Optical Microscopy Probe Research Articles

In Situ Characterization Techniques for Electrochemical Nitrogen Reduction Reaction.

The electrochemical reduction of nitrogen to produce ammonia is pivotal in modern society due to its environmental friendliness and the substantial influence that ammonia has on food, chemicals, and energy. However, the current electrochemical nitrogen reduction reaction (NRR) mechanism is still imperfect, which seriously impedes the development of NRR. In situ characterization techniques offer insight into the alterations taking place at the electrode/electrolyte interface throughout the NRR process, thereby helping us to explore the NRR mechanism in-depth and ultimately promote the development of efficient catalytic systems for NRR. Herein, we introduce the popular theories and mechanisms of the electrochemical NRR and provide an extensive overview on the application of various in situ characterization approaches for on-site detection of reaction intermediates and catalyst transformations during electrocatalytic NRR processes, including different optical techniques, X-ray-based techniques, electron microscopy, and scanning probe microscopy. Finally, some major challenges and future directions of these in situ techniques are proposed.

Propagation constant-based diameter measurement technique for a submicrometer-scale optical fiber.

Diameter is a critical parameter for determining the physical properties of a submicrometer optical fiber and requires an accurate measurement. In this study, we proposed, to our knowledge, a novel diameter measurement technique derived from the waveguide theory, utilizing the pitch of a standing-wave near-field light generated by two counter-propagating lights within the submicrometer optical fiber. In a submicrometer optical fiber, the propagating light extends into the surrounding air as near-field light, existing within a range approximately equivalent to one wavelength from the surface of the fiber. By generating the standing-wave near-field light with the incident lights from both ends of the fiber, the pitch of the standing-wave near-field light can be measured by scanning along the fiber's central axis with a scanning near-field optical microscopy probe. The fiber diameter is subsequently acquired by solving the optical fiber eigenvalue equation. Based on the feasibility verification experiment, a high-precision measurement of approximately 0.50 µm was realized for the diameter of the optical fiber.

Correlative multimodal optical and X-ray fluorescence imaging of brominated fluorophores.

Imaging with multiple modalities can maximise the information gained from the analysis of a single sample. probes for optical fluorescence and X-ray fluorescence microscopy based on brominated 4-amino-1,8-naphthalimide and BODIPY scaffolds have been successfully designed and synthesised. Herein we show that these prototype probes, based on each of these scaffolds, can be imaged in two different cancer cell lines, and that the respective optical fluorescence and X-ray fluorescence signals are well correlated in these images.

Adaptive Optical Two-Photon Fluorescence Microscopy Probes Cellular Organization of Ocular Lenses In Vivo.

The mammalian ocular lens is an avascular multicellular organ that grows continuously throughout life. Traditionally, its cellular organization is investigated using dissected lenses, which eliminates in vivo environmental and structural support. Therefore, in vivo optical imaging methods for studying lenses in their native context in live animals are urgently needed. Here, we demonstrated that two-photon fluorescence microscopy can visualize lens cells in vivo. To maintain subcellular resolution at depth, we used adaptive optics to correct aberrations owing to ocular and lens tissues, which led to substantial signal and resolution improvements. Imaging lens cells up to 980 µm deep, we observed novel cellular organizations including suture-associated voids, enlarged vacuoles, and large cavities, contrary to the conventional view of a highly ordered organization. We tracked these features longitudinally over weeks and observed the incorporation of new cells during growth. Taken together, noninvasive longitudinal in vivo imaging of lens morphology using adaptive optics two-photon fluorescence microscopy will allow us to observe the development or alterations of lens cellular organization in living animals directly.

Mechanism of near-field optical nanopatterning on noble metal nano-films by a nanosecond laser irradiating a cantilevered scanning near-field optical microscopy probe.

To overcome the diffraction limit, a laser irradiating cantilevered scanning near-field optical microscopy (SNOM) probe has been used in near-field optical nanopatterning. In this paper, the mechanism of nanopatterning on noble metal nano-films by this technique is investigated by the finite element method. It is proposed that the main mechanism of this phenomenon is the melt and reshaping of the nano-film under the SNOM tip. The melt is caused by the surface plasmon polariton-assisted enhancement and restriction within the SNOM tip aperture. The impacts of the gap g between the tip and substrate and the polarization of the laser are further analyzed.

Antibody Functionalization of Ultrasmall Fluorescent Core–Shell Aluminosilicate Nanoparticle Probes for Advanced Intracellular Labeling and Optical Super Resolution Microscopy

Fluorescent labeling of cellular substructures is commonly performed using antibody–organic dye conjugates. Organic dyes do not exhibit ideal optical properties in terms of brightness and photostability, however, in particular when it comes to advanced optical super-resolution microscopy (SRM) applications. Here, we demonstrate the efficient conjugation of widely available secondary antibodies and cationic species to ultrasmall (sub-10 nm) fluorescent silica core─poly(ethylene glycol) shell (core–shell) aluminosilicate nanoparticles (aC′ dots) encapsulating different color dyes for specific targeting and high-quality fluorescence imaging of structures of the cytoskeleton (tubulin and actin) and nucleus, respectively. We show that the different color aC′ dots provide enhanced brightness and photostability relative to their parent dyes. As recently discovered, we further demonstrate that they exhibit photo-induced blinking with low ON–OFF duty cycles enabling optical SRM, for example, in the form of stochastic optical reconstruction microscopy (STORM), without the need for complex imaging setups or cocktails. After carefully optimizing Ab–aC′ dot conjugation as well as cell structure labeling protocols in fixed and permeabilized HeLa and MDA-MB-231 cells, we demonstrate three-color STORM and exemplify improved resolution compared to standard antibody–dye conjugates. This work paves the way to next-generation multifunctional optical probes based on ultrasmall silica nanoparticle platforms for advanced applications in bioimaging, nanomedicine, and beyond.

Fabrication of nanostructure on Au nano-film by nanosecond laser coupled with cantilevered scanning near-field optical microscopy probe

Diffraction limit has been the constraint of the nanostructure fabrication. Because the scanning near-field optical microscopy (SNOM) can work in the evanescent near-field region, its application in nano-processing has received extensive attention from researchers globally. In this paper, we combined nanosecond laser with cantilevered SNOM probe. Utilizing the high precision of the confinement and enhancement effect of probe tip and the high instantaneous energy of the laser, we realized nanostructure fabrication and in situ detection on Au nano-film. Feature sizes down to 47 nm full width at half maximum were fabricated. We investigated the laser propagation through the SNOM tip aperture and the light field intensity distribution on the surface of substrate theoretically. The calculation results demonstrate that the laser is highly restricted within the SNOM aperture and enhanced on the exit plane at the rim of aperture. After the transmission, the light field intensity distribution on the surface of the Au nano-film was enhanced due to the localized surface plasmon resonance. The thermal distribution on the surface of Au nano-film indicates that the peak of the temperature distribution appeared at the surface right underneath the center of the aperture. It is proved that the simulation results are consistent with the experimental results.

Biochemical Interactions through Microscopic Techniques: Structural and Molecular Characterization.

Many researchers and scientists have contributed significantly to provide structural and molecular characterizations of biochemical interactions using microscopic techniques in the recent decade, as these biochemical interactions play a crucial role in the production of diverse biomaterials and the organization of biological systems. The properties, activities, and functionalities of the biomaterials and biological systems need to be identified and modified for different purposes in both the material and life sciences. The present study aimed to review the advantages and disadvantages of three main branches of microscopy techniques (optical microscopy, electron microscopy, and scanning probe microscopy) developed for the characterization of these interactions. First, we explain the basic concepts of microscopy and then the breadth of their applicability to different fields of research. This work could be useful for future research works on biochemical self-assembly, biochemical aggregation and localization, biological functionalities, cell viability, live-cell imaging, material stability, and membrane permeability, among others. This understanding is of high importance in rapid, inexpensive, and accurate analysis of biochemical interactions.

Measurement properties of electric field intensity distribution of whispering gallery mode with near-field optical probe

The distribution of the external electric field intensity of the whispering gallery mode (WGM) can be measured using a scanning near-field optical microscopy (SNOM) probe. As probing the resonator influences the optical resonance state, the measurement properties of the SNOM probe are worth studying. In this study, the measurement mechanism of WGMs using a glass SNOM probe was analyzed numerically. A probe with a nanometric-diameter is generally preferable. The results showed that the high-contrast measurement was possible; however, the signal was weak. Using a tip with a diameter equal to half the resonant wavelength, the signal strength was maximized with the same high contrast level as the nanoprobe. Interestingly, the measurement mechanism was different depending on tip size. With the nanoprobe, the interaction with the WGMs varied depending on the sensing locations; therefore, the resonant states were modulated during the measurements, which may have induced unexpected mode hopes. The resonance state was steady during measurements using a probe tip with a diameter of half the resonance wavelength. Although the mechanisms were different, the measured electric field intensity distributions were the same for both tip diameters.

Design and characterization of a new microscopy probe using COMSOL and ANSYS

This paper presents the design, simulation, and analysis of different 3D-shapes of scanning near-field optical microscopy probes, allowing the acquisition of both topographic and optical images. The study is conducted using COMSOL and ANSYS simulation tools to study the probe sensitivity and deflection. The simulation calculations of deflection and von Mises stress are denoted, analyzed, and compared based on the change in the probe shapes for the same applied force. The results obtained from the two finite element tools were similar, converged to the same ideal design, and showed the impact of the probe structure on the probe performance.

Quaternary uranium mineralization in the Qaidam Basin, northern Tibetan Plateau: Insights from petrographic and C-O isotopic evidences

There are several sandstone-type uraniferous basins around Tibetan Plateau. The Qaidam Basin is the largest sedimentary basin in the internal Tibetan Plateau, hosting important oil and coal resources, and has good potential for sandstone-hosted uranium resources. In this study, we examine the petrographic and mineralogical characteristics of a uranium mineralization interval at the Neogene-Quaternary transition (NQT) in the western Qaidam Basin using optical microscopy and electron probe microanalyzer (EPMA), including back scattered electron (BSE) imaging and energy-dispersive spectroscopy (EDS). The sedimentary lithofacies features and C-O stable isotopes of carbonate cement from two boreholes were analyzed, especially for the uraniferous interval. Whole-rock analyses of ores and barren rocks yielded highly variable U concentrations ranging from 1.5 to 2548 ppm. The main uranium minerals are coffinite and uraninite. The co-occurrence of uranium minerals with calcite indicates that uranium mineralization and calcite cementation were coeval. Coffinite mainly occurs at the interface between calcite cement and other minerals. The carbonates have δ13CV-PDB ranging from −29.67 to +3.93‰, suggesting involvement of organic carbon during uranium mineralization. This is also supported by the general trend of decreasing δ13CV-PDB and increasing U content from the conglomerate/coarse sandstone to the mudstone samples, and the overlap of δ13CV-PDB values between the calcite cement and organic matter in sedimentary rocks. The organic carbon may have been derived from hydrocarbons sourced from the deeper part of the basin and/or biogenic gases at shallow depths. The unconformity at the NQT may represent a favorable interval where oxidizing fluids carrying uranium met with reducing fluids carrying hydrocarbons and resulted in uranium mineralization. Thus, the NQT may serve as a guide for uranium exploration in this basin.

Far-Infrared Near-Field Optical Imaging and Kelvin Probe Force Microscopy of Laser-Crystallized and -Amorphized Phase Change Material Ge3Sb2Te6.

Chalcogenide phase change materials reversibly switch between non-volatile states with vastly different optical properties, enabling novel active nanophotonic devices. However, a fundamental understanding of their laser-switching behavior is lacking and the resulting local optical properties are unclear at the nanoscale. Here, we combine infrared scattering-type scanning near-field optical microscopy (SNOM) and Kelvin probe force microscopy (KPFM) to investigate four states of laser-switched Ge3Sb2Te6 (as-deposited amorphous, crystallized, reamorphized, and recrystallized) with nanometer lateral resolution. We find SNOM to be especially sensitive to differences between crystalline and amorphous states, while KPFM has higher sensitivity to changes introduced by melt-quenching. Using illumination from a free-electron laser, we use the higher sensitivity to free charge carriers of far-infrared (THz) SNOM compared to mid-infrared SNOM and find evidence that the local conductivity of crystalline states depends on the switching process. This insight into the local switching of optical properties is essential for developing active nanophotonic devices.

In-situ and ex-situ comparison of oxidation of Inconel 718 manufactured by selective laser melting and conventional methods up to 650 °C

This work reveals the initial stages of Inconel 718 (IN718) oxidation manufactured by selective laser melting (SLM). In-situ and ex-situ investigations were conducted on SLM-IN718 and a commercially obtained Inconel 718 sample (Comm-IN718) to compare their oxidation behavior. In-situ and ex-situ testing was performed using a unique synchronized system integrating precise thermal control with Raman spectroscopy, optical microscopy and scanning probe techniques. X-Ray diffractometry (XRD) and Scanning Electron Microscopy (SEM) were used for microstructure analyses before and after heating. Raman spectroscopy indicated that, in both samples, there is a threshold temperature for oxidation at around 300 °C. The highest rate of oxidation was observed up to 550 °C as different oxides form. After 550 °C, there was no noticeable formation of new compounds up to 650 °C. Extended heating at 650 °C resulted in further changes in the Comm-IN718 sample, however the SLM-IN718 sample was unchanged by longer heating times. XRD of cooled samples did not detect any oxides because of the structurally disordered nature of the oxides. After being cooled, Comm-IN718 showed undesirable oxides like iron oxides in an inhomogeneous crystalline oxide layer. For SLM-IN718 the continuous unbroken oxide layer on the cooled SLM-IN718 sample imparted more effective protection of the alloy.

Quantification of electron accumulation at grain boundaries in perovskite polycrystalline films by correlative infrared-spectroscopic nanoimaging and Kelvin probe force microscopy

Organic–inorganic halide perovskites are emerging materials for photovoltaic applications with certified power conversion efficiencies (PCEs) over 25%. Generally, the microstructures of the perovskite materials are critical to the performances of PCEs. However, the role of the nanometer-sized grain boundaries (GBs) that universally existing in polycrystalline perovskite films could be benign or detrimental to solar cell performance, still remains controversial. Thus, nanometer-resolved quantification of charge carrier distribution to elucidate the role of GBs is highly desirable. Here, we employ correlative infrared-spectroscopic nanoimaging by the scattering-type scanning near-field optical microscopy with 20 nm spatial resolution and Kelvin probe force microscopy to quantify the density of electrons accumulated at the GBs in perovskite polycrystalline thin films. It is found that the electron accumulations are enhanced at the GBs and the electron density is increased from 6 × 1019 cm−3 in the dark to 8 × 1019 cm−3 under 10 min illumination with 532 nm light. Our results reveal that the electron accumulations are enhanced at the GBs especially under light illumination, featuring downward band bending toward the GBs, which would assist in electron-hole separation and thus be benign to the solar cell performance.Correlative infrared-spectroscopic nanoimaging by the scattering-type scanning near-field optical microscopy and Kelvin probe force microscopy quantitatively reveal the accumulated electrons at GBs in perovskite polycrystalline thin films.

Design of Phase‐Change Memory Using Apertureless Scanning Near‐Field Optical Microscopy in the Near‐Infrared Region

A novel optical secondary storage memory operated in the near‐infrared (NIR) region is developed through the integration of an apertureless scanning near‐field optical microscopy probe with the conventional Ge2Sb2Te5 storage stack. The probe composite and the optical coefficients of the storage media stack, particularly for the indium tin oxide capping layer, are optimized according to a previously developed electromagnetic wave model, and a newly established density functional theory model, respectively. The dielectric core and the metal coating medium of the probe are devised to be glass and barium, respectively, to provide high electric field in the NIR region, while the thickness of the ITO capping layer is chosen to be 3 nm here to provide high optical transmittance simultaneously with exemption of complex fabrication process. The recording operation of the aforementioned optimized device is subsequently simulated by a newly established thermo‐optics model, and its feasibility of achieving ≥Tbit in−2, 108 bits per second, and picojoule energy consumption per bit is theoretically demonstrated.

How the Ligand Field in Lanthanide Coordination Complexes Determines Magnetic Susceptibility Anisotropy, Paramagnetic NMR Shift, and Relaxation Behavior.

ConspectusComplexes of lanthanide(III) ions are being actively studied because of their unique ground and excited state properties and the associated optical and magnetic behavior. In particular, they are used as emissive probes in optical spectroscopy and microscopy and as contrast agents in magnetic resonance imaging (MRI). However, the design of new complexes with specific optical and magnetic properties requires a thorough understanding of the correlation between molecular structure and electric and magnetic susceptibilities, as well as their anisotropies. The traditional Judd–Ofelt–Mason theory has failed to offer useful guidelines for systematic design of emissive lanthanide optical probes. Similarly, Bleaney’s theory of magnetic anisotropy and its modifications fail to provide accurate detail that permits new paramagnetic shift reagents to be designed rather than discovered.A key determinant of optical and magnetic behavior in f-element compounds is the ligand field, often considered as an electrostatic field at the lanthanide created by the ligands. The resulting energy level splitting is a sensitive function of several factors: the nature and polarizability of the whole ligand and its donor atoms; the geometric details of the coordination polyhedron; the presence and extent of solvent interactions; specific hydrogen bonding effects on donor atoms and the degree of supramolecular order in the system. The relative importance of these factors can vary widely for different lanthanide ions and ligands. For nuclear magnetic properties, it is both the ligand field splitting and the magnetic susceptibility tensor, notably its anisotropy, that determine paramagnetic shifts and nuclear relaxation enhancement.We review the factors that control the ligand field in lanthanide complexes and link these to aspects of their utility in magnetic resonance and optical emission spectroscopy and imaging. We examine recent progress in this area particularly in the theory of paramagnetic chemical shift and relaxation enhancement, where some long-neglected effects of zero-field splitting, magnetic susceptibility anisotropy, and spatial distribution of lanthanide tags have been accommodated in an elegant way.

Shaping 800 nm pulses of Yb/Tm co-doped laser: A control theoretic approach

Modern literature has demonstrated the use of fluorescent probes in optical microscopy. Most recently, Ytterbium (Yb3+) and Thulium (Tm3+) doped nanocrystals have been used to achieve the imaging of single upconversion nanoparticles in the Stimulated Emission Depletion (STED) microscope. However, precise control of the stimulated emission at 800 nm caused by the discharge of the metastable 3H4 energy level of the Tm3+ acceptor probe would provide enhanced imaging in modern microscopy by suppressing visible fluorescence emitted from the focal plane. In this interdisciplinary paper, Model-Free Control is combined with Sliding Control to shape 800 nm pulsed emission of the lanthanide co-doped dual-laser system. This is achieved by controlling the stimulated emission rate via automatic adjustment of the probing laser pump power. This new type of controller will not be impacted by model errors like its model-based counterparts and can be fabricated by complementary metal oxide semiconductor (CMOS) processes paving way to photonic integration. Numerical simulation of the controller is executed and shows that the error between desired pulsed emission and the system's output was below 0.0057%. Mathematical analysis of the control technique and the results obtained from numerical simulations are presented.

New Insights into the Mineralogy and Geochemistry of Sb Ores from Greece

Antimony is a common metalloid occurring in the form of Sb-sulfides and sulfosalts, in various base and noble metal deposits. It is also present in corresponding metallurgical products (concentrates) and, although antimony has been considered a penalty element in the past, recently it has gained interest due to its classification as a critical raw material (CRM) by the European Union (EU). In the frame of the present paper, representative ore samples from the main Sb-bearing deposits of Greece (Kilkis prefecture, Chalkidiki prefecture (Kassandra Mines), and Chios Isl.) have been investigated. According to optical microscopy and electron probe microanalysis (EPMA) data, the Greek ores contain stibnite (Sb2S3), boulangerite (Pb5Sb4S11), bournonite (PbCuSbS3), bertherite (FeSbS4), and valentinite (Sb2O3). Bulk analyses by inductively coupled plasma mass spectrometry (ICP-MS) confirmed, for the first time published, the presence of a significant Hg content in the Kilkis Sb-ore. Furthermore, Kassandra Mines ores are found to contain remarkable amounts of Bi, As, Sn, Tl, and Se (excluding Ag, which is a bonus element). The above findings could contribute to potential future exploration and exploitation of Sb ores in Greece.

Mineralogy and geochemistry of the coal seam of Shanxi Formation in Guotun Mine, Juye Coalfield, North China

This work investigated the mineralogy and geochemistry of the No. 3 coal seam in Permian Shanxi Formation in Guotun Mine, Juye Coalfield, north China, in order to understand the genesis of the minerals and the enrichment of trace elements. Approaches used were optical microscopy and electron probe microanalysis for minerals, X-ray fluorescence analysis for major elements and inductively coupled plasma mass spectrometry analysis for trace elements. The coal is comprised of dominant kaolinite and calcite, the claystone is characteristic of major kaolinite, montmorillonite, and proportional illite, and the sandstone contains mainly quartz and chalcedony, and a relative amount of feldspar and kaolinite. These minerals were derived dominantly from the weathered source rocks with volcanic and granitic constituents in the pre-diagenetic period, and minor from the hydrothermal deposit in the epigenetic period. The claystone is relatively enriched in Li, Cs, Be, Nb, Mo, U, Th, V, In, Pb, Bi, and Se, which may probably be controlled by the source rocks and the specific sedimentary environment. The enriched trace elements are mostly associated with minerals. Li may probably occur in montmorillonite and illite, while In, Pb, Bi, and Se occur mainly in selenio-galena.

Corrosion Assessment of ASME Qualified Welding Procedures for Grade 2101 Lean Duplex Stainless Steel

ASME qualified welding procedures do not guarantee suitable corrosion and passivation properties for lean duplex stainless steel welds. An evaluation of two ASME qualified welding procedures to optimize the corrosion performance of tungsten inert gas (TIG) welded grade 2101 duplex stainless steel using ER2209 weld consumable was conducted. The evolution of the microstructure was examined by optical and electron microscopy, ferrite-scope measurements, and scanning Kelvin probe force microscopy. An electrochemical mini-cell was then used to characterize the electrochemical behavior of different weld regions using the techniques such as the double loop electrochemical potentiokinetic reactivation test, standard potentiodynamic polarization tests, and cyclic potentiodynamic polarization. The fusion line was the most critical zone for localized corrosion for both welding procedures, due to the formation of Cr- and Mo-depleted zones, resulting in the highest degree of sensitization. The best performance was attributed to the weld face, due to the presence of higher Cr and Mo contents, highlighting the pitting corrosion resistance. A heat input range of 1.6 kJ/mm to 1.9 kJ/mm and low current density (WPS 1) indicated better corrosion performance of all weld regions. The electrochemical corrosion response was in all cases related to microstructural characteristics of the weld regions. The influence of weld parameters on microstructure development and corrosion performance is discussed.