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1.
Anal Chem ; 2021 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-34668693

RESUMO

The discharged state affects the charge transfer resistance of lithium-ion secondary batteries (LIBs), which is referred to as the depth of discharge (DOD). To understand the intrinsic charge/discharge property of LIBs, the DOD-dependent charge transfer resistance at the solid-liquid interface is required. However, in a general composite electrode, the conductive additive and organic polymeric binder are unevenly distributed, resulting in a complicated electron conduction/ion conduction path. As a result, estimating the DOD-dependent rate-determining factor of LIBs is difficult. In contrast, in micro/nanoscale electrochemical measurements, the primary or secondary particle is evaluated without using a conductive additive and providing an ideal mass transport condition. To control the DOD state of a single LiFePO4 active material and evaluate the DOD-dependent charge transfer kinetic parameters, we use scanning electrochemical cell microscopy (SECCM), which uses a micropipette to form an electrochemical cell on a sample surface. The difference in charge transfer resistance at the solid-liquid interface depending on the DOD state and electrolyte solution could be confirmed using SECCM.

2.
J Phys Chem Lett ; 12(33): 8039-8045, 2021 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-34402624

RESUMO

Calcite dissolution is initiated by the formation of a nanoscale etch pit followed by step edge propagation and hence strongly influenced by the interactions between surface diffusing ions and step edges. However, such atomic-scale dynamics are mostly inaccessible with current imaging tools. Here, we overcome this limitation by using our recent development of high-speed frequency modulation atomic force microscopy. By visualizing atomic-scale structural changes of the etch pits at the calcite surface in water, we found the existence of mobile and less-mobile surface adsorption layers (SALs) in the etch pits. We also found that some etch pits maintain their size for a long time without expansion, and their step edges are often associated with less-mobile SALs, suggesting their step stabilization effect.


Assuntos
Carbonato de Cálcio/química , Microscopia de Força Atômica/métodos , Nanoestruturas/química , Adsorção , Cristalografia , Estrutura Molecular , Solubilidade , Propriedades de Superfície , Água/química
3.
Sci Rep ; 11(1): 7756, 2021 04 08.
Artigo em Inglês | MEDLINE | ID: mdl-33833307

RESUMO

Over the last decade, nanoneedle-based systems have demonstrated to be extremely useful in cell biology. They can be used as nanotools for drug delivery, biosensing or biomolecular recognition inside cells; or they can be employed to select and sort in parallel a large number of living cells. When using these nanoprobes, the most important requirement is to minimize the cell damage, reducing the forces and indentation lengths needed to penetrate the cell membrane. This is normally achieved by reducing the diameter of the nanoneedles. However, several studies have shown that nanoneedles with a flat tip display lower penetration forces and indentation lengths. In this work, we have tested different nanoneedle shapes and diameters to reduce the force and the indentation length needed to penetrate the cell membrane, demonstrating that ultra-thin and sharp nanoprobes can further reduce them, consequently minimizing the cell damage.

4.
Nanoscale ; 13(13): 6661-6677, 2021 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-33885545

RESUMO

Exosomes have recently gained interest as mediators of cell-to-cell communication and as potential biomarkers for cancer and other diseases. They also have potential as nanocarriers for drug delivery systems. Therefore, detailed structural, molecular, and biomechanical characterization of exosomes is of great importance for developing methods to detect and identify the changes associated with the presence of cancer and other diseases. Here, we employed three-dimensional atomic force microscopy (3D-AFM) to reveal the structural and nanomechanical properties of exosomes at high spatial resolution in physiologically relevant conditions. The substructural details of exosomes released from three different cell types were determined based on 3D-AFM force mapping. The resulting analysis revealed the presence of distinct local domains bulging out from the exosome surfaces, which were associated with the exosomal membrane proteins present on the outer surface. The nanomechanical properties of individual exosomes were determined from the 3D-force maps. We found a considerably high elastic modulus, ranging from 50 to 350 MPa, as compared to that obtained for synthetic liposomes. Moreover, malignancy-dependent changes in the exosome mechanical properties were revealed by comparing metastatic and nonmetastatic tumor cell-derived exosomes. We found a clear difference in their Young's modulus values, suggesting differences in their protein profiles and other exosomal contents. Exosomes derived from a highly aggressive and metastatic k-ras-activated human osteosarcoma (OS) cell line (143B) showed a higher Young's modulus than that derived from a nonaggressive and nonmetastatic k-ras-wildtype human OS cell line (HOS). The increased elastic modulus of the 143B cell-derived exosomes was ascribed to the presence of abundant specific proteins responsible for elastic fiber formation as determined by mass spectroscopy and confirmed by western blotting and ELISA. Therefore, we conclude that exosomes derived from metastatic tumor cells carry an exclusive protein content that differs from their nonmetastatic counterparts, and thus they exhibit different mechanical characteristics. Discrimination between metastatic and nonmetastatic malignant cell-derived exosomes would be of great importance for studying exosome biological functions and using them as diagnostic biomarkers for various tumor types. Our findings further suggest that metastatic tumor cells release exosomes that express increased levels of elastic fiber-associated proteins to preserve their softness.


Assuntos
Neoplasias Ósseas , Exossomos , Osteossarcoma , Linhagem Celular Tumoral , Módulo de Elasticidade , Humanos , Microscopia de Força Atômica
5.
Anal Chem ; 93(14): 5831-5838, 2021 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-33783208

RESUMO

Boron-doped diamond (BDD) is most often grown by chemical vapor deposition (CVD) in polycrystalline form, where the electrochemical response is averaged over the whole surface. Deconvoluting the impact of crystal orientation, surface termination, and boron-doped concentration on the electrochemical response is extremely challenging. To tackle this problem, we use CVD to grow isolated single-crystal microparticles of BDD with the crystal facets (100, square-shaped) and (111, triangle-shaped) exposed and combine with hopping mode scanning electrochemical cell microscopy (HM-SECCM) for electrochemical interrogation of the individual crystal faces (planar and nonplanar). Measurements are made on both hydrogen- (H-) and oxygen (O-)-terminated single-crystal facets with two different redox mediators, [Ru(NH3)6]3+/2+ and Fe(CN)64-/3-. Extraction of the half-wave potential from linear sweep and cyclic voltammetric experiments at all measurement (pixel) points shows unequivocally that electron transfer is faster at the H-terminated (111) surface than at the H-terminated (100) face, attributed to boron dopant differences. The most dramatic differences were seen for [Ru(NH3)6]3+/2+ when comparing the O-terminated (100) surface to the H-terminated (100) face. Removal of the H-surface conductivity layer and a potential-dependent density of states were thought to be responsible for the behavior observed. Finally, a bimodal distribution in the electrochemical activity on the as-grown H-terminated polycrystalline BDD electrode is attributed to the dominance of differently doped (100) and (111) facets in the material.

6.
Anal Chem ; 92(23): 15388-15393, 2020 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-33205942

RESUMO

Glass nanopipettes are widely used for various applications in nanosciences. In most of the applications, it is important to characterize their geometrical parameters, such as the aperture size and the inner cone angle at the tip region. For nanopipettes with sub-10 nm aperture and thin wall thickness, transmission electron microscopy (TEM) must be most instrumental in their precise geometrical measurement. However, this measurement has remained a challenge because heat generated by electron beam irradiation would largely deform sub-10 nm nanopipettes. Here, we provide methods for preparing TEM specimens that do not cause deformation of such tiny nanopipettes.

7.
Sci Rep ; 10(1): 17436, 2020 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-33060692

RESUMO

In recent years, the atomic force microscope has proven to be a powerful tool for studying biological systems, mainly for its capability to measure in liquids with nanoscale resolution. Measuring tissues, cells or proteins in their physiological conditions gives us access to valuable information about their real 'in vivo' structure, dynamics and functionality which could then fuel disruptive medical and biological applications. The main problem faced by the atomic force microscope when working in liquid environments is the difficulty to generate clear cantilever resonance spectra, essential for stable operation and for high resolution imaging. Photothermal actuation overcomes this problem, as it generates clear resonance spectra free from spurious peaks. However, relatively high laser powers are required to achieve the desired cantilever oscillation amplitude, which could potentially damage biological samples. In this study, we demonstrate that the photothermal excitation efficiency can be enhanced by coating the cantilever with a thin amorphous carbon layer to increase the heat absorption from the laser, reducing the required excitation laser power and minimizing the damage to biological samples.

8.
Microscopy (Oxf) ; 69(6): 340-349, 2020 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-32780817

RESUMO

In-liquid frequency modulation atomic force microscopy (FM-AFM) has been used for visualizing subnanometer-scale surface structures of minerals, organic thin films and biological systems. In addition, three-dimensional atomic force microscopy (3D-AFM) has been developed by combining it with a three-dimensional (3D) tip scanning method. This method enabled the visualization of 3D distributions of water (i.e. hydration structures) and flexible molecular chains at subnanometer-scale resolution. While these applications highlighted the unique capabilities of FM-AFM, its force resolution, speed and stability are not necessarily at a satisfactory level for practical applications. Recently, there have been significant advancements in these fundamental performances. The force resolution was dramatically improved by using a small cantilever, which enabled the imaging of a 3D hydration structure even in pure water and made it possible to directly compare experimental results with simulated ones. In addition, the improved force resolution allowed the enhancement of imaging speed without compromising spatial resolution. To achieve this goal, efforts have been made for improving bandwidth, resonance frequency and/or latency of various components, including a high-speed phase-locked loop (PLL) circuit. With these improvements, now atomic-resolution in-liquid FM-AFM imaging can be performed at ∼1 s/frame. Furthermore, a Si-coating method was found to improve stability and reproducibility of atomic-resolution imaging owing to formation of a stable hydration structure on a tip apex. These improvements have opened up new possibilities of atomic-scale studies on solid-liquid interfacial phenomena by in-liquid FM-AFM.

9.
Biochem Soc Trans ; 48(4): 1675-1682, 2020 08 28.
Artigo em Inglês | MEDLINE | ID: mdl-32779720

RESUMO

Recently, there have been significant advancements in dynamic-mode atomic force microscopy (AFM) for biological applications. With frequency modulation AFM (FM-AFM), subnanometer-scale surface structures of biomolecules such as secondary structures of proteins, phosphate groups of DNAs, and lipid-ion complexes have been directly visualized. In addition, three-dimensional AFM (3D-AFM) has been developed by combining a high-resolution AFM technique with a 3D tip scanning method. This method enabled visualization of 3D distributions of water (i.e. hydration structures) with subnanometer-scale resolution on various biological molecules such as lipids, proteins, and DNAs. Furthermore, 3D-AFM also allows visualization of subnanometer-scale 3D distributions of flexible surface structures such as thermally fluctuating lipid headgroups. Such a direct local information at nano-bio interfaces can play a critical role in determining the atomic- or molecular-scale model to explain interfacial structures and functions. Here, we present an overview of these recent advancements in the dynamic-mode AFM techniques and their biological applications.


Assuntos
Microscopia de Força Atômica/métodos , DNA/química , Lipídeos/química , Estrutura Molecular , Nanotecnologia , Proteínas/química
10.
Chem Commun (Camb) ; 56(65): 9324-9327, 2020 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-32671368

RESUMO

To visualize the electrochemical reactivity and obtain the diffusion coefficient of the anode of lithium-ion batteries, we used scanning electrochemical cell microscopy (SECCM) in a glovebox. SECCM provided the facet-dependent diffusion coefficient on a Li4Ti5O12 (LTO) thin-film electrode and detected the metastable crystal phase of LixFePO4.


Assuntos
Fontes de Energia Elétrica , Compostos de Lítio/análise , Lítio/química , Microscopia Eletroquímica de Varredura , Nanopartículas/química , Difusão , Eletrodos , Cinética
11.
Sci Rep ; 10(1): 9133, 2020 06 04.
Artigo em Inglês | MEDLINE | ID: mdl-32499532

RESUMO

Small cantilevers with a megahertz-order resonance frequency provide excellent sensitivity and speed in liquid-environment atomic force microscopy (AFM). However, stable and accurate oscillation control of a small cantilever requires the photothermal excitation, which has hindered their applications to the studies on photo-sensitive materials. Here, we develop a magnetic excitation system with a bandwidth wider than 4 MHz, enabling a light-free excitation of small cantilevers. In the system, a cantilever with a magnetic bead is driven by a magnetic field generated by a coil. In the coil driver, a differentiation circuit is used for compensating the frequency dependence of the coil impedance and keeping the current constant. By implementing several differentiation circuits with different frequency ranges, we enable to drive various cantilevers having different resonance frequencies with sufficient excitation efficiency. In contrast to the conventional coil driver with a closed-loop circuit, the developed one consists of an open-loop circuit and hence can be stably operated regardless of the coil design. With the developed system, atomic-resolution imaging of mica in liquid using a small cantilever with a megahertz-order resonance frequency is demonstrated. This development should lead to the future applications of AFM with small cantilevers to the studies on various photo-sensitive materials and phenomena.

12.
Nanoscale ; 12(24): 12856-12868, 2020 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-32520063

RESUMO

In this study, we have investigated the influence of the tip on the three-dimensional scanning force microscopy (3D-SFM) images of calcite-water interfaces by experiments and simulations. We calculated 3D force images by simulations with the solvent tip approximation (STA), Ca, CO3 and OH tip models. For all the 3D images, the z profiles at the surface Ca and CO3 sites alternately show oscillatory peaks corresponding to the hydration layers. However, the peak heights and spacings become larger when the mechanical stability of the tip becomes higher. For analyzing the xy slices of the 3D force images, we developed the extended STA (E-STA) model which allowed us to reveal the strong correlation between the hydration structure just under the tip and the atomic-scale force contrasts. Based on these understandings on the image features showing the strong tip dependence, we developed a method for objectively estimating the similarity between 3D force images. With this method, we compared the simulated images with the three experimentally obtained ones. Among them, two images showed a relatively high similarity with the image obtained by the simulation with the Ca or the CO3 tip model. Based on these agreements, we characterized the hydration structure and mechanical stability of the experimentally used tips. The understanding and methodology presented here should help us to derive accurate information on the tip and the interfacial structure from experimentally obtained 3D-SFM images.

13.
Nanoscale ; 12(9): 5452-5463, 2020 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-32080696

RESUMO

Although common in nature, the self-assembly of small molecules at sold-liquid interfaces is difficult to control in artificial systems. The high mobility of dissolved small molecules limits their residence at the interface, typically restricting the self-assembly to systems under confinement or with mobile tethers between the molecules and the surface. Small hydrogen-bonding molecules can overcome these issues by exploiting group-effect stabilization to achieve non-tethered self-assembly at hydrophobic interfaces. Significantly, the weak molecular interactions with the solid makes it possible to influence the interfacial hydrogen bond network, potentially creating a wide variety of supramolecular structures. Here we investigate the nanoscale details of water and alcohols mixtures self-assembling at the interface with graphite through group-effect. We explore the interplay between inter-molecular and surface interactions by adding small amounts of foreign molecules able to interfere with the hydrogen bond network and systematically varying the length of the alcohol hydrocarbon chain. The resulting supramolecular structures forming at room temperature are then examined using atomic force microscopy with insights from computer simulations. We show that the group-based self-assembly approach investigated here is general and can be reproduced on other substrates such as molybdenum disulphide and graphene oxide, potentially making it relevant for a wide variety of systems.

14.
Angew Chem Int Ed Engl ; 59(9): 3601-3608, 2020 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-31777142

RESUMO

High-resolution scanning electrochemical cell microscopy (SECCM) is used to image and quantitatively analyze the hydrogen evolution reaction (HER) catalytically active sites of 1H-MoS2 nanosheets, MoS2 , and WS2 heteronanosheets. Using a 20 nm radius nanopipette and hopping mode scanning, the resolution of SECCM was beyond the optical microscopy limit and visualized a small triangular MoS2 nanosheet with a side length of ca. 130 nm. The electrochemical cell provides local cyclic voltammograms with a nanoscale spatial resolution for visualizing HER active sites as electrochemical images. The HER activity difference of edge, terrace, and heterojunction of MoS2 and WS2 were revealed. The SECCM imaging directly visualized the relationship of HER activity and number of MoS2 nanosheet layers and unveiled the heterogeneous aging state of MoS2 nanosheets. SECCM can be used for improving local HER activities by producing sulfur vacancies using electrochemical reaction at the selected region.

15.
Anal Chem ; 92(2): 2159-2167, 2020 01 21.
Artigo em Inglês | MEDLINE | ID: mdl-31840491

RESUMO

Dynamic reassembly of the cytoskeleton and structural changes represented by dendritic spines, cargo transport, and synapse formation are closely related to memory. However, the visualization of the nanoscale topography is challenging because of the diffraction limit of optical microscopy. Scanning ion conductance microscopy (SICM) is an effective tool for visualizing the nanoscale topography changes of the cell surface without labeling. The temporal resolution of SICM is a critical issue of live-cell time-lapse imaging. Here, we developed a new scanning method, automation region of interest (AR)-mode SICM, to select the next imaging region by predicting the location of a cell, thus improving the scanning speed of time-lapse imaging. The newly developed algorithm reduced the scanning time by half. The time-lapse images provided not only novel information about nanoscale structural changes but also quantitative information on the dendritic spine and synaptic bouton volume changes and formation process of the neural network that are closely related to memory. Furthermore, translocation of plasmalemmal precursor vesicles (ppvs), for which fluorescent labeling has not been established, were also visualized along with the rearrangement of the cytoskeleton at the growth cone.


Assuntos
Hipocampo/química , Microscopia Eletroquímica de Varredura/métodos , Nanopartículas/metabolismo , Neurônios/química , Algoritmos , Animais , Feminino , Hipocampo/citologia , Hipocampo/metabolismo , Camundongos , Camundongos Endogâmicos ICR , Nanopartículas/análise , Neurônios/citologia , Neurônios/metabolismo , Gravidez
16.
Nihon Yakurigaku Zasshi ; 154(4): 192-196, 2019.
Artigo em Japonês | MEDLINE | ID: mdl-31597898

RESUMO

Primary cilia are non-motile cilia consisting of a centriole-derived basal body and a microtubule-based axoneme. In recent years, the structure and function of primary cilia have been attracting attention due to the relation with the onset of ciliary disease. Scanning ion conductance microscopy (SICM) is a probe microscopy used to measure the topography and functions of living cells at nanoscale. Furthermore, the labelling procedure is not necessary for SICM measurement compare to fluorescence imaging. We compared the structures of primary cilia of human retinal pigment epithelial cell line (RPE-1 cells) and Madin-Darby canine kidney cell line (MDCK cells) at nanoscale by using SICM. In addition, high resolution SICM images have also succeeded in visualizing ciliary pockets that difficult to be fluorescently labeled.


Assuntos
Cílios/fisiologia , Microscopia de Varredura por Sonda , Animais , Cães , Humanos , Íons , Células Madin Darby de Rim Canino , Epitélio Pigmentado da Retina/citologia
17.
Nihon Yakurigaku Zasshi ; 153(6): 267-272, 2019.
Artigo em Japonês | MEDLINE | ID: mdl-31178531

RESUMO

Scanning electrochemical microscopy (SECM), which utilizes microelectrodes as a probe to measure the chemicals released and consumed by cells as current signal, is a promising tool for measuring the metabolites of cells. We have improved SECM resolution for single cell imaging by miniaturizing the size of the electrode and developing hybrid system of SECM and scanning ion conductance microscopy (SICM), which utilizes nanopipette as a probe to measure live cell topography. SECM-SICM provides simultaneous imaging of concentration profiles of chemical substances and cell surface topography. Using this system, we successfully measured the release of neurotransmitters from PC12 cells. In addition, the nanoscale electrodes are useful for intracellular chemical detection by inserting the electrodes into cells and measured reactive oxygen species (ROS).


Assuntos
Microscopia/métodos , Análise de Célula Única/métodos , Animais , Eletrodos , Íons , Ratos , Espécies Reativas de Oxigênio/análise
18.
J Nanosci Nanotechnol ; 19(6): 3551-3557, 2019 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-30744784

RESUMO

For increasing the output of biofuel cells, increasing the cooperation between enzyme reaction and electron transfer on the electrode surface is essential. Highly oriented immobilization of enzymes onto a carbon nanotube (CNT) with a large specific surface area and excellent conductivity would increase the potential for their application as biosensors and biofuel cells, by utilizing the electron transfer between the electrode-molecular layer. In this study, we prepared a CNT-enzyme complex with highly oriented immobilization of enzyme onto the CNT surface. The complex showed excellent electrical characteristics, and could be used to develop biodevices that enable efficient electron transfer. Multi-walled carbon nanotubes (MWCNT) were dispersed by pyrene butyric acid N-hydroxysuccinimide ester, and then N-(5-amino-1-carboxypentyl) iminodiacetic acid (AB-NTA) and NiCl2 were added to modify the NTA-Ni2+ complex on the CNT surface. Pyrroloquinoline quinone (PQQ)-dependent glucose dehydrogenase (GDH) was immobilized on the CNT surface through a genetically introduced His-tag. Formation of the MWCNT-enzyme complex was confirmed by monitoring the catalytic current electrochemically to indicate the enzymatic activity. PQQ-GDH was also immobilized onto a highly ordered pyrolytic graphite surface using a similar process, and the enzyme monolayer was visualized by atomic force microscopy to confirm its structural properties. A biofuel cell was constructed using the prepared CNT-enzyme complex and output evaluation was carried out. As a result, an output of 32 µW/cm² could be obtained without mediators.


Assuntos
Fontes de Energia Bioelétrica , Técnicas Biossensoriais , Nanotubos de Carbono , Eletrodos , Enzimas Imobilizadas , Glucose , Pirenos
19.
ACS Nano ; 12(12): 11785-11797, 2018 12 26.
Artigo em Inglês | MEDLINE | ID: mdl-30422619

RESUMO

Hydration layers are ubiquitous in life and technology. Hence, interfacial aqueous layers have a central role in a wide range of phenomena from materials science to molecular and cell biology. A complete understanding of those processes requires, among other things, the development of very-sensitive and high-resolution instruments. Three-dimensional atomic force microscopy (3D-AFM) represents the latest and most successful attempt to generate atomically resolved three-dimensional images of solid-liquid interfaces. This review provides an overview of the 3D-AFM operating principles and its underlying physics. We illustrate and explain the capability of the instrument to resolve atomic defects on crystalline surfaces immersed in liquid. We also illustrate some of its applications to imaging the hydration structures on DNA or proteins. In the last section, we discuss some perspectives on emerging applications in materials science and molecular biology.

20.
ACS Nano ; 12(11): 11610-11624, 2018 11 27.
Artigo em Inglês | MEDLINE | ID: mdl-30335960

RESUMO

Hydrophilic surface chemistries can strongly bind water to produce surfaces that are highly resistant to protein adsorption and fouling. The interfacial bound water and its distinct properties have intrigued researchers for decades, yet the relationship between the water three-dimensional structure and function in antifouling coatings remains elusive. Here, we use hydrophilic, epoxy organosilane modified silica nanoparticles to demonstrate cheap, robust, and practically applied coatings that we discover have broad-ranging, ultralow fouling properties when challenged by various proteins, bacteria, and fungal spores. To understand their excellent antifouling properties, frequency modulation-atomic force microscopy is used to directly observe the interfacial water structure at subatomic resolution, which we validate using all-atom molecular dynamic simulations that strikingly predict similar structures of water layers on the original and ultralow fouling surfaces. The convergence of experimental and modeling data reveals that suitably spaced, flexible chains with hydrophilic groups interact with water molecules to produce a connective, quasi-stable layer, consisting of dynamic interfacial water, that provides a basis for antifouling performance of ultrathin, hydrophilic surface chemistries.

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