ABSTRACT
High-conducting single-molecule junctions have attracted a great deal of attention, but insulating single-molecule junctions, which are critical in molecular circuits, have been less investigated due to the long-standing challenges. Herein, the in situ formation of a Au-C linker via electrical-potential-mediated sp2 C-H bond metalation of polyfluoroarenes with the assistance of scanning tunneling microscope-based break junction technique is reported. This metalation process is bias-dependent and occurs with an electropositive electrode, and the formed junction is highly oriented. Surprisingly, these polyfluoroarenes exhibit unexpected low conductance even under short molecular lengths and are superior molecular insulators. Flicker noise analysis and DFT calculations confirm that the insulating properties of polyfluoroarenes are ascribed to their multiple fluorine substituents. Our results pave a way for constructing oriented asymmetric molecular junctions and provide an efficient strategy to suppress the single-molecule conductance, which will aid in the design of molecular insulators and advance the development of self-integrating functional molecular circuits.
ABSTRACT
Cobalt-bridged organometallic molecular wires (p-Co-p, p-Co-m and m-Co-m) are synthesized, and their charge transport properties are studied. The experimental results show that the quantum interference (QI) effects of cobalt-bridged organometallic wires are determined by the anchoring group. Interestingly, the cobalt-bridge reduces the conductance of the junctions and tunes the QI effect of the wires. These results demonstrate the unique property of metal-bridged organometallic molecular wires and their potential applications in molecular electronics.
ABSTRACT
Here, we report that the molecule-electrode interface of a single-molecule junction can be regulated by a side chain. Based on this regulation, a single-molecule junction probe, PyCHO, was developed, which could distinguish cysteine (Cys) and homocysteine (Hcy) with high selectivity and sensitivity. PyCHO reacts with Cys/Hcy at ambient conditions to form thiazolidine/thiazinane products PyCHO+Cys/PyCHO+Hcy. Single molecular conductance measurement shows PyCHO+Cys and PyCHO+Hcy have different conductance. Control experiments and theoretical results reveal that the side thiazolidine/thiazinane rings have a distinct effect on the Au-π interaction of the pyridine anchor, resulting in their different conductances.
ABSTRACT
The molecular conductance of 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyano-quinodimethane (F4TCNQ) with different electronic states (neutral, radical anion, and dianion) was investigated by the scanning tunneling microscope break junction (STM-BJ) technique. These electronic states have distinct conductance, and the conductance decreases in the order of neutral > radical anion > dianion. Surprisingly, the molecular conductance of the neutral F4TCNQ junction reaches 10-1.17G0, attributed to its LUMO energy level being close to the Fermi level of the gold electrode. Moreover, we found that neutral F4TCNQ can be gradually reduced to radical anions under a relatively low bias voltage of 100 mV. These results will advance the development of organic optoelectronic devices and molecule electronics.
ABSTRACT
Myeloid-derived suppressor cells (MDSCs), a population derived from immature myeloid progenitors, are present in the tumors of patients and highly protumorigenic. However, the molecular mechanisms regulating MDSC infiltration remain unclear. Neddylation pathway is overactivated in multiple cancers and has a significant role in tumor progression. We established a subcutaneous transplantation model of Lewis lung cancer in mice and showed that inactivation of neddylation pathway inhibits MDSC infiltration and impairs lung cancer growth. A high expression level of neuronal precursor cell-expressed developmentally downregulated protein 8 (NEDD8) is positively correlated with MDSC infiltration in human lung adenocarcinomas (LUADs). Moreover, inactivation of neddylation pathway inhibits the expression of murine CXCL5 (mCXCL5; human homolog CXCL6, hCXCL6), an important cytokine implicated in MDSC recruitment. Mechanistically, inactivation of neddylation pathway inhibits activity of Cullin-RING ligase 1, a typical neddylation substrate, and induces accumulation of phosphorylated IκBα and subsequent blockage of NF-κB translocation, thus suppressing transcriptional activation of mCxcl5 or hCXCL6. Collectively, our data suggest that neddylation-NF-κB-mCXCL5 axis is involved in MDSC recruitment to the tumor sites and demonstrate that neddylation pathway is a good therapeutic target for patients with LUAD, particularly those receiving anti-MDSC therapy.
Subject(s)
Lung Neoplasms , Myeloid-Derived Suppressor Cells , Humans , Mice , Animals , NF-kappa B/metabolism , Myeloid-Derived Suppressor Cells/metabolism , Cell Line, Tumor , Lung Neoplasms/drug therapy , Signal TransductionABSTRACT
The single molecular conductance of viologen derivative VSMe and supramolecular compound VSMe-PA[5] (pillararene[5]) was investigated. The difference of their conductance demonstrated the gating effect of cation-π interaction. Theoretical calculations showed that the higher conductance of VSMe-PA[5] is a result of the planar structure of the VSMe component and the narrowed HOMO-LUMO bandgap of VSMe-PA[5], which is due to the cation-π interaction between the VSMe and PA[5] components.
