Single-Atom Control of Single-Molecule van der Waals Junctions with Semimetallic Transition Metal Dichalcogenide Electrodes

Electrodes play an essential role in controlling electrode-molecule coupling. However, conventional metal electrodes require linkers to anchor the molecule. Van der Waals interaction offers a versatile strategy to connect the electrode and molecule without anchor groups. Except for graphene, the potential of other materials as electrodes to fabricate van der Waals molecular junctions remains unexplored. Herein, we utilize semimetallic transition metal dichalcogenides (TMDCs) 1T'-WTe as electrodes to fabricate WTe /metalated tetraphenylporphyrin (M-TPP)/WTe junctions via van der Waals interaction. Compared with chemically bonded Au/M-TPP/Au junctions, the conductance of these M-TPP van der Waals molecular junctions is enhanced by ∼736%. More importantly, WTe /M-TPP/WTe junctions exhibit the tunable conductance from 10 to 10 (1.15 orders of magnitude) via single-atom control, recording the widest tunable range of conductance for M-TPP molecular junctions. Our work demonstrates the potential of two-dimensional TMDCs for constructing highly tunable and conductive molecular devices

Room-temperature quantum interference in single perovskite quantum dot junctions

钙钛矿材料由于其高量子产率、载流子迁移率和独特的光致发光特性而在光电材料领域存在诸多潜在的重要应用。研究钙钛矿材料在纳米尺度下电荷输运的独特尺寸效应对钙钛矿光电器件的设计和开发具有重要的指导意义。洪文晶教授课题组基于机械可控裂结技术自主研发了具有皮米级位移调控灵敏度和飞安级电学测量精度的精密科学仪器，对南开大学李跃龙副教授团队合成的钙钛矿量子点进行了深入表征，研究工作成功将量子干涉的研究体系拓展至在光电领域具有重要应用的钙钛矿材料领域，为未来制备基于量子干涉效应的新型钙钛矿器件提供了一种全新的思路。 这一跨学科国际合作研究工作是在化学化工学院洪文晶教授、英国Lancaster 大学物理系Colin J. Lambert教授以及南开大学电子信息与光电工程学院李跃龙副教授的共同指导下完成的。化工系硕士研究生郑海宁、Lancaster University大学Songjun Hou博士、南开大学硕士研究生辛晨光为论文第一作者。博士后林禄春，博士研究生谭志冰、郑珏婷，硕士研究生蒋枫、张珑漪，本科生何文翔、李庆民等参与了论文的研究工作。刘俊扬特任副研究员、师佳副教授和萨本栋微纳米研究院杨扬副教授也参与了部分指导工作。The studies of quantum interference effects through bulk perovskite materials at the Ångstrom scale still remain as a major challenge. Herein, we provide the observation of roomtemperature quantum interference effects in metal halide perovskite quantum dots (QDs) using the mechanically controllable break junction technique. Single-QD conductance measurements reveal that there are multiple conductance peaks for the CH3NH3PbBr3 and CH3NH3PbBr2.15Cl0.85 QDs, whose displacement distributions match the lattice constant of QDs, suggesting that the gold electrodes slide through different lattice sites of the QD via Auhalogen coupling. We also observe a distinct conductance ‘jump’ at the end of the sliding process, which is further evidence that quantum interference effects dominate charge transport in these single-QD junctions. This conductance ‘jump’ is also confirmed by our theoretical calculations utilizing density functional theory combined with quantum transport theory. Our measurements and theory create a pathway to exploit quantum interference effects in quantum-controlled perovskite materials.This work was supported by the National Key R&D Program of China (2017YFA0204902, 2014DFE60170, 2018YFB1500105), the National Natural Science Foundation of China (Nos. 21673195, 21503179, 21490573, 61674084, 61874167), the Open Fund of the Key Laboratory of Optical Information Science & Technology (Nankai University) of China, the Fundamental Research Funds for the Central Universities of China (63181321, 63191414, 96173224), and the 111 Project (B16027), the Tianjin Natural Science Foundation (17JCYBJC41400), FET Open project 767187—QuIET, the EU project BAC-TO-FUEL and the UK EPSRC projects EP/N017188/1, EP/M014452/1. 该工作得到国家重点研发计划课题（2017YFA0204902）、国家自然科学基金（21673195、21503179、21490573）、厦门大学“人工智能分析引擎”双一流重大专项等项目的资助，也得到了固体表面物理化学国家重点实验室、能源材料化学协同创新中心的支持

Room-temperature quantum interference in single perovskite quantum dot junctions.

The studies of quantum interference effects through bulk perovskite materials at the Ångstrom scale still remain as a major challenge. Herein, we provide the observation of room-temperature quantum interference effects in metal halide perovskite quantum dots (QDs) using the mechanically controllable break junction technique. Single-QD conductance measurements reveal that there are multiple conductance peaks for the CH3NH3PbBr3 and CH3NH3PbBr2.15Cl0.85 QDs, whose displacement distributions match the lattice constant of QDs, suggesting that the gold electrodes slide through different lattice sites of the QD via Au-halogen coupling. We also observe a distinct conductance ’jump’ at the end of the sliding process, which is further evidence that quantum interference effects dominate charge transport in these single-QD junctions. This conductance ’jump’ is also confirmed by our theoretical calculations utilizing density functional theory combined with quantum transport theory. Our measurements and theory create a pathway to exploit quantum interference effects in quantum-controlled perovskite materials

Room-temperature quantum interference in single perovskite quantum dot junctions

The studies of quantum interference effects through bulk perovskite materials at the Ångstrom scale still remain as a major challenge. Herein, we provide the observation of room-temperature quantum interference effects in metal halide perovskite quantum dots (QDs) using the mechanically controllable break junction technique. Single-QD conductance measurements reveal that there are multiple conductance peaks for the CH3NH3PbBr3 and CH3NH3PbBr2.15Cl0.85 QDs, whose displacement distributions match the lattice constant of QDs, suggesting that the gold electrodes slide through different lattice sites of the QD via Au-halogen coupling. We also observe a distinct conductance ‘jump’ at the end of the sliding process, which is further evidence that quantum interference effects dominate charge transport in these single-QD junctions. This conductance ‘jump’ is also confirmed by our theoretical calculations utilizing density functional theory combined with quantum transport theory. Our measurements and theory create a pathway to exploit quantum interference effects in quantum-controlled perovskite materials

Multiwavelet prestack Kirchhoff migration

The problems of stretching and aliasing usually occur in prestack Kirchhoff migration. A multiwavelet-based approach is proposed to provide an alternative approach to resolve these problems. Two steps are involved in the multiwavelet-based algorithm: The first step is the decomposition of the seismic traces with a series of wavelets of different dominant frequencies. This step is based on the principle of basis pursuit and is enhanced for more accurate and sparse decomposition by adding an adaptive subdictionary that is associated with the minima and maxima of a seismic trace. The second step is wavelet migration based on the Kirchhoff formulation using a novel approach. The outer iteration is the wavelets of the input seismic traces, which ensures that an input wavelet is only used once in the entire migration process. This enables output of multiple migrated images of different wavelets of dominant frequency ranges, elimination of noisy images, and composition of images for specific interpretation and reservoir characterization purposes with very little extra computational cost. The stretching and aliasing problems are naturally resolved because interpolation on the seismic trace is not required in the migration. We tested the algorithm using a synthetic model with a dipping layer and a 2D real seismic section. We compared our results with results obtained by conventional Kirchhoff migration. </jats:p

Conductance Quantization in 2D Semi‐Metallic Transition Metal Dichalcogenides

Conductance quantization of 2D materials is significant for understanding the charge transport at the atomic scale, which provides a platform to manipulate the quantum states, showing promising applications for nanoelectronics and memristors. However, the conventional methods for investigating conductance quantization are only applicable to materials consisting of one element, such as metal and graphene. The experimental observation of conductance quantization in transition metal dichalcogenides (TMDCs) with complex compositions and structures remains a challenge. To address this issue, an approach is proposed to characterize the charge transport across a single atom in TMDCs by integrating in situ synthesized 1T’‐WTe2 electrodes with scanning tunneling microscope break junction (STM‐BJ) technique. The quantized conductance of 1T’‐WTe2 is measured for the first time, and the quantum states can be modulated by stretching speed and solvent. Combined with theoretical calculations, the evolution of quantized and corresponding configurations during the break junction process is demonstrated. This work provides a facile and reliable avenue to characterize and modulate conductance quantization of 2D materials, intensively expanding the research scope of quantum effects in diverse materials

Genome-wide CRISPR Screening Reveals Pyrimidine Metabolic Reprogramming in 5-FU Chronochemotherapy of Colorectal Cancer

ObjectiveDisruption of the circadian rhythm is associated with cancer occurrence, response to chemotherapy, and poor prognosis. Thus, using internal clock-based chronotherapy to optimize the administration time may improve the therapeutic effects of anticancer drugs while reducing the side effects. Chronotherapy with 5-fluorouracil (5-FU) has been observed in colorectal cancer (CRC) for a long time, but its effect is under controversial and the mechanism remains unclear.MethodsGenome-wide clustered regularly interspaced short palindromic repeats (CRISPR) screening and RNA-sequencing were combined to identify the potential genes or pathways involved in 5-FU chronochemotherapy. Genetic deletion or overexpression of pyrimidine metabolic pathway genes were conducted to examine cellular viability with or without 5-FU via flow cytometry. Western blotting, qPCR, chromatin immunoprecipitation, gain-of-function and loss-of-function assays of several CRC cell lines in vitro and in vivo were used to elaborate and validate the mechanism of 5-FU chronotherapeutic effects.ResultsChronochemotherapeutic effects of 5-FU on CRC in vivo were verified. Furthermore, 5-FU chronochemotherapy related genes such as UPP2, UCK2 and UMPS in the pyrimidine metabolic pathway were identified. Disturbance in these genes, especially UMPS, perturbs 5-FU treatment outcomes in CRC cells. Mechanistically, the core circadian gene, brain and muscle aryl hydrocarbon receptor nuclear translocator-like protein-1 (BMAL1), extensively regulate gene expression in pyrimidine metabolic pathway by binding to E-box element in the promoter region of key genes such as UMPS and perturb their enzymatic activities, thereby maintain diurnal efficacy of 5-FU in CRC cells.ConclusionThis study uncovered a new mechanism by which a core circadian gene BMAL1 increases the effectiveness of 5-FU by enhancing the expression and enzymatic activities of key genes in the pyrimidine metabolic pathway in CRC cells. The findings suggest a novel strategy for CRC chemotherapy by targeting chrono-modulated genes of the 5-FU metabolic pathway.</jats:sec