Potential-Resolved Ratio Electrochemiluminescence Biosensor Based on Perylene Diimide-MOF and DNA Nanoflowers-CdS Quantum Dots for Detection of Dual Targets.

BRCA1 gene and carcinoembryonic antigen (CEA) are important markers of breast cancer, so accurate detection of them is significant for early detection and diagnosis of breast cancer. In this study, a potential-resolved ratio electrochemiluminescence (ECL) biosensor using perylene diimide (PDI)-metal-organic framework and DNA nanoflowers (NFs)-CdS quantum dots (QDs) was constructed for detection of BRCA1 and CEA. Specifically, PDI-MOF and CdS QDs can generate potential-resolved intense ECL signals only using one coreactant, so the detection procedure can be effectively simplified. PDI-MOF was first attached to the electrode by graphene oxide, and the dopamine (DA) probe was linked to quench the ECL signal by DNA hybridization. In the presence of target BRCA1, it can form a bipedal DNA walker, so the quenching molecules (DA) were detached from the electrode via the walker amplification process aided by Mg2+, so that the PDI signal at -0.25 V was restored for the BRCA1 assay. Moreover, CdS QDs@DNA NFs as amplified signal probes were formed by self-assembly, and the target CEA-amplified product introduced the CdS QDs@DNA NFs to the electrode, so the QD ECL signal at -1.42 V was enhanced, while the ECL signal of PDI is unchanged; thus, CEA detection was achieved by the ratio value between them. Therefore, the detection accuracy is guaranteed by detection of two cancer markers and a ratio value. This biosensor has a great contribution to the development of new ECL materials and a novel ECL technique for fast and efficient multitarget assays, showing great significance for the early monitoring and diagnosis of breast cancer.

Triple quenching effect of nanozyme catalyzed precipitation combined with enzyme-free amplification for photoelectrochemical biosensing of circulating tumor DNA.

In this work, a new photoelectrochemical (PEC) biosensor based on triple quenching effect of nanozyme catalyzed precipitation to PEC signal of MgIn2S4 was constructed for ultrasensitive detection of circulating tumor DNA (ctDNA). Enzyme-free amplification technology was used to convert target ctDNA into a large number of product chains (PC) to improve the detection sensitivity. Co3O4 nanozyme with excellent peroxidase (POD)-like activity was introduced to the surface of MgIn2S4 by PC. Co3O4 could oxidize chromogenic agent 3-Amino-9-ethylcarbazole (AEC) to produce red insoluble precipitation in the presence of H2O2, resulting in the PEC signal "off" of MgIn2S4 to achieve ultrasensitive detection of ctDNA. In particular, Co3O4 nanozyme showed three synergistic quenching effects on PEC signal of MgIn2S4, which contributed greatly to improving the detection sensitivity. Firstly, the light absorption range of Co3O4 could reach 1000 nm, and compete with MgIn2S4 for light absorption. Secondly, the produced red precipitation belonged to the insulating material and had large electrochemical impedance, which hindered the transmission of photogenerated carriers. Thirdly, the precipitation also prevented the electron donor ascorbic acid (AA) from transferring electrons to MgIn2S4. This biosensor provided a promising sensitive PEC detection technology for ctDNA, and further broadened the application of nanozymes in the field of PEC analysis.

Electrochemical Benzylic C-H Amination via N-Aminopyridinium.

An electrochemical protocol for benzylic C(sp3)-H aminopyridylation via direct C-H/N-H cross-coupling of alkylarenes with N-aminopyridinium triflate has been developed. This method features excellent site-selectivity, broad substrate scope, redox reagent-free and facile scalability. The generated benzylaminopyridiniums can be readily converted to benzylamines via electroreductive N-N bond cleavage.

Recyclable polyurethane foam loaded with carboxymethyl chitosan for adsorption of methylene blue.

Novel composite foam (CMCTS-PUF-s) was prepared by immobilizing carboxymethyl chitosan (CMCTS) on polyurethane foam (PUF) in which amino groups in CMCTS reacted with isocyanate groups in polyurethane prepolymer. The adsorption capacity of the optimal composite foam (CMCTS-PUF-5) reached to 118.2 mg/g with 5% CMCTS loading. The removal rate to methylene blue (MB) was up to 97.1%, which was obviously higher than 18.9% of PUF. After recycling for five times, the removal rate still reached 83.2%, which strongly proved the excellent reusability of immobilizing CMCTS modified PUF. The characterization results of FTIR and TG showed that CMCTS was well loaded on PUF by covalent bond. The Young's modulus and tensile strength of CMCTS-PUF-5 were increased by 252% and 97% compared with that of PUF. MIP characterization result showed the porosity of CMCTS-PUF-5 was 73.99% and the pore sizes were mainly distributed between 50 and 150 µm, which provide sufficient diffusion channels and active sites for MB dyes. The adsorption kinetics and isotherm proved pseudo-second-order kinetic model and Langmuir isotherm model could well describe the adsorption process of CMCTS-PUF-5. Therefore, CMCTS-PUF-s presents excellent recoverability, high stability and attractive adsorption efficiency, shows the potential application in future treatment of dye wastewater.