Raman spectroscopy offers a great power to detect,analyze and identify molecules,and monitor their temporal dynamics and evolution when combined with single-molecule surface-enhanced Raman scattering(SM-SERS)substrate...Raman spectroscopy offers a great power to detect,analyze and identify molecules,and monitor their temporal dynamics and evolution when combined with single-molecule surface-enhanced Raman scattering(SM-SERS)substrates.Here we present a SM-SERS scheme that involves simultaneously giant chemical enhancement from WS22D materials,giant electromagnetic enhancement from plasmonic nanogap hot spot,and inhibition of molecular fluorescence influence under near-infrared laser illumination.Remarkably we find Coulomb attraction between analyte and gold nanoparticle can trigger spontaneous formation of molecule-hotspot pairing with high precision,stability and robustness.The scheme has enabled realization of universal,robust,fast,and large-scale uniform SM-SERS detection for three Raman molecules of rhodamine B,rhodamine 6G,and crystal violet with a very low detection limit of 10−16 M and at a very fast spectrum acquisition time of 50 ms.展开更多
Gaining insights into charge transport related to conformational changes and ion transport in valinomycin(VM)is crucial for understanding the underlying physiological processes and advancing ion carrier applications.O...Gaining insights into charge transport related to conformational changes and ion transport in valinomycin(VM)is crucial for understanding the underlying physiological processes and advancing ion carrier applications.Observing these processes in single molecules provides deeper insights and precision than those obtained through conventional ensemble measurements.Herein,we employed a single-molecule conductance measurement method based on the scanning tunneling microscopy break-junction(STM-BJ)to measure the charge transport of individual VM molecules in both non-polar and polar solvents,as well as when mediated by K^(+)ions.Single-molecule conductance measurements revealed that the bracelet and propeller-type conformations of VM in both non-polar and polar solvents significantly affect its conductance.In polar solvents,the propeller-type conformation of VM demonstrated a well-defined conductance signature,single-molecule rectification feature,and through-space transmission mechanism.Specifically,the introduction of K^(+)ions in polar solvents induced a conformational transition from the propeller-type to the bracelet-type form,facilitating K^(+)binding recognition.These observations were further supported by density functional theory combined with non-equilibrium Green’s function calculations.This study enhanced the fundamental understanding of the electronic transport mechanisms in VM and valinomycin-K^(+)molecular junctions,offering insights into VM ionophores and promoting supramolecular sensing applications.展开更多
Manipulating magnetic couplings in molecular magnets is of great importance in improving the mag-netic properties of such materials.It has been proved that by adjusting the strength of magnetic cou-plings and the arra...Manipulating magnetic couplings in molecular magnets is of great importance in improving the mag-netic properties of such materials.It has been proved that by adjusting the strength of magnetic cou-plings and the arrangement of the intermolecular magnetic dipoles,magnetic blocking can be significantly enhanced.Herein manipulating the intramolecular dipole interactions by ligand modifica-tion was attempted with the use of three closely related dinuclear Er(Ⅲ)complexes of a common chemical formula of[(COT^(R))Er(μ-CI)(THF)]_(2)(COT^(R)is monosubstituted cyclooctatetraenide dianions with R=diphenylmethylsilyl(Ph_(2)MeS)for 1,triethylsilyl(TES)for 2,and triisopropylsilyl(TIPS)for 3).Each of these complexes features a centrosymmetric dinuclear core unit with their component Er(Ⅲ)ions doubly bridged by two chloro ligands and further coordinated with a capping substituted corR ligand and a coordinated THF molecule.Magnetic studies reveal that the complexes display similar ferromagnetic couplings with comparable single-molecule magnetic behaviors.The ferromagnetic couplings dominated by the intramolecular dipole interactions are found to be 0.7614,0.7380,and 0.5635 cm^(-1)for 1,2,and 3,respectively.The angles(θ)between the magnetic easy axes and the intramolecular Er-Er lines are 24.88(2)°,25.23(1),and 31.85(5),leading to transversal dipole fields of 0.0114,0.0113,and 0.0125 T for 1,2,and 3,respectively.Although the different ligand substitution generates a sizable difference of about 7 in theθangle,the resulting difference in the dipole interactions is not sufficiently strong to cause any significant differences in their magnetic properties.Further change in theθangles to the"side-by-side"(θ=90°)or"head-to-tail"(θ=0°)arrangement of the magnetic easy axes,achievable by rational mo-lecular design,is expected to lead to molecular magnetic materials with much enhanced properties.展开更多
DNA imaging and visualization techniques are crucial in biological experiments and have also emerged as a powerful method for single-molecule studies.Traditional intercalating dyes(e.g.,SYTOX,EtBr,GelRed)can stain DNA...DNA imaging and visualization techniques are crucial in biological experiments and have also emerged as a powerful method for single-molecule studies.Traditional intercalating dyes(e.g.,SYTOX,EtBr,GelRed)can stain DNA but may alter its structure and mechanical properties,and cause photocleavage.Recently,a novel fluorescent DNA-binding protein(FP-DBP)was introduced,which can stain DNA without sequence preference and without inducing photocleavage.In this study,using a custom-built magnetic tweezers system,we performed DNA stretching,twisting and unzipping experiments to compare the mechanical properties of DNA with and without two kinds of intercalating dyes(SYTOX Orange and GelRed)and mCherry FP-DBP.Our results show that mCherry FP-DBP does not affect DNA structure or mechanics,unlike SYTOX Orange and GelRed,making FP-DBP a promising tool for DNA visualization in single-molecule experiments.展开更多
Sodium alginate(SA)is generally considered highly hydrophilic due to two hydroxyl groups and a carboxylate group on each pyranose ring.However,SA will form a gel after dissolving in water for a certain period.The two ...Sodium alginate(SA)is generally considered highly hydrophilic due to two hydroxyl groups and a carboxylate group on each pyranose ring.However,SA will form a gel after dissolving in water for a certain period.The two properties of SA,hydrophilicity and gelation,seem to be paradoxical.In this study,to explore the mechanism behind these paradoxical properties,the single-chain behaviors of SA in various liquid environments have been investigated by using single-molecule force spectroscopy(SMFS).In nonpolar solvents such as nonane,SA exhibits its single-chain inherent elasticity consistent with the theoretical elasticity derived from quantum mechanical(QM)calculations.Notably,the experimental curve of SA obtained in water shows a long plateau in the low force region.Further research reveals that this phenomenon is driven by the hydrophobic effect.Additionally,SA shows greater rigidity than its inherent elasticity in the middle and high force regions due to electrostatic repulsion between carboxylate groups on adjacent sugar rings.Comparative single-molecule studies suggest that SA exhibits considerable hydrophobicity,offering new insights into the gelation process in water.展开更多
Clustering is a pivotal data analysis method for deciphering the charge transport properties of single molecules in break junction experiments.However,given the high dimensionality and variability of the data,feature ...Clustering is a pivotal data analysis method for deciphering the charge transport properties of single molecules in break junction experiments.However,given the high dimensionality and variability of the data,feature extraction remains a bottleneck in the development of efficient clustering methods.In this regard,extensive research over the past two decades has focused on feature engineering and dimensionality reduction in break junction conductance.However,extracting highly relevant features without expert knowledge remains an unresolved challenge.To address this issue,we propose a deep clustering method driven by task-oriented representation learning(CTRL)in which the clustering module serves as a guide for the representation learning(RepL)module.First,we determine an optimal autoencoder(AE)structure through a neural architecture search(NAS)to ensure efficient RepL;second,the RepL process is guided by a joint training strategy that combines AE reconstruction loss with the clustering objective.The results demonstrate that CTRL achieves excellent performance on both the generated and experimental data.Further inspection of the RepL step reveals that joint training robustly learns more compact features than the unconstrained AE or traditional dimensionality reduction methods,significantly reducing misclustering possibilities.Our method provides a general end-to-end automatic clustering solution for analyzing single-molecule break junction data.展开更多
The forming processes of 4,40-dipyridyl-based single-molecule junctions and mechanically induced conductance switching as well as the side-group effects are systematically investigated by applying the ab initio-based ...The forming processes of 4,40-dipyridyl-based single-molecule junctions and mechanically induced conductance switching as well as the side-group effects are systematically investigated by applying the ab initio-based adiabatic geometric optimization method and the one-dimensional transmission combined with three-dimensional correction approximation(OTCTCA)method.The numerical results show that for the 4,40-dipyridyl with a p-conjugated phenyl-phosphoryl or diphenylsilyl side group,the pyridyl vertically anchors on the second atomic layer of the pyramid-shaped Au tip electrode at small inter-electrode distances by laterally pushing the apical Au atom aside,which induces stronger pyridyl-electrode coupling and high-conductance state of the formed junctions.As the inter-electrode distance increases,the pyridyl shifts to the apical Au atom of the tip electrode.This apical Au atom introduces additional scatterings to the tunneling electrons and significantly decreases the conductance of the junctions.Furthermore,for the 4,40-dipyridyl with a phenyl-phosphoryl side group,the probability of manifesting the high-conductance state is decreased due to the oxygen atom reducing the probability of the pyridyl adsorbing on the second layer of Au tip electrode.In contrast,for the 4,40-dipyridyl with a nonconjugated cyclohexyl-phosphoryl side group,the steric hindrance from the bulky cyclohexyl group leads the molecule to preferentially form the O-Au contact,which prevents both the high conductance and mechanically induced conductance switching of the junction.Our results provide a theoretical understanding of the side-group effects on electronic transport properties of single-molecule junctions,offering an alternative explanation for the experimental observations.展开更多
Quinoid structures are considered to be conducive to the charge transport of organic molecules,but this hypothesis is rarely proven at single-molecule level.Herein,as a proof of concept,the single-molecule conductance...Quinoid structures are considered to be conducive to the charge transport of organic molecules,but this hypothesis is rarely proven at single-molecule level.Herein,as a proof of concept,the single-molecule conductance of two furan-based isomers,3,3'-bis(4-(methylthio)phenyl)-2,2'-bifuran(2,2'-SMPBF)and 4,4'-bis(4-(methylthio)phenyl)-3,3'-bifuran(3,3'-SMPBF),is investigated by the scanning tunneling microscopy break junction(STM-BJ)technique and theoretical simulation.2,2'-SMPBF prefers to adopt a nearly planar conformation with intact alternating single and double bonds extended via2,2'-bifuran moiety and therefore exhibits goodπ-conjugation and a prominent quinoid structure.However,theπ-conjugation of 3,3'-SMPBF is interrupted due to ineffective cross-conjugation in the 3,3'-bifuran moiety,leading to the absence of a quinoid structure.2,2'-SMPBF displays switchable multiple conductances induced by the interconversion between folded and unfolded conformations and an abnormal rebound of conductance along with the increases of electrode displacement,which is demonstrated to be caused by the quinoid structure in a nearly planar conformation during the stretching process.However,3,3'-SMPBF without a quinoid structure in unfolded conformation exhibits extremely low conductance that cannot be captured in STM-BJ measurements.These results reveal the significant contribution of quinoid structure to molecular charge transport and provide valuable information on the structure-transport relationship for the design of efficient organic semiconductors.展开更多
Due to the ionic feature of the lanthanide ions,to straightly bridge two lanthanide(Ln)ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnet...Due to the ionic feature of the lanthanide ions,to straightly bridge two lanthanide(Ln)ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization(QTM)for single-molecule magnets(SMMs),a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent.Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ)complexes-{[LnL_(A)(4-NH_(2)py)_(5)]_(2)(μ-Cl)}[BPh_(4)]_(3)(For L_(A)^(-)=1-AdO^(-),1Ln;for L_(A)^(-)=~tBuO^(-),2Ln;Ln=Dy,Gd).More uniquely,the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ)ions with local C_(5v)symmetry.The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K(τ_(2K)=2706.89 and 1437.05 s for 1Dy and 2Dy)compared to the diluted ones with the approaching magnetic property of the C_(5v)motifs(τ_(2K)=0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y).Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic,it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.展开更多
Despite the ongoing increase in the efficiency of perovskite solar cells(PSCs),residual lead iodide(PbI2and moisture sensitivity issues continue to constrain their further commercialization.Herein,we propose a thermal...Despite the ongoing increase in the efficiency of perovskite solar cells(PSCs),residual lead iodide(PbI2and moisture sensitivity issues continue to constrain their further commercialization.Herein,we propose a thermally mediated in situ repair and encapsulation strategy to construct high-performance PSCs by incorporating piperazine thioctic acid salt(TAPPZ)as a dopant into the perovskite precursor Thermally dissociated piperazine(PPZ)from TAPPZ integrates microcrystals to form larger grain(>2000 nm),while the carboxylic acid in thioctic acid(TA)and the amine salt in TAPPZ synergistically passivate and transform PbI_(2),significantly reducing its residual amount.Additionally,TAPPZ undergoe thermal self-crosslinking during perovskite annealing,enabling melt-polymerization to form in situ encapsulation for enhanced water resistance.The TAPPZ-incorporated device achieves a remarkable efficiency of 25.65% and exhibits excellent operational stability,retaining over 90% of its initial efficiency after 2000 h under ambient conditions(20-30℃,20%-30% relative humidity).This study provide new insights into the construction of high-performance perovskite solar cells by designing and synthe sizing multifunctional single molecules for in situ repair and encapsulation of perovskites.展开更多
The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These n...The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These novel fiuorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule whitelight materials with high fiuorescence quantum yields. The robust organic and low-cost white lightemitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared(NIR) fiuorescence materials with large Stokes shifts based on the olefination of heterocycles.展开更多
The single-molecule detection tech-nique plays a pivotal role in elucidat-ing the fundamental mechanisms of various scientific processes at the molecular level,and holds essential im-portance in multiple fields includ...The single-molecule detection tech-nique plays a pivotal role in elucidat-ing the fundamental mechanisms of various scientific processes at the molecular level,and holds essential im-portance in multiple fields including physics,biology,and chemistry.Re-cently,single-molecule detection has garnered increasing attention owing to its practical utility in medical diagno-sis,primarily due to its exceptional sensitivity and the minimal sample volume required for analysis.However,the conventional single-molecule technique,represented by total internal reflection microscopy,faces challenges such as sophisticated operation procedures and limited detection throughput,thereby impeding its broader application.To address these limitations,we have demonstrated single-molecule detection using an integrated silicon photonic chip,of-fering a cost-effective and user-friendly alternative.By employing basic optics,we efficiently introduce the excitation source for single-molecule fluorescence by harnessing the strong evanescent field of high refractive-index waveguides.Subsequently,fluorescence signals are collected using basic optics comprising a water-immersion objective,relay optics,and a digi-tal camera.Our results highlight a low-cost,high-throughput single-molecule technique achieved through the integrated silicon photonic chip.This innovative approach is promised to facilitate the widespread adoption of single-molecule fluorescence in medical diagnosis.展开更多
Orientation-dependent transport properties induced by anisotropic molecules are enticing in single-molecule junctions.Here,using the first-principles method,we theoretically investigate spin transport properties and p...Orientation-dependent transport properties induced by anisotropic molecules are enticing in single-molecule junctions.Here,using the first-principles method,we theoretically investigate spin transport properties and photoresponse characteristics in trimesic acid magnetic single-molecule junctions with different molecular adsorption orientations and electrode contact sites.The transport calculations indicate that a single-molecule switch and a significant enhancement of spin transport and photoresponse can be achieved when the molecular adsorption orientation changes from planar geometry to upright geometry.The maximum spin polarization of current and photocurrent in upright molecular junctions exceeds 90%.Moreover,as the Ni tip electrode moves,the tunneling magnetoresistance of upright molecular junctions can be increased to 70%.The analysis of the spin-dependent PDOS elucidates that the spinterfaces between organic molecule and ferromagnetic electrodes are modulated by molecular adsorption orientation,where the molecule in upright molecular junctions yields higher spin polarization.Our theoretical work paves the way for designing spintronic devices and optoelectronic devices with anisotropic functionality base on anisotropic molecules.展开更多
Force spectrum measurements with constant loading rates are widely used in single-molecule manipulation experiments to study the mechanical stability and force response of biomolecules.Force-dependent transition rates...Force spectrum measurements with constant loading rates are widely used in single-molecule manipulation experiments to study the mechanical stability and force response of biomolecules.Force-dependent transition rates can be obtained from the transition force distribution,but it is limited to the force range with non-zero force distribution.Although constant loading rate control can be realized with magnetic tweezers,the loading rate range is limited due to the slow movement of permanent magnets.Non-linear exponential and exponential squared force loading functions are more feasible in magnetic tweezers,while there is no theoretical result available for these two kinds of non-linear force loading functions.In this study,we solved the unfolding process of a protein following Bell's model under nonlinear exponential and exponential squared force loading functions,which offer a broader range of unfolding force distribution compared to the traditional constant loading rate experiments.Furthermore,we derived two force loading functions,which can produce uniform unfolding force distribution.This research contributes fundamental equations for the analysis of experimental data obtained through single-molecule manipulation under nonlinear force loading controls,paving the way for the use of nonlinear force control in magnetic tweezer experiments.展开更多
Single-molecule junctions,integrating individual molecules as active components between electrodes,serve as fundamental building blocks for advanced electronic and sensing technologies.The application of ionic liquids...Single-molecule junctions,integrating individual molecules as active components between electrodes,serve as fundamental building blocks for advanced electronic and sensing technologies.The application of ionic liquids in single-molecule junctions represents a cutting-edge and rapidly evolving field of research at the intersection of nanoscience,materials chemistry,and electronics.This review explores recent advances where ionic liquids function as electrolytes,dielectric layers,and structural elements within single-molecule junctions,reshaping charge transport,redox reactions,and molecular behaviors in these nanoscale systems.We comprehensively dissect fundamental concepts,techniques,and modulation mechanisms,elucidating the roles of ionic liquids as gates,electrochemical controllers,and interface components in singlemolecule junctions.Encompassing applications from functional device construction to unraveling intricate chemical reactions,this review maps the diverse applications of ionic liquids in single-molecule junctions.Moreover,we propose critical future research topics in this field,including catalysis involving ionic liquids at the single-molecule level,functionalizing single-molecule devices using ionic liquids,and probing the structure and interactions of ionic liquids.These endeavors aim to drive technological breakthroughs in nanotechnology,energy,and quantum research.展开更多
Moleculardeviceswith highswitchingperformance and/or the perfect spin filtering effect have always been the pursuit with the development of molecular electronics.Hereb,yusingthe 2001.0V nonequilibrium.Green's func...Moleculardeviceswith highswitchingperformance and/or the perfect spin filtering effect have always been the pursuit with the development of molecular electronics.Hereb,yusingthe 2001.0V nonequilibrium.Green's function method in combination with the density functionaltheory,the switching performance and spin filtering properties of dimethyldihydropyrene(DHP)/cyclophanediene(CPD)photoswitchable molecule connected by carbon atomic chains(CACs)to two zigzag graphene nanoribbon electrodes have been theoretically investigated.The results show that DHP is more conductive than CPD and therefore an evident switching effect is demonstrated,and the switching ratio(RON/OFF)can reach 4.5×103.It is further revealed that the RoON/OF of DHP/CPD closely depends on the length of CACs.More specifically,the RoN/OFF values of DHP/CPD with odd-numbered CACs are larger than those with even-numbered CACs.More interestingly,a high or even perfect spin filtering effect can be obtained in these investigated DHP/CPD single-molecule devices.Our study is helpful for future design of single-molecule switches and spin filters and provides a way to optimize their performance by means of varying the length of bridging CACs.展开更多
Physical biology is an interdisciplinary field that bridges biology with physical sciences and engineering.Singlemolecule physical biology focuses on dynamics of individual biomolecules and complexes,aiming to answeri...Physical biology is an interdisciplinary field that bridges biology with physical sciences and engineering.Singlemolecule physical biology focuses on dynamics of individual biomolecules and complexes,aiming to answering basic questions about their functions and mechanisms.It takes advantages of physical methodologies to gain quantitative understanding of biological processes,often engaging precise physical measurements of reconstructed objects to avoid interference from unnecessary complications.In this review,we(i)briefly introduce concepts of single-molecule physical biology,(ii)describe extensively used single-molecule methodologies that have been developed to address key questions in two important objects of single-molecule physical biology,namely,nucleic acid-interacting proteins and membraneinteracting proteins,and(iii)show by a few successful examples how one may use single-molecule methods to deepen our understanding of protein machines.展开更多
Single-molecule junctions are building blocks for constructing molecular devices.However,intermolecular interactions like winding bring additional interference among the surrounding molecules,which inhibits the intrin...Single-molecule junctions are building blocks for constructing molecular devices.However,intermolecular interactions like winding bring additional interference among the surrounding molecules,which inhibits the intrinsic coherent transport through single-molecule junctions.Here,we employed a nanocavity(dimethoxypillar[5]arene,DMP[5]),which is analogous to electric cables,to confine the conformation of flexible chains(1,8-diaminooctane,DAO)via host-vip interaction.Single-molecule conductance measurements indicate that the conductance of DAO encapsulated with DMP[5]is as high as that of pure DAO,as reproduced by theoretical simulations.Intriguingly,the molecular lengths of the DAO encapsulated with DMP[5]increase from 1.13 nm to 1.46 nm compared with the pure DAO,indicating that DMP[5]keeps DAO upright-standing via the confinement effect.This work provides a new strategy to decouple the intermolecular interaction by employing an insulating sheath,enabling the high-density integration of single-molecule devices.展开更多
A series of isomeric sandwich-type dysprosiacarboranyl complexes,including[Na(THF)_(5)][3.2'-(THF)_(2)-3.2-Dy(1,2-C_(2)B_(9)H_(11))_(x)(1'7'-C_(2)B_(9)H_(11))_(2-x))(o/m-Dy)and[Na(THF)_(5)][2.2'-(THF)_...A series of isomeric sandwich-type dysprosiacarboranyl complexes,including[Na(THF)_(5)][3.2'-(THF)_(2)-3.2-Dy(1,2-C_(2)B_(9)H_(11))_(x)(1'7'-C_(2)B_(9)H_(11))_(2-x))(o/m-Dy)and[Na(THF)_(5)][2.2'-(THF)_(2)-2.2'-Dy(1,7-C_(2)B_(9)H_(11))2](m-Dy)were synthesized by using the isomeric dicarbollide ligands,namely[nido-7,8-C2BgH_(11)]^(2-)and[nido-7,9-C_(2)B_(9)H_(11)]^(2-).The structural details of o/m-Dy and m-Dy and magnetic dynamics of m-Dy were investigated to compare with the previous study on[Na(THF)_(5)][2.2'-(THF)_(2)-2.2'-Dy(1,2-C_(2)B_(9)H_(11))_(2)]o-Dy.The bending angles of sandwiched dysprosiacarboranes are straightened so as to improve energy bar-riers(U_(eff))from 430(5)to 591(0)K.Magneto-structural correlations show that the introduction of meta-C sites within the π-electron delocalized heterocyclic ring can effectively shorten the Dy-C_(2)B_(3)centroid distance and increase the C_(2)B_(3)centroid...Dy...C_(2)B_(3)centroid bending angle which is attributed to the dif-ferences in electronegativity between C and B atoms on the ring of C_(2)B_(3)^(2-).Therefore,to further enhance the performance of single-molecule magnets(SMMs)on this basis,future endeavors should focus on diminishing the equatorial solvent molecules to make a wider C2B3...Dy...C_(2)B_(3)bending angle.展开更多
Monitoring the dynamics of cellular pseudopodia at nanoscale has become essential for understanding their diverse and complex functions in living cells.This is made possible by combining single-molecule localization m...Monitoring the dynamics of cellular pseudopodia at nanoscale has become essential for understanding their diverse and complex functions in living cells.This is made possible by combining single-molecule localization microscopy(SMLM)with self-blinking dyes.However,existing self-blinking dyes often face limitations,such as nonspecific blinking and low photostability,which can bring background noise and yield erroneous localization signals,hindering their effectiveness for nanoscale visualization.Here,we present a method for long-term SMLM imaging of cellular pseudopodia dynamics using a blinkogenic probe that exhibits self-blinking activation upon molecular recognition.This approach enabled the precise tracking of various pseudopodia structures,including filopodia,lamellipodia,and(tunneling nanotubes)-nanoscale(TNTs),in living cells.We monitored the growth and fusion of filopodia,as well as the extension and shrinkage of lamellipodia,in real-time.Additionally,we identified two distinct fusion modes between filopodia and lamellipodia and captured the formation of TNTs and their interactions with filopodia,demonstrating the probe's utility in visualizing real-time pseudopodia dynamics at nanoscale.展开更多
基金financial support from Science and Technology Project of Guangdong(2020B010190001)National Natural Science Foundation(12434016).
文摘Raman spectroscopy offers a great power to detect,analyze and identify molecules,and monitor their temporal dynamics and evolution when combined with single-molecule surface-enhanced Raman scattering(SM-SERS)substrates.Here we present a SM-SERS scheme that involves simultaneously giant chemical enhancement from WS22D materials,giant electromagnetic enhancement from plasmonic nanogap hot spot,and inhibition of molecular fluorescence influence under near-infrared laser illumination.Remarkably we find Coulomb attraction between analyte and gold nanoparticle can trigger spontaneous formation of molecule-hotspot pairing with high precision,stability and robustness.The scheme has enabled realization of universal,robust,fast,and large-scale uniform SM-SERS detection for three Raman molecules of rhodamine B,rhodamine 6G,and crystal violet with a very low detection limit of 10−16 M and at a very fast spectrum acquisition time of 50 ms.
基金supported by the National Key R&D Program of China(Nos.2022YFB3204402,2020YFA0714703 and 2022YFC2205003)the National Natural Science Foundation of China(No.22204135)+2 种基金Hunan Provincial Natural Science Foundation of China(No.2023JJ40619)the Education Department of Hunan Province(No.23A0114)the Science and Technology Innovation Program of Hunan Province(No.2022RC3027)。
文摘Gaining insights into charge transport related to conformational changes and ion transport in valinomycin(VM)is crucial for understanding the underlying physiological processes and advancing ion carrier applications.Observing these processes in single molecules provides deeper insights and precision than those obtained through conventional ensemble measurements.Herein,we employed a single-molecule conductance measurement method based on the scanning tunneling microscopy break-junction(STM-BJ)to measure the charge transport of individual VM molecules in both non-polar and polar solvents,as well as when mediated by K^(+)ions.Single-molecule conductance measurements revealed that the bracelet and propeller-type conformations of VM in both non-polar and polar solvents significantly affect its conductance.In polar solvents,the propeller-type conformation of VM demonstrated a well-defined conductance signature,single-molecule rectification feature,and through-space transmission mechanism.Specifically,the introduction of K^(+)ions in polar solvents induced a conformational transition from the propeller-type to the bracelet-type form,facilitating K^(+)binding recognition.These observations were further supported by density functional theory combined with non-equilibrium Green’s function calculations.This study enhanced the fundamental understanding of the electronic transport mechanisms in VM and valinomycin-K^(+)molecular junctions,offering insights into VM ionophores and promoting supramolecular sensing applications.
基金the National Natural Science Foundation of China(92261203,22101116,21971106)the Science Research Foun dation of jilin Province(YDZJ202301ZYTS478)。
文摘Manipulating magnetic couplings in molecular magnets is of great importance in improving the mag-netic properties of such materials.It has been proved that by adjusting the strength of magnetic cou-plings and the arrangement of the intermolecular magnetic dipoles,magnetic blocking can be significantly enhanced.Herein manipulating the intramolecular dipole interactions by ligand modifica-tion was attempted with the use of three closely related dinuclear Er(Ⅲ)complexes of a common chemical formula of[(COT^(R))Er(μ-CI)(THF)]_(2)(COT^(R)is monosubstituted cyclooctatetraenide dianions with R=diphenylmethylsilyl(Ph_(2)MeS)for 1,triethylsilyl(TES)for 2,and triisopropylsilyl(TIPS)for 3).Each of these complexes features a centrosymmetric dinuclear core unit with their component Er(Ⅲ)ions doubly bridged by two chloro ligands and further coordinated with a capping substituted corR ligand and a coordinated THF molecule.Magnetic studies reveal that the complexes display similar ferromagnetic couplings with comparable single-molecule magnetic behaviors.The ferromagnetic couplings dominated by the intramolecular dipole interactions are found to be 0.7614,0.7380,and 0.5635 cm^(-1)for 1,2,and 3,respectively.The angles(θ)between the magnetic easy axes and the intramolecular Er-Er lines are 24.88(2)°,25.23(1),and 31.85(5),leading to transversal dipole fields of 0.0114,0.0113,and 0.0125 T for 1,2,and 3,respectively.Although the different ligand substitution generates a sizable difference of about 7 in theθangle,the resulting difference in the dipole interactions is not sufficiently strong to cause any significant differences in their magnetic properties.Further change in theθangles to the"side-by-side"(θ=90°)or"head-to-tail"(θ=0°)arrangement of the magnetic easy axes,achievable by rational mo-lecular design,is expected to lead to molecular magnetic materials with much enhanced properties.
基金supported by the National Natural Science Foundation of China(Grant No.32371284)the Open Fund of the State Key Laboratory of Optoelectronic Materials and Technologies,Sun Yatsen University(Grant No.OEMT-2024-ZTS-04)support from the Physical Research Platform in the School of Physics,Sun Yatsen University(Grant No.PRPSP,SYSU).
文摘DNA imaging and visualization techniques are crucial in biological experiments and have also emerged as a powerful method for single-molecule studies.Traditional intercalating dyes(e.g.,SYTOX,EtBr,GelRed)can stain DNA but may alter its structure and mechanical properties,and cause photocleavage.Recently,a novel fluorescent DNA-binding protein(FP-DBP)was introduced,which can stain DNA without sequence preference and without inducing photocleavage.In this study,using a custom-built magnetic tweezers system,we performed DNA stretching,twisting and unzipping experiments to compare the mechanical properties of DNA with and without two kinds of intercalating dyes(SYTOX Orange and GelRed)and mCherry FP-DBP.Our results show that mCherry FP-DBP does not affect DNA structure or mechanics,unlike SYTOX Orange and GelRed,making FP-DBP a promising tool for DNA visualization in single-molecule experiments.
基金financially supported by the National Natural Science Foundation of China(No.22273079)。
文摘Sodium alginate(SA)is generally considered highly hydrophilic due to two hydroxyl groups and a carboxylate group on each pyranose ring.However,SA will form a gel after dissolving in water for a certain period.The two properties of SA,hydrophilicity and gelation,seem to be paradoxical.In this study,to explore the mechanism behind these paradoxical properties,the single-chain behaviors of SA in various liquid environments have been investigated by using single-molecule force spectroscopy(SMFS).In nonpolar solvents such as nonane,SA exhibits its single-chain inherent elasticity consistent with the theoretical elasticity derived from quantum mechanical(QM)calculations.Notably,the experimental curve of SA obtained in water shows a long plateau in the low force region.Further research reveals that this phenomenon is driven by the hydrophobic effect.Additionally,SA shows greater rigidity than its inherent elasticity in the middle and high force regions due to electrostatic repulsion between carboxylate groups on adjacent sugar rings.Comparative single-molecule studies suggest that SA exhibits considerable hydrophobicity,offering new insights into the gelation process in water.
基金supported by Guangxi Science and Technology Program(No.GuiKeAD23026291)Guangxi Science and Technology Major Project(No.AA22068057).
文摘Clustering is a pivotal data analysis method for deciphering the charge transport properties of single molecules in break junction experiments.However,given the high dimensionality and variability of the data,feature extraction remains a bottleneck in the development of efficient clustering methods.In this regard,extensive research over the past two decades has focused on feature engineering and dimensionality reduction in break junction conductance.However,extracting highly relevant features without expert knowledge remains an unresolved challenge.To address this issue,we propose a deep clustering method driven by task-oriented representation learning(CTRL)in which the clustering module serves as a guide for the representation learning(RepL)module.First,we determine an optimal autoencoder(AE)structure through a neural architecture search(NAS)to ensure efficient RepL;second,the RepL process is guided by a joint training strategy that combines AE reconstruction loss with the clustering objective.The results demonstrate that CTRL achieves excellent performance on both the generated and experimental data.Further inspection of the RepL step reveals that joint training robustly learns more compact features than the unconstrained AE or traditional dimensionality reduction methods,significantly reducing misclustering possibilities.Our method provides a general end-to-end automatic clustering solution for analyzing single-molecule break junction data.
基金supported by the National Natural Science Foundation of China(Grant Nos.12474286,22173052,and 12204281).
文摘The forming processes of 4,40-dipyridyl-based single-molecule junctions and mechanically induced conductance switching as well as the side-group effects are systematically investigated by applying the ab initio-based adiabatic geometric optimization method and the one-dimensional transmission combined with three-dimensional correction approximation(OTCTCA)method.The numerical results show that for the 4,40-dipyridyl with a p-conjugated phenyl-phosphoryl or diphenylsilyl side group,the pyridyl vertically anchors on the second atomic layer of the pyramid-shaped Au tip electrode at small inter-electrode distances by laterally pushing the apical Au atom aside,which induces stronger pyridyl-electrode coupling and high-conductance state of the formed junctions.As the inter-electrode distance increases,the pyridyl shifts to the apical Au atom of the tip electrode.This apical Au atom introduces additional scatterings to the tunneling electrons and significantly decreases the conductance of the junctions.Furthermore,for the 4,40-dipyridyl with a phenyl-phosphoryl side group,the probability of manifesting the high-conductance state is decreased due to the oxygen atom reducing the probability of the pyridyl adsorbing on the second layer of Au tip electrode.In contrast,for the 4,40-dipyridyl with a nonconjugated cyclohexyl-phosphoryl side group,the steric hindrance from the bulky cyclohexyl group leads the molecule to preferentially form the O-Au contact,which prevents both the high conductance and mechanically induced conductance switching of the junction.Our results provide a theoretical understanding of the side-group effects on electronic transport properties of single-molecule junctions,offering an alternative explanation for the experimental observations.
基金financially supported by the National Natural Science Foundation of China(Nos.U23A20594,22375066 and 21788102)Guang Dong Basic and Applied Basic Research Foundation(No.2023B1515040003)。
文摘Quinoid structures are considered to be conducive to the charge transport of organic molecules,but this hypothesis is rarely proven at single-molecule level.Herein,as a proof of concept,the single-molecule conductance of two furan-based isomers,3,3'-bis(4-(methylthio)phenyl)-2,2'-bifuran(2,2'-SMPBF)and 4,4'-bis(4-(methylthio)phenyl)-3,3'-bifuran(3,3'-SMPBF),is investigated by the scanning tunneling microscopy break junction(STM-BJ)technique and theoretical simulation.2,2'-SMPBF prefers to adopt a nearly planar conformation with intact alternating single and double bonds extended via2,2'-bifuran moiety and therefore exhibits goodπ-conjugation and a prominent quinoid structure.However,theπ-conjugation of 3,3'-SMPBF is interrupted due to ineffective cross-conjugation in the 3,3'-bifuran moiety,leading to the absence of a quinoid structure.2,2'-SMPBF displays switchable multiple conductances induced by the interconversion between folded and unfolded conformations and an abnormal rebound of conductance along with the increases of electrode displacement,which is demonstrated to be caused by the quinoid structure in a nearly planar conformation during the stretching process.However,3,3'-SMPBF without a quinoid structure in unfolded conformation exhibits extremely low conductance that cannot be captured in STM-BJ measurements.These results reveal the significant contribution of quinoid structure to molecular charge transport and provide valuable information on the structure-transport relationship for the design of efficient organic semiconductors.
基金supported by the National Natural Science Foundation of China(No.22375157)the State Key Laboratory of Electrical Insulation and Power Equipment(No.EIPE23405)+2 种基金the Fundamental Research Funds for Central Universities(No.xtr052023002)the Special Support Plan of Shaanxi Province for Young Top-notch Talentthe Medical-Engineering Cross Project of the First Affiliated Hospital of XJTU(No.QYJC02)。
文摘Due to the ionic feature of the lanthanide ions,to straightly bridge two lanthanide(Ln)ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization(QTM)for single-molecule magnets(SMMs),a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent.Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ)complexes-{[LnL_(A)(4-NH_(2)py)_(5)]_(2)(μ-Cl)}[BPh_(4)]_(3)(For L_(A)^(-)=1-AdO^(-),1Ln;for L_(A)^(-)=~tBuO^(-),2Ln;Ln=Dy,Gd).More uniquely,the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ)ions with local C_(5v)symmetry.The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K(τ_(2K)=2706.89 and 1437.05 s for 1Dy and 2Dy)compared to the diluted ones with the approaching magnetic property of the C_(5v)motifs(τ_(2K)=0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y).Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic,it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.
基金supported by the National Natural Science Foundation of China(22238002 and 22208047)the China Postdoctoral Science Foundation(2024T170086 and 2022M720639)+1 种基金the Research and Innovation Team Project of Dalian University of Technology(DUT2022TB10)the Fundamental Research Funds for the Central Universities(DUT22LAB610)。
文摘Despite the ongoing increase in the efficiency of perovskite solar cells(PSCs),residual lead iodide(PbI2and moisture sensitivity issues continue to constrain their further commercialization.Herein,we propose a thermally mediated in situ repair and encapsulation strategy to construct high-performance PSCs by incorporating piperazine thioctic acid salt(TAPPZ)as a dopant into the perovskite precursor Thermally dissociated piperazine(PPZ)from TAPPZ integrates microcrystals to form larger grain(>2000 nm),while the carboxylic acid in thioctic acid(TA)and the amine salt in TAPPZ synergistically passivate and transform PbI_(2),significantly reducing its residual amount.Additionally,TAPPZ undergoe thermal self-crosslinking during perovskite annealing,enabling melt-polymerization to form in situ encapsulation for enhanced water resistance.The TAPPZ-incorporated device achieves a remarkable efficiency of 25.65% and exhibits excellent operational stability,retaining over 90% of its initial efficiency after 2000 h under ambient conditions(20-30℃,20%-30% relative humidity).This study provide new insights into the construction of high-performance perovskite solar cells by designing and synthe sizing multifunctional single molecules for in situ repair and encapsulation of perovskites.
基金the Fundamental Research Funds for the Central Universities (Nos. 2024CDJXY0022023CDJYGRH-YB17+4 种基金2022CDJXY-025)the Venture & Innovation Support Program for Chongqing Overseas Returnees (No. cx2022061)the Natural Science Foundation of Chongqing (No. CSTB2022NSCQ-MSX1123)the Chongqing Talents: Exceptional Young Talents Project (No. cstc2021ycjh-bgzxm0067)the Hongshen Young Scholars Program from Chongqing University (No. 0247001104426) for financial support。
文摘The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These novel fiuorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule whitelight materials with high fiuorescence quantum yields. The robust organic and low-cost white lightemitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared(NIR) fiuorescence materials with large Stokes shifts based on the olefination of heterocycles.
基金supported by the National Key Research and Development Program(No.2022YFE0107400)the internal research funding from Photonic View Technology Technology Co.,Ltd.the GuangCi Deep Mind Project of Ruijin Hospital Shanghai Jiao Tong University School of Medicine.
文摘The single-molecule detection tech-nique plays a pivotal role in elucidat-ing the fundamental mechanisms of various scientific processes at the molecular level,and holds essential im-portance in multiple fields including physics,biology,and chemistry.Re-cently,single-molecule detection has garnered increasing attention owing to its practical utility in medical diagno-sis,primarily due to its exceptional sensitivity and the minimal sample volume required for analysis.However,the conventional single-molecule technique,represented by total internal reflection microscopy,faces challenges such as sophisticated operation procedures and limited detection throughput,thereby impeding its broader application.To address these limitations,we have demonstrated single-molecule detection using an integrated silicon photonic chip,of-fering a cost-effective and user-friendly alternative.By employing basic optics,we efficiently introduce the excitation source for single-molecule fluorescence by harnessing the strong evanescent field of high refractive-index waveguides.Subsequently,fluorescence signals are collected using basic optics comprising a water-immersion objective,relay optics,and a digi-tal camera.Our results highlight a low-cost,high-throughput single-molecule technique achieved through the integrated silicon photonic chip.This innovative approach is promised to facilitate the widespread adoption of single-molecule fluorescence in medical diagnosis.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11974217,12204281,and 21933002)the Shandong Provincial Natural Science Foundation (Grant No.ZR2022QA068)。
文摘Orientation-dependent transport properties induced by anisotropic molecules are enticing in single-molecule junctions.Here,using the first-principles method,we theoretically investigate spin transport properties and photoresponse characteristics in trimesic acid magnetic single-molecule junctions with different molecular adsorption orientations and electrode contact sites.The transport calculations indicate that a single-molecule switch and a significant enhancement of spin transport and photoresponse can be achieved when the molecular adsorption orientation changes from planar geometry to upright geometry.The maximum spin polarization of current and photocurrent in upright molecular junctions exceeds 90%.Moreover,as the Ni tip electrode moves,the tunneling magnetoresistance of upright molecular junctions can be increased to 70%.The analysis of the spin-dependent PDOS elucidates that the spinterfaces between organic molecule and ferromagnetic electrodes are modulated by molecular adsorption orientation,where the molecule in upright molecular junctions yields higher spin polarization.Our theoretical work paves the way for designing spintronic devices and optoelectronic devices with anisotropic functionality base on anisotropic molecules.
基金supported by the National Natural Science Foundation of China (Grant Nos. 12174322 to HC, 12204124 to ZG, 32271367 and 12204389 to SL)the 111 project (Grant No. B16029)the Research Fund of Wenzhou Institute
文摘Force spectrum measurements with constant loading rates are widely used in single-molecule manipulation experiments to study the mechanical stability and force response of biomolecules.Force-dependent transition rates can be obtained from the transition force distribution,but it is limited to the force range with non-zero force distribution.Although constant loading rate control can be realized with magnetic tweezers,the loading rate range is limited due to the slow movement of permanent magnets.Non-linear exponential and exponential squared force loading functions are more feasible in magnetic tweezers,while there is no theoretical result available for these two kinds of non-linear force loading functions.In this study,we solved the unfolding process of a protein following Bell's model under nonlinear exponential and exponential squared force loading functions,which offer a broader range of unfolding force distribution compared to the traditional constant loading rate experiments.Furthermore,we derived two force loading functions,which can produce uniform unfolding force distribution.This research contributes fundamental equations for the analysis of experimental data obtained through single-molecule manipulation under nonlinear force loading controls,paving the way for the use of nonlinear force control in magnetic tweezer experiments.
基金primary financial supports from the National Key R&D Program of China(2021YFA1200102,2021YFA1200101,and 2022YFE0128700)the National Natural Science Foundation of China(22173050,22150013,21727806,and 21933001)+4 种基金the New Cornerstone Science Foundation through the XPLORER PRIZEthe Natural Science Foundation of Beijing(2222009)Beijing National Laboratory for Molecular Sciences(BNLMS202105)the Fundamental Research Funds for the Central Universities(63223056)“Frontiers Science Center for New Organic Matter”at Nankai University(63181206).
文摘Single-molecule junctions,integrating individual molecules as active components between electrodes,serve as fundamental building blocks for advanced electronic and sensing technologies.The application of ionic liquids in single-molecule junctions represents a cutting-edge and rapidly evolving field of research at the intersection of nanoscience,materials chemistry,and electronics.This review explores recent advances where ionic liquids function as electrolytes,dielectric layers,and structural elements within single-molecule junctions,reshaping charge transport,redox reactions,and molecular behaviors in these nanoscale systems.We comprehensively dissect fundamental concepts,techniques,and modulation mechanisms,elucidating the roles of ionic liquids as gates,electrochemical controllers,and interface components in singlemolecule junctions.Encompassing applications from functional device construction to unraveling intricate chemical reactions,this review maps the diverse applications of ionic liquids in single-molecule junctions.Moreover,we propose critical future research topics in this field,including catalysis involving ionic liquids at the single-molecule level,functionalizing single-molecule devices using ionic liquids,and probing the structure and interactions of ionic liquids.These endeavors aim to drive technological breakthroughs in nanotechnology,energy,and quantum research.
基金This work is supported by the National Natural Sci-ence Foundation China(No.22173052 of and No.11974217).
文摘Moleculardeviceswith highswitchingperformance and/or the perfect spin filtering effect have always been the pursuit with the development of molecular electronics.Hereb,yusingthe 2001.0V nonequilibrium.Green's function method in combination with the density functionaltheory,the switching performance and spin filtering properties of dimethyldihydropyrene(DHP)/cyclophanediene(CPD)photoswitchable molecule connected by carbon atomic chains(CACs)to two zigzag graphene nanoribbon electrodes have been theoretically investigated.The results show that DHP is more conductive than CPD and therefore an evident switching effect is demonstrated,and the switching ratio(RON/OFF)can reach 4.5×103.It is further revealed that the RoON/OF of DHP/CPD closely depends on the length of CACs.More specifically,the RoN/OFF values of DHP/CPD with odd-numbered CACs are larger than those with even-numbered CACs.More interestingly,a high or even perfect spin filtering effect can be obtained in these investigated DHP/CPD single-molecule devices.Our study is helpful for future design of single-molecule switches and spin filters and provides a way to optimize their performance by means of varying the length of bridging CACs.
基金supported by the National Key Research and Development Program of China(Grant No.2019YFA0709304)the National Natural Science Foundation of China(Grant Nos.12090051 and 12022409)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB37000000)the Youth Innovation Promotion Association of CAS(Grant Nos.2021009 and Y2021003)
文摘Physical biology is an interdisciplinary field that bridges biology with physical sciences and engineering.Singlemolecule physical biology focuses on dynamics of individual biomolecules and complexes,aiming to answering basic questions about their functions and mechanisms.It takes advantages of physical methodologies to gain quantitative understanding of biological processes,often engaging precise physical measurements of reconstructed objects to avoid interference from unnecessary complications.In this review,we(i)briefly introduce concepts of single-molecule physical biology,(ii)describe extensively used single-molecule methodologies that have been developed to address key questions in two important objects of single-molecule physical biology,namely,nucleic acid-interacting proteins and membraneinteracting proteins,and(iii)show by a few successful examples how one may use single-molecule methods to deepen our understanding of protein machines.
基金supported by the National Natural Science Foundation of China(Nos.22205084,42307566,22325303,22250003,T2222002,21991130,22032004)Fujian Provincial Natural Science Foundation of China(No.2022H6014)+4 种基金the China Postdoctoral Science Foundation(Nos.2023M741039,2023M742199)Project funded by National&Local Joint Engineering Research Center for Mineral Salt Deep Utilization(No.SF202303)State Key Laboratory of Efficient Utilization for Low Grade Phosphate Rock and Its Associated Resources WFKF(2023)013the Fundamental Research Funds for the Central Universities(Xiamen University,No.20720240053)State Key Laboratory of Vaccines for Infectious Diseases,Xiang An Biomedicine Laboratory(No.2023XAKJ0103074)。
文摘Single-molecule junctions are building blocks for constructing molecular devices.However,intermolecular interactions like winding bring additional interference among the surrounding molecules,which inhibits the intrinsic coherent transport through single-molecule junctions.Here,we employed a nanocavity(dimethoxypillar[5]arene,DMP[5]),which is analogous to electric cables,to confine the conformation of flexible chains(1,8-diaminooctane,DAO)via host-vip interaction.Single-molecule conductance measurements indicate that the conductance of DAO encapsulated with DMP[5]is as high as that of pure DAO,as reproduced by theoretical simulations.Intriguingly,the molecular lengths of the DAO encapsulated with DMP[5]increase from 1.13 nm to 1.46 nm compared with the pure DAO,indicating that DMP[5]keeps DAO upright-standing via the confinement effect.This work provides a new strategy to decouple the intermolecular interaction by employing an insulating sheath,enabling the high-density integration of single-molecule devices.
基金the National Natural Science Foundation of China(22375157)the Programme of Introducing Talents of Discipline to Universities(B23025)+4 种基金State Key Laboratory of Electrical Insulation and Power Equipment(EIPE23402,EIPE23405)SpecialSupportPlanof ShaanxiProvincefor Young Top-notch Talent,the Fundamental Research Funds for Central Universities(xtr052023002,xzy012023024)the China Postdoctoral Science Foundation(2023M742783)Shaanxi Postdoctoral Science Foundation(2023BSHYDZZ12)the"Scientists+engineers"Team Building Project of Qin Chuang Yuan(2022KXJ-088).
文摘A series of isomeric sandwich-type dysprosiacarboranyl complexes,including[Na(THF)_(5)][3.2'-(THF)_(2)-3.2-Dy(1,2-C_(2)B_(9)H_(11))_(x)(1'7'-C_(2)B_(9)H_(11))_(2-x))(o/m-Dy)and[Na(THF)_(5)][2.2'-(THF)_(2)-2.2'-Dy(1,7-C_(2)B_(9)H_(11))2](m-Dy)were synthesized by using the isomeric dicarbollide ligands,namely[nido-7,8-C2BgH_(11)]^(2-)and[nido-7,9-C_(2)B_(9)H_(11)]^(2-).The structural details of o/m-Dy and m-Dy and magnetic dynamics of m-Dy were investigated to compare with the previous study on[Na(THF)_(5)][2.2'-(THF)_(2)-2.2'-Dy(1,2-C_(2)B_(9)H_(11))_(2)]o-Dy.The bending angles of sandwiched dysprosiacarboranes are straightened so as to improve energy bar-riers(U_(eff))from 430(5)to 591(0)K.Magneto-structural correlations show that the introduction of meta-C sites within the π-electron delocalized heterocyclic ring can effectively shorten the Dy-C_(2)B_(3)centroid distance and increase the C_(2)B_(3)centroid...Dy...C_(2)B_(3)centroid bending angle which is attributed to the dif-ferences in electronegativity between C and B atoms on the ring of C_(2)B_(3)^(2-).Therefore,to further enhance the performance of single-molecule magnets(SMMs)on this basis,future endeavors should focus on diminishing the equatorial solvent molecules to make a wider C2B3...Dy...C_(2)B_(3)bending angle.
基金supported by the National Natural Science Foundation of China(Nos.22225806,22078314,22278394,22378385)Dalian Institute of Chemical Physics(Nos.DICPI202227,DICPI202436)。
文摘Monitoring the dynamics of cellular pseudopodia at nanoscale has become essential for understanding their diverse and complex functions in living cells.This is made possible by combining single-molecule localization microscopy(SMLM)with self-blinking dyes.However,existing self-blinking dyes often face limitations,such as nonspecific blinking and low photostability,which can bring background noise and yield erroneous localization signals,hindering their effectiveness for nanoscale visualization.Here,we present a method for long-term SMLM imaging of cellular pseudopodia dynamics using a blinkogenic probe that exhibits self-blinking activation upon molecular recognition.This approach enabled the precise tracking of various pseudopodia structures,including filopodia,lamellipodia,and(tunneling nanotubes)-nanoscale(TNTs),in living cells.We monitored the growth and fusion of filopodia,as well as the extension and shrinkage of lamellipodia,in real-time.Additionally,we identified two distinct fusion modes between filopodia and lamellipodia and captured the formation of TNTs and their interactions with filopodia,demonstrating the probe's utility in visualizing real-time pseudopodia dynamics at nanoscale.
