Electrochemiluminescence immunoassay system based on PCN-224-Mn and gold-platinum bimetallic nanoflowers for sensitive detection of ochratoxin A.

In this work, a novel Electrochemiluminescence Immunosensor was constructed using PCN-224-Mn and gold-platinum nanoflowers (AuPt NFs) for the ultrasensitive detection of ochratoxin A (OTA). PCN-224 modified with Mn (II) was synthesized as a probe material. The interaction efficiency of PCN-224 with S2O82- was also greatly improved. AuPt NFs were used as the substrate material for the electrodes. It has favorable biocompatibility, large specific surface area and can bind more antigen. Also greatly increased the electroactive surface area and conductivity of the electrode. OTA was detected using a competitive immunoassay strategy, in which OTA in the sample competes with the encapsulated antigen for a finite number of antibodies. ECLIA for the detection of OTA was designed to be highly sensitive, with a linear range from 0.0002 ng mL-1 to 1000 ng mL-1 and a LOD as low as 0.067 pg mL-1. In addition, it was evident from the electrochemical analyses that PCN-224-Mn had a stronger and more stable ECL signal compared to the plain PCN-224. The successful preparation of specific, sensitive and reproducible ECL immunosensors confirms the great promise for the detection of OTA or other small molecule mycotoxins.

Pregnenolone 16-Alpha Carbonitrile, an Agonist of Rodent Pregnane X Receptor, Regulates Testosterone Biosynthesis in Rodent Leydig Cells.

Leydig cells (LCs) in the testes produce the male sex hormone testosterone (T). Several xenobiotics, including clinical drugs, supplements, and environmental chemicals, are known to disrupt T homeostasis. Notably, some of these xenobiotics are known to activate the pregnane X receptor (PXR), a ligand-dependent nuclear receptor. However, it is currently unknown whether PXR is expressed in LCs and whether PXR activation alters T synthesis in rodent LCs. Therefore, in this study, we sought to determine whether PXR is expressed in rodent LCs and whether pregnenolone 16-alpha carbonitrile (PCN), the prototype agonist of rodent PXR, regulates T biosynthesis in rodent LCs. Hormonal as well as protein and gene expression analyses were conducted in rat primary LCs and MA-10 mouse Leydig cells. Results showed that PXR was expressed at the mRNA and protein level in both rat primary LCs and MA-10 cells. Incubation of rat primary LCs with PCN resulted in a significant decrease in T secretion. This PCN-induced decrease in T secretion was associated with decreased protein expression of key steroidogenic enzymes such as 3ß-HSD and CYP17A1. RNA-seq results from MA-10 cells showed that PCN down-regulated the transcripts of steroidogenic enzymes and proteins involved in the T synthesis pathway. Together, these results suggest that PCN, an agonist of rodent PXR, can regulate T biosynthesis in rodent LCs by down-regulating the expression of the steroidogenic enzymes involved in T biosynthesis. Our results are significant as they provide a potential novel mechanism for disruption of testosterone homeostasis by a variety of xenobiotics.

Control interfacial charge transfer behavior by creating surface defects on structure unit of heterojunction to drive carrier separation for enhancing photocatalytic CO2 reduction.

Controlling interfacial charge transfer behavior of heterojunction is an arduous issue to efficiently drive separation of photogenerated carriers for improving the photocatalytic activity. Herein, the interface charge transfer behavior is effectively controlled by fabricating an unparalleled VO-NiWO4/PCN heterojunction that is prepared by encapsulating NiWO4 nanoparticles rich in surface oxygen vacancies (VO-NiWO4) in the mesoporous polymeric carbon nitride (PCN) nanosheets. Experimental and theoretical investigations show that, differing with the traditional p-n junction, the direction of built-in electric field between p-type NiWO4 and n-type PCN is reversed interestingly. The strongly codirectional built-in electric field is also produced between the surface defect region and inside of VO-NiWO4 besides in the space charge region, the dual drive effect of which forcefully propels interface charge transfer through triggering Z-Scheme mechanism, thus significantly improving the separation efficiency of photogenerated carriers. Moreover, the unique mesoporous encapsulation structure of VO-NiWO4/PCN heterostructure can not only afford the confinement effect to improve the reaction kinetics and specificity in the CO2 reduction to CO, but also significantly reduce mass transfer resistance of molecular diffusion towards the reaction sites. Therefore, the VO-NiWO4/PCN heterostructure demonstrates the preeminent activity, stability and reusability for photocatalytic CO2 reduction to CO reaction. The average evolution rate of CO over the optimal 10 %-VO-NiWO4/PCN composite reaches around 2.5 and 1.8 times higher than that of individual PCN and VO-NiWO4, respectively. This work contributes a fresh design approach of interface structure in the heterojunction to control charge transfer behaviors and thus improve the photocatalytic performance.

Point-of-care testing of Pseudomonas aeruginosa using PCN-222(Pt) prepared by nanoconfinement-guided protocol to catalyze gas generation reaction.

BACKGROUND: Pathogenic bacteria are keeping threatening global public health since they can cause many infectious diseases. The traditional microorganism identification and molecular diagnostic techniques are insufficiently sensitive, time-consuming, or expensive. Thus it is of great interest to establish pressure signal-based sensing platforms for point-of-care testing of pathogenic bacteria to achieve timely diagnosis of infectious diseases. Rational design and synthesis of nano-sized probes with high peroxidase-mimicking activity have been a long-term cherished goal for improving the sensitivity of pressure signal-based sensing methods. RESULTS: Guided by nanoconfinement effect, PCN-222(Pt) was prepared by confining Pt clusters within the channels of a zirconium porphyrin MOFs material termed as PCN-222. In comparison to regular platinum nanoparticles, palladium@platinum core-shell nanodendrites, and platinum-coated gold nanoparticles, the prepared PCN-222(Pt) displayed superior peroxidase-mimicking activity with outstanding efficiency for catalyzing the decay of H2O2 to produce O2. Thus it was used as a pressure signal probe to establish a sensitive method on a hydrogel pellets platform for analyzing Pseudomonas aeruginosa (P. aeruginosa), for which polymyxin B and a phage termed as JZ1 were used as recognition agents for the target pathogen. P. aeruginosa was quantified with a handheld pressure meter within a broad range of 2.2 × 102-2.2 × 107 cfu mL-1. This method was used to quantify P. aeruginosa in various biological and food samples with acceptable accuracy and reliability. SIGNIFICANCE: The proposed nanoconfinement-guided protocol provides a novel approach for rational design and preparation of nano-sized probes with high peroxidase-mimicking activity for catalyzing gas-generation reaction. Thus this study opens an avenue for establishment of sensitive pressure signal-based sensing methods for pathogenic bacteria, which shows broad application prospects in medical diagnosis of infectious diseases.

Metal-Organic Frameworks for Enhanced Hydrogen Generation from Syngas: A Density Functional Theory Approach.

Although methane poses environmental concerns, it is employed in hydrogen production processes such as steam-methane reforming (SMR), which has an issue of by-products released. Initiatives are being pursued to address CO and CO2 emissions using carbon capture methods, with the goal of minimizing environmental harm while improving pure hydrogen generation from syngas. In this study, porous coordination network (PCN-250) has been studied for its selective adsorption property towards CO, CO2 and H2O as syngas mixture to obtain pure hydrogen. For this purpose, the trimetallic cluster node Fe2M (where Fe2 represents the 3+ oxidation state and M is Cr(II), Mn(II), Fe(II), Co(II), Ni(II), and Zn(II)) has been considered. Fe(III) in combination with metal atoms like Cr(II), Co(II), or Ni(II) has been found to exhibit enhanced adsorption properties towards CO, CO2 and H2O. The molecule with the strongest interaction was found to be H2O over Fe(III)2Zn(II) cluster and weakest interaction was found between H2 and Fe(III)2Ni(II). Charge transfer, natural bond orbital (NBO) and spin density analyses reveal the electronic structural properties of this combination, leading to enhanced adsorption of CO and CO2.

Interface-regulated S-type core-shell PCN-224@TiO2 heterojunction for visible-light-driven generation of singlet oxygen for selective photooxidation of 2-chloroethyl ethyl sulfide.

Selective oxidation of sulfur mustard gas (HD) to non-toxic sulfoxide by the visible-light-catalyzed generation of singlet oxygen (1O2) is a promising degradation strategy. Although PCN-224 can absorb visible light, it suffers from rapid electron-hole recombination and low redox capacity, which limits the performance of HD degradation. Titanium dioxide (TiO2) is an excellent photocatalyst but it lacks visible-light-activity in degrading HD. In this study, PCN-224@TiO2 heterojunction with S-type core-shell structure was synthesized by in-situ growth method to prolong the visible light absorption capacity of TiO2 and inhibit the rapid recombination of PCN-224. The interface formation and internal electric field were optimized by adjusting the Zr/Ti ratio to enhance the charge transfer, redox capacity, electron-hole separation, and visible light absorption. In this study, the formation of heterojunction composites based on Zr-O-Ti linkages is demonstrated by a series of characterization methods. It is demonstrated by experiments and theoretical calculations that PCN-224@TiO2 can generate nearly 100 % 1O2 under visible light conditions without a sacrificial agent, resulting in efficient and selective oxidation of 2-chloroethyl ethyl sulfide (CEES), a simulant of HD, to non-toxic sulfoxide form.

A novel dual-signal output strategy for POCT of CEA based on a smartphone electrochemical aptasensing platform.

A smartphone-based electrochemical aptasensing platform was developed for the point-of-care testing (POCT) of carcinoembryonic antigen (CEA) based on the ferrocene (Fc) and PdPt@PCN-224 dual-signal labeled strategy. The prepared PdPt@PCN-224 nanocomposite showed a strong catalytic property for the reduction of H2O2. Phosphate group-labeled aptamer could capture PdPt@PCN-224 by Zr-O-P bonds to form PdPt@PCN-224-P-Apt. Therefore, a dual signal labeled probe was formed by the hybridization between Fc-DNA and PdPt@PCN-224-P-Apt. The presence of CEA forced PdPt@PCN-224-P-Apt to leave the electrode surface due to the specific affinity, leading to the decrease of the reduction current of H2O2. At the same time, the Fc-DNA strand changed to hairpin structure, which made Fc closer to the electrode and resulted in the increase of the oxidation current of Fc. Thus, CEA can be accurately determined through both signals: the decrease of H2O2 reduction current and the increase of Fc oxidation current, which could avoid the false positive signal. Under the optimal conditions, the prepared aptasensor exhibited a wide linear range from 1 pg·mL-1 to 100 ng·mL-1 and low detection limits of 0.98 pg·mL-1 and 0.27 pg·mL-1 with Fc and PdPt@PCN-224 as signal labels, respectively. The aptasensor developed in this study has successfully demonstrated its capability to detect CEA in real human serum samples. These findings suggest that the proposed sensing platform will hold great potential for clinical tumor diagnosis and monitoring.

Improving the efficiency and environmental safety of emamectin benzoate through a pH-responsive metal-organic framework microencapsulation strategy.

Herein, we developed a technique for loading nanopesticides onto Metal-Organic Frameworks (MOFs) to control Spodoptera litura. The average short-axis length of the synthesized carrier emamectin benzoate@PCN-222 @hyaluronic acid (EB@PCN-222 @HA) was ∼40 nm, with an average long-axis length of ∼80 nm. This enabled the manipulation of its size, contact angle, and surface tension on the surface of leaves. Pesticide-loading capacity, determined via thermogravimetric analysis, was measured at ∼16 %. To ensure accurate pesticide release in the alkaline intestine of Spodoptera litura, EB@PCN-222 @HA was engineered to decompose under alkaline conditions. In addition, the carrier delayed the degradation rate of EB, enhancing EB's stability. Loading Nile red onto PCN-222 @HA revealed potential entry into the insect body through feeding, which was supported by bioassay experiments. Results demonstrated the sustained-release performance of EB@PCN-222 @HA, extending its effective duration. The impact of different carrier concentrations on root length, stem length, fresh weight, and germination rate of pakchoi and tomato were assessed. Promisingly, the carrier exhibited a growth-promoting effect on the fresh weight of both the crops. Furthermore, cytotoxicity experiments confirmed its safety for humans. In cytotoxicity assays, PCN-222 @HA showed minimal toxicity at concentrations up to 100 mg/L, with cell survival rates above 80 %. Notably, the EB@PCN-222 @HA complex demonstrated reduced cytotoxicity compared to EB alone, supporting its safety for human applications. This study presents a safe and effective approach for pest control using controlled-release pesticides with extended effective durations.

Zr-based multivariate metal-organic framework for rapid extraction of sulfonamide antibiotics from water and food samples.

Based on multiple ligands strategy, a series of multivariate metal organic frameworks (MTV-MOFs) named as PCN-224-DCDPSx were prepared using one-pot solvothermal method to extract and remove sulfonamide antibiotics (SAs). The pore structure and adsorption performance can be further regulated by modulating the doping ratios of medium-tetra(4-carboxylphenyl) porphyrin and 4,4'-dicarboxydiphenyl sulfones. The MTV-MOFs of PCN-224-DCDPS1.0 possesses very large specific surface area (1625 m2/g). Using PCN-224-DCDPS1.0 as sorbent, a dispersive solid-phase extraction method was developed to extract and preconcentrate SAs from water, eggs, and milk prior to high performance liquid chromatography analysis. The limits of detection of method were determined between 0.17 and 0.27 ng/mL with enrichment factors ranging 214-327. The adsorption can be finished within 30 s, and the recovery rate remains above 80 % after 10 repeated uses. The adsorption capacities of sorbent were determined from 300 to 621 mg/g for sulfadiazine, sulphapyridine, sulfamethoxydiazine, sulfachlorpyridazine, sulfabenzamide, and sulfadimethoxine. The adsorption mechanisms were investigated and can be attributed to π-π interactions, hydrogen bonds, and electrostatic interactions. This work represents a method for preparation of MTV-MOFs and uses as sorbent for extraction and enrichment of trace pollutants from complex samples.

Highly sensitive and selective demethylase FTO detection using a DNAzyme-mediated CRISPR/Cas12a signal cascade amplification electrochemiluminescence biosensor with C-CN/PCNV heterojunction as emitter.

Fat mass and obesity-associated protein (FTO) has gained attention as the first RNA N6-methyladenosine (m6A) modification eraser due to its overexpression being associated with various cancers. In this study, an electrochemiluminescence (ECL) biosensor for the detection of demethylase FTO was developed based on DNAzyme-mediated CRISPR/Cas12a signal cascade amplification system and carboxylated carbon nitride nanosheets/phosphorus-doped nitrogen-vacancy modified carbon nitride nanosheets (C-CN/PCNV) heterojunction as the emitter. The biosensor was constructed by modifying the C-CN/PCNV heterojunction and a ferrocene-tagged probe (ssDNA-Fc) on a glassy carbon electrode. The presence of FTO removes the m6A modification on the catalytic core of DNAzyme, restoring its cleavage activity and generating activator DNA. This activator DNA further activates the trans-cleavage ability of Cas12a, leading to the cleavage of the ssDNA-Fc and the recovery of the ECL signal. The C-CN/PCNV heterojunction prevents electrode passivation and improves the electron-hole recombination, resulting in significantly enhanced ECL signal. The biosensor demonstrates high sensitivity with a low detection limit of 0.63 pM in the range from 1.0 pM to 100 nM. Furthermore, the biosensor was successfully applied to detect FTO in cancer cell lysate and screen FTO inhibitors, showing great potential in early clinical diagnosis and drug discovery.