Versatile Metal-Organic Framework Incorporating Ag2S for Constructing a Photoelectrochemical Immunosensor for Two Breast Cancer Markers.

Breast cancer poses the significance of early diagnosis and treatment. Here, we developed an innovative photoelectrochemical (PEC) immunosensor characterized by high-level dual photocurrent signals and exceptional sensitivity. The PEC sensor, denoted as MIL&Ag2S, was constructed by incorporating Ag2S into a metal-organic framework of MIL-101(Cr). This composite not only enhanced electron-hole separation and conductivity but also yielded robust and stable dual photocurrent signals. Through the implementation of signal switching, we achieved the combined detection of cancer antigen 15-3 (CA15-3) and carcinoembryonic antigen (CEA) with outstanding stability, reproducibility, and specificity. The results revealed a linear range for CEA detection spanning 0.01-32 ng/mL, with a remarkably low detection limit of 0.0023 ng/mL. Similarly, for CA15-3 detection, the linear range extended from 0.1 to 320 U/mL, with a low detection limit of 0.014 U/mL. The proposed strategy introduces new avenues for the development of highly efficient, cost-effective, and user-friendly PEC sensors. Furthermore, it holds promising prospects for early clinical diagnosis, contributing to potential breakthroughs in medical detection and ultimately improving patient outcomes.

Molecularly imprinted polymer photoelectrochemical sensor for the detection of triazophos in water based on carbon quantum dot-modified titanium dioxide.

Widely used organophosphorus pesticide triazophos (TAP) can easily cumulate in aquatic system due to its high stability chemically and photochemically and thus posing significant threat to aquatic creatures and humans' health. Urging demand for rapid determining TAP in water has risen. Photoelectrochemical (PEC) sensing turns out to be a good candidate for its simplicity in fabrication and swiftness in detection. Nevertheless, traditional PEC sensors often lack selectivity as their signal generation primarily relies on the oxidation of organic compounds in the electrolyte by photo-induced holes. To address this limitation, molecularly imprinted polymers (MIPs) can be in combined with PEC sensors to significantly enhance the selectivity. Here, we present a novel approach utilizing a PEC sensor enhanced by carbon-modified titanium dioxide molecularly imprinted polymers (MIP/C/TiO2 NTs). Carbon quantum dot (CQD) modification of titanium dioxide nanotube arrays (C/TiO2 NTs) was achieved through a one-step anodization process, effectively enhancing visible light absorption by narrowing the band gap of TiO2, and CQDs also function as sensitizer accelerating charge transfer for improved and stable photocurrent signals during detection. Our method further incorporates MIPs to heighten the selectivity of the PEC sensor. Electro-polymerization using cyclic voltammetry was employed to polymerize MIPs with pyrrole as the functional monomer and triazophos as the target molecule. The resultant MIP/C/TiO2 NT sensor exhibited remarkable sensitivity, with a detection limit of 0.03 nM (S/N = 3), alongside exceptional selectivity and stability for triazophos detection in water. This offers a promising avenue for efficient, cost-effective, and rapid monitoring of pesticide contaminants in aquatic environments, contributing to the broader goals of environmental preservation and public health.

Nonmetallic Nitrogen-Doped MnO2 as Highly Efficient Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries.

Zinc-air batteries (ZABs) have been considered as one of the most promising energy storage devices to solve the problem of energy crisis and environmental pollution. In this work, we reported the synthesis of nitrogen-doped MnO2 (N-MnO2 ) to replace the noble metal electrocatalysts for air cathode in ZABs. The doped N atoms here introduced more Mn3+ and oxygen vacancies for MnO2 , enhancing charge transfer property and accelerating surface intermediate product during the oxygen reduction reaction (ORR). Hence, the best N-MnO2 achieved remarkable electrocatalytic activities towards ORR (half-wave potential of 0.797 V vs. RHE), and reversible oxygen overpotential of around 0.842 V, which is better than or comparable to the Pt/C and Mn-based catalysts reported recently. Moreover, the homemade ZABs based on N-MnO2 showed the maximum power density of 132.8 mW cm-2 and excellent cyclic stability.

Au/TiO2-based molecularly imprinted photoelectrochemical sensor for dibutyl phthalate detection.

A photoelectrochemical molecular imprinting sensor based on Au/TiO2 nanocomposite was constructed for the detection of dibutyl phthalate. Firstly, TiO2 nanorods were grown on fluorine-doped tin oxide substrate by hydrothermal method. Then, gold nanoparticles were electrodeposited on TiO2 to fabricate Au/TiO2. Finally, molecular imprinted polymer was electropolymerized on the Au/TiO2 surface to construct MIP/Au/TiO2 PEC sensor for DBP. The conjugation effect of MIP accelerates the electron transfer between TiO2 and MIP, which can greatly improve the photoelectric conversion efficiency and sensitivity of the sensor. In addition, MIP can also provide sites for highly selective recognition of dibutyl phthalate molecules. Under optimal experimental conditions, the prepared photoelectrochemical sensor was used for the quantitative determination of DBP and the results showed a wide linear range (50 to 500 nM), a low limit of detection (0.698 nM), and good selectivity. The sensor was used in a study of real water samples to show that it has promising applications in environmental analysis.

Exploiting Dynamic Nonlinearity in Upconversion Nanoparticles for Super-Resolution Imaging.

Single-beam super-resolution microscopy, also known as superlinear microscopy, exploits the nonlinear response of fluorescent probes in confocal microscopy. The technique requires no complex purpose-built system, light field modulation, or beam shaping. Here, we present a strategy to enhance this technique's spatial resolution by modulating excitation intensity during image acquisition. This modulation induces dynamic optical nonlinearity in upconversion nanoparticles (UCNPs), resulting in variations of nonlinear fluorescence response in the obtained images. The higher orders of fluorescence response can be extracted with a proposed weighted finite difference imaging algorithm from raw fluorescence images to generate an image with higher resolution than superlinear microscopy images. We apply this approach to resolve single nanoparticles in a large area, improving the resolution to 132 nm. This work suggests a new scope for the development of dynamic nonlinear fluorescent probes in super-resolution nanoscopy.

Photoelectrochemical aptasensor based on nanocomposite of CdSe@SnS2 for ultrasensitive and selective detection of sulfamethazine.

A photoelectrochemical (PEC) aptasensor based on CdSe@SnS2 nanocomposite has been developed to detect sulfamethazine (SMZ). The introduction of CdSe into SnS2 displayed an amplified PEC signal, which was higher than that of pure CdSe and SnS2, attributable to its enhanced light harvesting capacity and promoted PEC energy conversion efficiency. Due to the formation of specific non-covalent bonds, the SMZ-binding aptamer (SBA) has significant specificity and sensitivity. When SMZ was incubated on a CdSe@SnS2 modified electrode fixed with aminated SBA, the formation of the SMZ/SBA complex increased the space resistance of electron transfer and hindered the electronic migration between the electrodes, resulting in a decrease in photocurrent. The greater the adsorbed amount on the SBA, the lower the photocurrent produced.  Under optimized conditions the photocurrent response of MCH/SBA/CdSe@SnS2/FTO was inversely proportional to the SMZ concentration in the range 0.1 to 100 pM, with a detection limit (3 S/N) of 0.025 pM (at 0 V vs. Hg/HgCl). The recoveries ranged from 95.8 to 104% with relative standard deviations (RSDs) < 6.3% (n = 3) in actual water sample. This PEC aptasensor which shows considerable potential in SMZ detection applications has high selectivity, reproducibility, and good stability.

Mo2 C/Reduced Graphene Oxide Composites with Enhanced Electrocatalytic Activity and Biocompatibility for Microbial Fuel Cells.

A simple, cost-effective strategy was developed to effectively improve the electron transfer efficiency as well as the power output of microbial fuel cells (MFCs) by decorating the commercial carbon paper (CP) anode with an advanced Mo2 C/reduced graphene oxide (Mo2 C/RGO) composite. Benefiting from the synergistic effects of the superior electrocatalytic activity of Mo2 C, the high surface area, and prominent conductivity of RGO, the MFC equipped with this Mo2 C/RGO composite yielded a remarkable output power density of 1747±37.6 mW m-2 , which was considerably higher than that of CP-MFC (926.8±6.3 mW m-2 ). Importantly, the composite also facilitated the formation of 3D hybrid biofilm and could effectively improve the bacteria-electrode interaction. These features resulted in an enhanced coulombic efficiency up 13.2 %, nearly one order of magnitude higher than that of the CP (1.2 %).

Controlled Construction of an Exquisite Three-Component Co-assembly Supramolecular Structure at the Liquid-Solid Interface.

A three-component supramolecular co-assembly structure formed at the liquid-solid interface by employing a shape-persistent π-conjugated macrocycle (16mer) and two guest molecules (COR and C60) is demonstrated. Scanning tunneling microscopy (STM) observations revealed that 16mer can serve as a versatile host molecule that can co-assemble with both COR and C60 guest molecules to form stable two-component structures, where the COR guest molecule filled in the gap between the side chains of adjacent 16mer molecules, and the C60 guest molecule entered the inner cavity of 16mer. It was found that the adding sequence of COR and C60 guest molecules is crucial to the resulting co-adsorption structure in the three-component system. To obtain the intriguing 16mer-COR-C60 three-component co-assembly structure, the 16mer and COR two-component co-assembly structure should first be constructed on a HOPG surface, followed by addition of C60. Based on the analysis of the STM results and the density functional theory (DFT) calculations, the formation mechanism of the assembled structures was revealed.

Electrochemiluminescence Investigation of Glucose Transporter 4 Expression at Skeletal Muscle Cells Surface Based on a Graphene Hydrogel Electrode.

In situ detection of the expression level of cell-surface receptors has become a hotspot study in recent years. We propose in this manuscript a novel strategy for sensitive electrochemiluminescence (ECL) detection of glucose transporter 4 (GLUT4) on human skeletal muscle cells (HSMCs). Graphene hydrogel (GH) was selected to fabricate a permeable electrode with the purpose of overcoming the steric hindrance of cells on electrode, which leads to errors in the detection of cell-surface receptors. GLUT4 was labeled with carbon dots (CDs), which generate ECL emission at the interface between GH and cells, so about half the amount of GLUT4 expressed at the cell surface could be determined, which provided an accurate GLUT4 expression quantification. The prepared cytosensor exhibited good analytical performance for HSMC cells, ranging from 500 to 1.0 × 106 cells·mL-1, with a detection limit of 200 cells·mL-1. The average amount of GLUT4 per HSMC cell was calculated to be 1.88 × 105. Furthermore, GLUT4 on HSMC surface had a 2.3-fold increase under the action of insulin. This strategy is capable of evaluating the receptors on the cell surface, which may push the application of ECL for disease diagnosis.

Bilayer Adsorption of Porphyrin Molecules Substituted with Carboxylic Acid atop the NN4A Network Revealed by STM and DFT.

Bottom-up technology is a bridge connecting a two-dimensional (2D) monolayer structure with a three-dimensional (3D) bulk structure. From 2D to 3D, it helps us to understand the driving force of an organization process to control the molecular arrangement in the 3D phase. Here, we aimed at the fabrication of multilayer nanostructures on solid substrates. Bis(3,5-diacidic)diazobenzene (NN4A) was chosen as one molecule because of its photosensitive azo group and carboxylic group possessing hydrogen bonding effect, while porphyrin molecules composed of different numbers and positions of carboxylic acid groups were used as the other component. It was found that the porphyrin molecules could adopt different adsorption configurations because of the influence of carboxylic groups, leading to different subsequent coassemblies on the solid surface. The NN4A/porphyrin systems underwent structural transformation when NN4A molecules were adsorbed on the highly oriented pyrolytic graphite surface with predeposited porphyrin. This work displayed an efficient method on the construction of multilayer nanostructures in the molecular surface engineering and provided a new way to construct 3D structures based on the molecular design.

Theoretical studies on the purine radical induced purine-purine type intrastrand cross-links.

At the density functional theory (DFT) level, addition reactions between the guanine-8-yl radical and its 3'/5' neighboring purine deoxynucleosides forming the purine-purine type intrastrand cross-links were studied. It is found that addition of the guanine-8-yl radical to the C8 site of its 5' neighboring deoxyguanosine or deoxyadenosine is a two-step reaction consisting of a structurally relatively unfavourable conformational transformation step, while the corresponding 3' C8 addition is straightforward and kinetically more efficient. The 3' C8 preference of the guanine-8-yl radical additions indicates the existence of an obvious sequence effect, which is completely opposite to that observed in the formation of pyrimidine radicals induced DNA intrastrand cross-links. The detrimental effects from steric hindrance and stabilizing weak interactions make these addition reactions markedly suppressed in double stranded DNA. This work broadens our knowledge about the possible types of DNA intrastrand cross-links.

Voltammetric determination of levofloxacin using silver nanoparticles deposited on a thin nickel oxide porous film.

The authors describe a simplified chemical precipitation method and silver mirror reaction to synthesize a nanocomposite consiting of silver nanoparticles on a thin and porous nickel oxide film. Placed on a glassy carbon electrode (GCE), it allows for the determination of levofloxacin (LEV) via square wave voltammetry (SWV). Under optimal detection conditions, the voltammetric signal (typically measured at around 0.96 V vs. SCE) increases linearly in the 0.25-100 µM LEV concentration range. And the detection limit was calculated as 27 nM (at S/N = 3). The sensor is highly selective, stable and repeatable. It was applied to the determination of LEV in spiked human serum samples, and the satisfactory results confirm the applicability of this sensor to practical analyses. Graphical abstract Schematic of a two-step method to synthesize a nanocomposite consisting of nickel oxide porous thin-film supported silver nanoparticles. The composite was used for improved voltammetric determination of levofloxacin.

A Stable Quasi-Solid-State Sodium-Sulfur Battery.

Ambient-temperature sodium-sulfur (Na-S) batteries are considered a promising energy storage system due to their high theoretical energy density and low costs. However, great challenges remain in achieving a high rechargeable capacity and long cycle life. Herein we report a stable quasi-solid-state Na-S battery enabled by a poly(S-pentaerythritol tetraacrylate (PETEA))-based cathode and a (PETEA-tris[2-(acryloyloxy)ethyl] isocyanurate (THEICTA))-based gel polymer electrolyte. The polymeric sulfur electrode strongly anchors sulfur through chemical binding and inhibits the shuttle effect. Meanwhile, the in situ formed polymer electrolyte with high ionic conductivity and enhanced safety successfully stabilizes the Na anode/electrolyte interface, and simultaneously immobilizes soluble Na polysulfides. The as-developed quasi-solid-state Na-S cells exhibit a high reversible capacity of 877 mA h g-1 at 0.1 C and an extended cycling stability.

Enhanced Photoelectrochemical Activity by Autologous Cd/CdO/CdS Heterojunction Photoanodes with High Conductivity and Separation Efficiency.

The development for hydrogen from solar energy has attracted great attention due to the global demand for clean, environmentally friendly energy. Herein, autologous Cd/CdO/CdS heterojunctions were prepared in a carefully controlled process with metallic Cd as the inner layer and CdO as the interlayer. Further research revealed that the transportation and separation of photogenerated pairs were enhanced due to low resistance of the Cd inner layer and the type II CdO/CdS heterojunction. As a result, the optimized Cd/CdO/CdS heterojunction photoanode showed outstanding and long-term photoelectrochemical activity for water splitting, with a current density of 3.52 mA cm-2 , or a benchmark specific hydrogen production rate of 1.65 µmol cm-2 min-1 at -0.3 V versus Ag/AgCl, by using the environmental pollutants of sulfide and sulfite as sacrificial agents.

Formation of pyrimidine-pyrimidine type DNA intrastrand cross-links: a theoretical verification.

Pyrimidine-type radicals have been demonstrated to be able to attack their 3' or 5' neighboring purine nucleotides forming diverse DNA intrastrand cross-links, but whether or not these radicals can attack their surrounding pyrimidine nucleotides forming pyrimidine-pyrimidine type DNA intrastrand cross-links remains unclear. To resolve this question, probable additions of the uracil-5-methyl (˙UCH2) radical to the C5[double bond, length as m-dash]C6 double bond of its 3'/5' neighboring pyrimidine nucleotides in the four models, 5'-T(˙UCH2)-3', 5'-C(˙UCH2)-3', 5'-(˙UCH2)T-3', and 5'-(˙UCH2)C-3', are explored in the present work employing density functional theory (DFT) methods. The C6 site of its 5' neighboring thymidine is the preferred target for ˙UCH2 radical addition, while additions of the ˙UCH2 radical to the C6 and C5 sites of its 5' neighboring deoxycytidine are found to be competitive reactions. The ˙UCH2 radical can react with both the C6 and C5 sites of its 3' neighboring pyrimidine nucleotides, but the efficiencies of these reactions are predicted to be much lower than those of the corresponding addition reactions to its 5' neighboring pyrimidine nucleotides, indicating the existence of an obvious sequence effect. All the addition products could be finally transformed into closed-shell intrastrand cross-links, the molecular masses of which are found to be exactly the same as certain MS values determined in a recent study of an X-irradiated deoxygenated aqueous solution of calf thymus DNA. The present study thus not only definitely corroborates the fact that the reactive ˙UCH2 radical can attack its 3'/5' neighboring pyrimidine nucleotides forming several pyrimidine-pyrimidine type DNA intrastrand cross-links, but also provides a plausible explanation for the identities of these structurally unknown intrastrand cross-links.

DNA intrastrand cross-links induced by the purine-type deoxyguanosine-8-yl radical: a DFT study.

Currently, all known DNA intrastrand cross-links are found to be induced by pyrimidine-type radicals; however, whether or not purine-type radicals are able to cause DNA intrastrand cross-links remains unclear. In the present study, probable additions of the highly reactive deoxyguanosine-8-yl radical to its 3'/5' neighboring pyrimidine nucleotides in four model compounds, 5'-G˙T-3', 5'-TG˙-3', 5'-G˙C-3', and 5'-CG˙-3', were studied using density functional theory (DFT) methods. In single-stranded DNA, the deoxyguanosine-8-yl radical is preferred to efficiently attack the C5 site of its 3' neighboring deoxythymidine or deoxycytidine, forming the G[8-5]T or G[8-5]C intrastrand cross-link rather than the C6 site forming the G[8-6]T or G[8-6]C intrastrand cross-link. The four corresponding sequence isomers, namely T[5-8]G, T[6-8]G, C[5-8]G, and C[6-8]G, formed by additions of deoxyguanosine-8-yl radical to its 5' neighboring pyrimidine nucleotides are predicted to be formed inefficiently. In double-stranded DNA, considering the detrimental effects of stabilizing weak interactions on related structural adjustments required in each addition reaction path, relatively lower reaction yields are suggested for the G[8-5]T and G[8-5]C intrastrand cross-links, while the formation of the other six intrastrand cross-links becomes quite difficult. All calculations definitely demonstrate that, in addition to pyrimidine-type radicals, the purine-type deoxyguanosine-8-yl radical is able to attack its 3'/5' neighboring pyrimidine nucleotides forming several DNA intrastrand cross-links.

The Facile Synthesis of Branch-Trunk Ag Hierarchical Nanostructures and Their Applications for High-Performance H2O2 Electrochemical Sensors.

A novel branch-trunk Ag hierarchical nanostructure was synthesized via a galvanic replacement reaction combined with microwave-assisted synthesis using Te nanowire as a sacrificial template. The Te nanowire was synthesized via a hydrothermal process. We further investigated the potential application of the obtained hierarchical nanostructures in electrochemical sensor analysis. The results showed that the as-prepared sensor exhibited a wide linear range with 0.05 µM to 1.925 mM (R = 0.998) and the detection limit was estimated to be 0.013 µM (S/N = 3). These results indicate the branch-truck Ag hierarchical nanostructures are an excellent candidate material for sensing applications.

Regenerated Ni-Doped LiCoO2 from Spent Lithium-Ion Batteries as a Stable Cathode at 4.5 V.

In the context of the increasing number of spent lithium-ion batteries, it is urgent to explore cathode regeneration and upcycling solutions to reduce environmental pollution, promote resource reuse, and meet the demand for high-energy cathode materials. Here, a closed-loop recycling method is introduced, which not only reclaims cobalt and lithium elements from spent lithium-ion batteries but also converts them into high-voltage LiCoO2 (LCO) materials. This approach involved pretreatment, chlorination roasting, water leaching, and ion doping to regenerate nickel-doped LCO (Ni-RLCO) materials. The doping of nickel effectively enhances the electrochemical stability of the LCO cathode at 4.5 V. The Ni-RLCO cathode exhibited a high discharge specific capacity of 185.28 mAh/g at a rate of 0.5 C with a capacity retention of 86.3% after 50 cycles and excellent rate capacity of 156.21 mAh/g at 2 C. This work offers a approach in significance for upcycling spent LCO into high-energy-density batteries with long-term cycling stability under high voltage.

An in-situ method for SERS substrate preparation and optimization based on galvanic replacement reaction.

BACKGROUND: Various surface-enhanced Raman spectroscopy (SERS) substrate preparation methods have been reported, however, how to tune the "gap" between nanostructures to make more "hot spots" is still a barrier that restricts their application. The gap between nanostructures is usually fixed when the substrates are prepared. In other words, it is hard to tune interparticle distances for maximum electromagnetic coupling during substrate preparation process. Therefore, an in-situ substrate optimization method that could monitor the SERS signal intensity changes, i.e., to find the optimum gap width and particle size, during substrate preparation process is needed. RESULTS: A method based on the galvanic replacement reaction (GRR) is proposed for the in-situ gap width tuning between nanostructures as well as for the optimization of SERS substrates. Noble metal nanoparticles (NPs) form and grow on the sacrificial templates' surface while noble metal ions are reduced by sacrificial metal (oxides) in GRR. Along with the fresh and clean NPs' surface generated, the gap between two noble metal NPs decreases with the growth of the NPs. To demonstrate this strategy, cuprous oxide/Ti (Cu2O/Ti) sacrificial templates were prepared, and then a GRR was carried out with HAuCl4. The real-time SERS detection during GRR show that the optimum reaction time (ORT) is 300 ± 30 s. Furthermore, SERS performance testing was conducted on the optimized substrate, revealing that the detection limit for crystal violet can reach 1.96 × 10-11 M, confirming the feasibility of this method. SIGNIFICANCE AND NOVELTY: By monitoring the in-situ SERS signal of probes during GRR will obtain an "optimal state" of the SERS substrate with optimal gap width and particle size. The SERS substrate preparation and optimization strategy proposed in this article not only provides a simple, efficient, and low-cost method to fabricate surface-clean noble NPs but also paves the way for the in-situ optimization of NPs size and gap width between NPs which could achieve wider applications of SERS.

Optical Nonlinearity Enabled Super-Resolved Multiplexing Microscopy.

Optical multiplexing for nanoscale object recognition is of great significance within the intricate domains of biology, medicine, anti-counterfeiting, and microscopic imaging. Traditionally, the multiplexing dimensions of nanoscopy are limited to emission intensity, color, lifetime, and polarization. Here, a novel dimension, optical nonlinearity, is proposed for super-resolved multiplexing microscopy. This optical nonlinearity is attributable to the energy transitions between multiple energy levels of the doped lanthanide ions in upconversion nanoparticles (UCNPs), resulting in unique optical fingerprints for UCNPs with different compositions. A vortex beam is applied to transport the optical nonlinearity onto the imaging point-spread function (PSF), creating a robust super-resolved multiplexing imaging strategy for differentiating UCNPs with distinctive optical nonlinearities. The composition information of the nanoparticles can be retrieved with variations of the corresponding PSF in the obtained image. Four channels multiplexing super-resolved imaging with a single scanning, applying emission color and nonlinearity of two orthogonal imaging dimensions with a spatial resolution higher than 150 nm (1/6.5λ), are demonstrated. This work provides a new and orthogonal dimension - optical nonlinearity - to existing multiplexing dimensions, which shows great potential in bioimaging, anti-counterfeiting, microarray assays, deep tissue multiplexing detection, and high-density data storage.