg mL-1 (S/N = 3). Moreover, the photothermal assay for CEA detection possesses a linear range from 0.5 to 100 ng mL-1 with a LOD of 0.21 ng mL-1. In addition, the designed sensing platform only relies on devices with portability that are permitted for point-of-care detection.

Cation Exchange Reaction-Mediated Photothermal and Polarity-Switchable Photoelectrochemical Dual-Readout Biosensor.

The use of photocatalytic solar energy to drive CO2 reduction is beneficial for addressing fossil fuel shortages and environmental pollution issues. We synthesized a twin S-scheme g-C3N4/CuFe2O4/ZnIn2S4 heterojunction, which was used to construct a self-supporting three-phase system for photocatalytic CO2 reduction. Two built-in electric fields in this heterojunction induced effective migration of photogenerated carriers, resulting in a wide light response range and strong oxidation ability. This twin S-scheme photocatalytic system without a sacrificial agent had high CH4 selectivity (96.8%) and surprise production rate of CH4 (267.4 μmol g–1 h–1), and still maintained an excellent cycle rate (249–267.4 μmol g–1 h–1) during five cycles. In addition, g-C3N4/CuFe2O4/ZnIn2S4 heterojunction possessed both hydrophilicity and hydrophobicity, which achieved an efficient transformation of CO2 into CH4 by controlling interface wettability. g-C3N4 as a hydrophobic layer promoted CO2 mass transfer to achieve the enrichment of CO2 on the heterojunction surface; ZnIn2S4 as a hydrophilic layer could well adsorb H2O, which was further oxidized by the photogenerated holes into many protons (H+). Finally, DFT calculations found that Fe–N bonds located between g-C3N4 and CuFe2O4 played a crucial role during the photocatalytic CO2 reduction. They served as a bridge for electron transfer to induce the bending adsorption of CO2, which enhanced the adsorption of *CO and stabilization of *H. 

Twin S-Scheme g-C3N4/CuFe2O4/ZnIn2S4 Heterojunction with a Self-Supporting Three-Phase System for Photocatalytic CO2 Reduction: Mechanism Insight and DFT Calculations

Abstract Although S‐scheme artificial photosynthesis shows promise for photocatalytic hydrogen production, traditional methods often overly concentrate on a single reduction site. This limitation results in inadequate redox capability and inefficient charge separation, which hampers the efficiency of the photocatalytic hydrogen evolution reaction. To overcome this limitation, a double S‐scheme system is proposed that leverages dual reduction sites, thereby preserving energetic photo‐electrons and holes to enhance apparent quantum efficiency. The design features a double S‐scheme junction consisting of CdS nanospheres decorated with anatase TiO 2 nanoparticles coupled with graphitic C 3 N 4 . The as‐prepared catalyst exhibits a hydrogen evolution rate of 26.84 mmol g −1 h −1 and an apparent quantum efficiency of 40.2% at 365 nm. This enhanced photocatalytic hydrogen evolution is ascribed to the efficient charge separation and transport induced by the double S‐scheme. Both theoretical calculations and comprehensive spectroscopy tests (both in situ and ex situ) affirm the efficient charge transport across the catalyst interface. Moreover, substituting the reduction‐type catalyst CdS with other similar sulfides like ZnIn 2 S 4 , ZnS, MoS 2 and In 2 S 3 further confirms the feasibility of the proposed double S‐scheme configuration. The findings provide a pathway to designing more effective double S‐scheme artificial photosynthetic systems, opening up fresh perspectives in enhancing photocatalytic hydrogen evolution performance. 

Artificial Photosynthetic System with Spatial Dual Reduction Site Enabling Enhanced Solar Hydrogen Production.

The development of alternative catalytic systems toward high‐performance CO2 photoreduction is considered to be a promising approach to address the future energy demand and reduce the CO2 emissions. However, CO2 molecules are thermodynamically stable in nature, and thus the adsorption and activation of CO2 on the surface of catalysts are the key factors to determine the conversion efficiency. Herein, a porous liquid (NH2‐UIO‐66 PL) is demonstrated for efficiently facilitating the adsorption and activation of CO2 by modification of metal–organic framework (NH2‐UIO‐66) with ionic liquid via amide bonds. CdS/NH2‐UIO‐66 PL exhibits high‐performance CO2‐to‐CO photoreduction with CO yield of 71.37 µmol g−1 h−1 and selectivity of 100%. Experiments and theoretical calculations show that the introduced amide moieties not only enriched the electron density at Zr4+ active sites but also stabilize *COOH intermediate. The achievements provide an effective strategy for the development of metal–organic frameworks for energy catalysis.

Amide‐Engineered Metal–Organic Porous Liquids Toward Enhanced CO2 Photoreduction Performance

Metal nanoparticles (M-NPs) have garnered significant attention due to their unique properties, driving diverse applications across packaging, biomedicine, electronics, and environmental remediation. However, the potential health risks associated with M-NPs must not be disregarded. M-NPs' ability to accumulate in organs and traverse the blood-brain barrier poses potential health threats to animals, humans, and the environment. The interaction between M-NPs and various cellular components, including DNA, multiple proteins, and mitochondria, triggers the production of reactive oxygen species (ROS), influencing several cellular activities. These interactions have been linked to various effects, such as protein alterations, the buildup of M-NPs in the Golgi apparatus, heightened lysosomal hydrolases, mitochondrial dysfunction, apoptosis, cell membrane impairment, cytoplasmic disruption, and fluctuations in ATP levels. Despite the evident advantages M-NPs offer in diverse applications, gaps in understanding their biocompatibility and toxicity necessitate further research. This review provides an updated assessment of M-NPs' pros and cons across different applications, emphasizing associated hazards and potential toxicity. To ensure the responsible and safe use of M-NPs, comprehensive research is conducted to fully grasp the potential impact of these nanoparticles on both human health and the environment. By delving into their intricate interactions with biological systems, we can navigate the delicate balance between harnessing the benefits of M-NPs and minimizing potential risks. Further exploration will pave the way for informed decision-making, leading to the conscientious development of these nanomaterials and safeguarding the well-being of society and the environment. 

Oxidative stress and potential effects of metal nanoparticles: A review of biocompatibility and toxicity concerns.

It is facing a tremendous challenge to develop the desirable hybrids for photocatalytic H2 generation by integrating the advantages of a single semiconductor. Herein, an all-sulfide ZnIn2 S4 /CdS/PdS heterojunction is constructed for the first time, where CdS and PdS nanoparticles anchor in the spaces of ZnIn2 S4 micro-flowers due to the confinement effects. The morphology engineering can guarantee rapid charge transfer owing to the short carrier migration distances and the luxuriant reactive sites provided by ZnIn2 S4 . The S-scheme mechanism between ZnIn2 S4 and CdS assisted by PdS cocatalyst is testified by in situ irradiated X-ray photoelectron spectroscopy and electron paramagnetic resonance (EPR), where the electrons and holes move in reverse driven by work function difference and built-in electric field at the interfaces. The optimal ZnIn2 S4 /CdS/PdS performs a glaring photocatalytic activity of 191.9 µmol h-1 (10 mg of catalyst), and the largest AQE (apparent quantum efficiency) can reach a high value of 26.26%. This work may afford progressive tactics to design multifunctional photocatalysts.

Construction of ZnIn2 S4 /CdS/PdS S-Scheme Heterostructure for Efficient Photocatalytic H2 Production.

The increasing use of metal oxide-based nanoparticles (MNPs) and their release into the environment cast concerns about their environmental impacts. Massive efforts have been focused on environmental behaviours and ecotoxicities to figure out the potential threats posed by MNPs. This review systematically summarises and re-analyses published data about the MNP interactions and transformation processes in freshwater and the toxicological effects of MNPs on invertebrates. A case study was conducted through meta-analysis to examine the impacts of silver nanoparticle exposure to freshwater invertebrates. The conclusions categorized the current understanding of the outcome and ecotoxicity of MNPs in freshwater. The adverse outcome pathway (AOP) is recommended for environmental risk assessment as it provides a rapid and accurate risk assessment of an increasing number of novel compounds consuming fewer resources and animal tests. Invertebrates contribute significantly towards developing robust AOPs thanks to a shorter life cycle, allowing chronic and complete life cycle toxicity tests.

/pdf/emerging-investigator-series-metal-nanoparticles-in-2oldcv9a.pdf

Emerging investigator series: metal nanoparticles in freshwater: transformation, bioavailability and effects on invertebrates

Chronic and transgenerational effects of silver nanoparticles in freshwater gastropod Lymnaea stagnalis.

https://doi.org/10.1016/j.envpol.2022.119999

Comparative study of the sensitivity of two freshwater gastropods, Lymnaea stagnalis and Planorbarius corneus, to silver nanoparticles: bioaccumulation and toxicity.

A bipolar pyridine-functionalized porphyrin with hybrid charge-storage for dual-ion batteries.

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