The electromagnetic mill (EMM) promoted mechanochemical solvent-free palladium-catalyzed borylation of aryl bromides using low palladium catalyst loading (0.05−0.5 mol %) was realized. This protocol exhibits many advantages, such as broad substrate scope, good functional group tolerance, short reaction times, no additional heating, and practical gram-scale synthesis. This EMM system not only showed excellent prospects for industrial application but also unlocked broad areas of solventfree solid-state metal-catalyzed syntheses.
The self-luminescence behavior of lanthanide MOFs (Ln-MOFs) due to the unique antenna effect is considered to be a promising electrochemiluminescence (ECL) emission for biosensors. It is more challenging for Ln-MOFs on account of the difficulty to stimulate Ln ions with the desired energy-transfer efficiency to produce stronger ECL emissions at a low potential. Here, guided by a second ligand-assisted energy-transfer strategy, we present an efficient self-enhanced luminescence mixed-ligand Eu-MOF as an ECL signal probe for an oriented antibody-decorated biosensing platform with a low detection limit and a broad detection range. Diamino terephthalic acid (NH2–H2BDC) and 1,10-phenanthroline (Phen) were selected as the first and second ligands, respectively, to form highly conjugated structures, as well as suppress the nonradiative energy transfer. Impressively, Phen precisely adjusts the energy gap between the triplet ligand and the excited state of Eu3+, realizing the self-enhancement of ECL efficiency of the Eu-MOF. The mixed ligand adjusted the molar ratio to obtain the stable and strong ECL signal at a lowered triggering potential (0.83 V). In addition, FeCo@CNT features densely active FeCo sites along with a rich hierarchy conductive carbon nanotube (CNT) network, which is efficiently a co-reaction accelerator to produce more TPA•+ radicals to accelerate the reduction process of the Eu-MOF for achieving the ECL emission amplification. FeCo@CNT with heptapeptide HWRGWVC (HWR) constructed a matrix biosensing interface that allowed the fragment antigen-binding (Fab) regions to target specific antigens and enhance the incubation efficiency. The present study has gone some way toward designing a self-enhanced luminous Eu-MOF, thus giving new fresh impetus to develop high-performance ECL emitters for biological analysis.
An early diagnosis of cardiovascular disease is of great importance to patients. Herein, a sandwich-type immunosensor for the detection of cardiac troponin I (cTnI) is prepared by using gold nanoparticles (Au NPs) and a composite (CuPtRh CNBs/NH2–Ti3C2) of trimetallic hollow CuPtRh cubic nanobox (CNB)-embedded few-layer ultrathin ammoniated MXene (NH2–Ti3C2). The embedding of the CuPtRh CNBs into NH2–Ti3C2 successfully prevents the restacking of NH2–Ti3C2 and offers more active sites for catalytic H2O2 reduction, which can effectively increase the current signal of the immunosensor. The designed sandwich-type electrochemical immunosensor for detection cTnI has a detection range of 25 fg mL–1 to 100 ng mL–1, and the detection limit is 8.3 fg mL–1 (S/N = 3). Moreover, the immunosensor also demonstrates high sensitivity, acceptable reproducibility, and good stability. More importantly, the designed system offers a direction for early clinical testing of cardiovascular and cerebrovascular diseases.
Currently, the construction of heterojunctions as a method to enhance photoelectrochemical (PEC) activity has shown prospective applications in the analytical field. Restricted by carrier separation at the interface, developing a heterojunction sensing platform with high sensitivity remains challenging. Here, a double-photoelectrode PEC sensing platform was fabricated based on an antennalike strategy by integrating MIL-68(In)−NH 2 , a p-type metal−organic framework (MOF) photocatalyst, as a photocathode with the type-II heterojunction of CdSe/ MgIn 2 S 4 as a photoanode synchronously. According to the ligand-to-metal charge transition (LMCT), the photo-generated carriers of MIL-68(In)−NH 2 transferred from the organic ligand to the metal cluster, which provides an efficient antennalike transfer path for the charge at the heterojunction interface. In addition, the sufficient Fermi energy difference between the double photoelectrode provides the continuous internal driving force required for rapid carrier separation at the anode detection interface, significantly improving the photoelectric conversion efficiency. Hence, compared with the traditional heterojunction single electrode, the photocurrent response of the double-photoelectrode PEC sensing platform developed using the antenna-like strategy is 2.5 times stronger. Based on this strategy, we constructed a PEC biosensor for the detection of programed death-ligand 1 (PD-L1). The elaborated PD-L1 biosensor exhibited sensitive and precise detection capability with a detection range of 1 × 10 −5 to 1 × 10 3 ng/mL and a lower detection limit of 3.26 × 10 −6 ng/mL and demonstrated the feasibility of serum sample detection, providing a novel and viable approach for the unmet clinical need of PD-L1 quantification. More importantly, the charge separation mechanism at the heterojunction interface proposed in this study provides new creative inspiration for designing sensors with high-sensitivity PEC performance.
Here, a sandwich-type electrochemical immunosensor was constructed to detect cardiac troponin I (cTnI) via asymmetric bowl-shaped PdAgFe mesoporous nanospheres (PdAgFe ABMS) as a signal amplification label and core-shell cubic Au/Co-LDH@ZIF-67 as a substrate material. PdAgFe ABMS prepared by dual-template directional anisotropic island growth method has abundant mesoporous channels to accelerate molecular mass transfer in solution. In particular, the asymmetric bowl-like structure allows more active sites to be exposed, which improves the utilization of atoms to stabilize and high current response signals. The synergistic effect between PdAgFe increased the activation energy of the catalytic reaction and further amplified the current signal. In addition, the biosensing interface based on Au/Co-LDH@ZIF-67 not only exhibits a high electron transfer rate, but also can capture more bioactive molecules. Under optimal conditions, the constructed immunosensor was detected to exhibit a low limit of detection (LOD, 4.47 fg/mL) and a wide detection range (10 fg/mL - 100 ng/mL). This work provides an accurate and convenient scheme for the clinical detection of cTnI.
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