• Title/Summary/Keyword: in situ spectroscopy

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Looking through the Mass-to-Charge Ratio: Past, Present and Future Perspectives

  • Shin, Seung Koo
    • Mass Spectrometry Letters
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    • v.12 no.4
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    • pp.126-130
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    • 2021
  • The mass spectrometry (MS) provides the mass-to-charge ratios of atoms, molecules, stable/metastable complexes, and their fragments. I have taken a long journey with MS to address outstanding issues and problems by experiments and theory and gain insights into underlying principles in chemistry. By looking through the mass-to-charge ratio, I have studied thermochemical problems in silicon chemistry, the infrared multiphoton dissociation spectroscopy of organometallic intermediates, unimolecular dissociations of halotoluene radical cations, and the kinetics of association/dissociation of alkali halide triple ions with Lewis bases. Various MS platforms have been used to characterize non-covalent interactions between porphyrins and fullerenes and those between the group IIB ions and trioctylchalcogenides, and to examine the binding of the group IA, IIA and porphyrin ions to G-quadruplex DNA. Recently, I have focused on mass-balanced H/D isotope dipeptide tags for MS-based quantitative proteomics, a simple chemical modification method for MS-based lipase assay, and the kinetics and dynamics of energy-variable collision-induced dissociation of chemically modified peptides. Now, I see an important role of MS in global issues in the post-COVID era, as the society demands high standards for indoor air quality to contain the airborne-pathogen transmission as well as in-situ monitoring and tracking of carbon emissions to reduce global warming.

In-situ electron beam growth of $YBa_2Cu_3O_{7-x}$ coated conductors on metal substrates

  • Jo, W.;Ohnishi, T.;Huh, J.;Hammond, R.H.;Beasley, M.R.
    • Progress in Superconductivity
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    • v.8 no.2
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    • pp.175-180
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    • 2007
  • High temperature superconductor $YBa_2Cu_3O_{7-x}$ (YBCO) films have been grown by in-situ electron beam evaporation on artificial metal tapes such as ion-beam assisted deposition (IBAD) and rolling assisted biaxially textured substrates (RABiTS). Deposition rate of the YBCO films is $10{\sim}100{\AA}/sec$. X-ray diffraction shows that the films are grown epitaxially but have inter-diffusion phases, like as $BaZrO_3\;or\;BaCeO_3$, at their interfaces between YBCO and yttrium-stabilized zirconia (YSZ) or $CeO_2$, respectively. Secondary ion mass spectroscopy depth profile of the films confirms diffused region between YBCO and the buffer layers, indicating that the growth temperature ($850{\sim}900^{\circ}C$) is high enough to cause diffusion of Zr and Ba. The films on both the substrates show four-fold symmetry of in-plane alignment but their width in the -scan is around $12{\sim}15^{\circ}$. Transmission electron microscopy shows an interesting interface layer of epitaxial CuO between YBCO and YSZ, of which growth origin may be related to liquid flukes of Ba-Cu-O. Resistivity vs temperature curves of the films on both substrates were measured. Resistivity at room temperature is between 300 and 500 cm, the extrapolated value of resistivity at 0 K is nearly zero, and superconducting transition temperature is $85{\sim}90K$. However, critical current density of the films is very low, ${\sim}10^3A/cm^2$. Cracking of the grains and high-growth-temperature induced reaction between YBCO and buffer layers are possible reasons for this low critical current density.

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Maximizing TPBs through Ni-self-exsolution on GDC based composite anode in solid oxide fuel cells

  • Tan, Je-Wan;Lee, Dae-Hui;Kim, Bo-Gyeong;Kim, Ju-Seon;Mun, Ju-Ho
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.402.1-402.1
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    • 2016
  • The performance of solid oxide fuel cells (SOFCs) is directly related to the electrocatalytic activity of composite electrodes in which triple phase boundaries (TPBs) of metallic catalyst, oxygen ion conducting support, and gas should be three-dimensionally maximized. The distribution morphology of catalytic nanoparticle dispersed on external surfaces is of key importance for maximized TPBs. Herein in situ grown nickel nanoparticle onto the surface of fluorite oxide is demonstrated employing gadolium-nickel co-doped ceria ($Gd0.2-xNixCe0.8O2-{\delta}$, GNDC) by reductive annealing. GNDC powders were synthesized via a Pechini-type sol-gel process while maximum doping ratio of Ni into the cerium oxide was defined by X-ray diffraction. Subsequently, NiO-GNDC composite were screen printed on the both sides of yttrium-stabilized zirconia (YSZ) pellet to fabricate the symmetrical half cells. Electrochemical impedance spectroscopy (EIS) showed that the polarization resistance was decreased when it was compared to conventional Ni-GDC anode and this effect became greater at lower temperature. Ex situ microstructural analysis using scanning electron microscopy after the reductive annealing exhibited the exsolution of Ni nanoparticles on the fluorite phases. The influence of Ni contents in GNDC on polarization characteristics of anodes were examined by EIS under H2/H2O atmosphere. Finally, the addition of optimized GNDC into the anode functional layer (AFL) dramatically enhanced cell performance of anode-supported coin cells.

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Hydrogen-bonded clusters in transformed Lewis acid to new Brønsted acid over WOx/SiO2 catalyst

  • Boonpai, Sirawat;Wannakao, Sippakorn;Panpranot, Joongjai;Praserthdam, Supareak;Chirawatkul, Prae;Praserthdam, Piyasan
    • Advances in nano research
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    • v.12 no.3
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    • pp.291-300
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    • 2022
  • The behavior of hydrogen species on the surface of the catalyst during the Lewis acid transformation to form Brønsted acid sites over the spherical silica-supported WOx catalyst was investigated. To understand the structure-activity relationship of Lewis acid transformation and hydrogen bonding interactions, we explore the potential of using the in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) with adsorbed ammonia and hydrogen exposure. From the results of in situ DRIFTS measurements, Lewis acid sites on surface catalysts were transformed into new Brønsted acid sites upon hydrogen exposure. The adsorbed NH3 on Lewis acid sites migrated to Brønsted acid sites forming NH4+. The results show that the dissociated H atoms present on the catalyst surface formed new Si-OH hydroxyl species - the new Brønsted acid site. Besides, the isolated Si-O-W species is the key towards H-bond and Si-OH formation. Additionally, the H atoms adsorbed surrounding the Si-O-W species of mono-oxo O=WO4 and di-oxo (O=)2WO2 species, where the Si-O-W species are the main species presented on the Inc-SSP catalysts than that of the IWI-SSP catalysts.

Surface Coating and Electrochemical Properties of LiNi0.8Co0.15Al0.05O2 Polyaniline Composites as an Electrode for Li-ion Batteries

  • Chung, Young-Min;Ryu, Kwang-Sun
    • Bulletin of the Korean Chemical Society
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    • v.30 no.8
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    • pp.1733-1737
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    • 2009
  • A new cathode material based on Li$Ni_{0.8}Co_{0.15}Al_{0.05}O_2$ (LNCA)/polyaniline (Pani) composite was prepared by in situ self-stabilized dispersion polymerization in the presence of LNCA. The materials were characterized by fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-Vis), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Electrochemical properties including galvanostatic charge-discharge ability, cyclic voltammetry (CV), capacity, cycling performance, and AC impedance were measured. The synthesized LNCA/Pani had a similar particle size to LNCA and exhibited good electrochemical properties at a high C rate. Pani (the emeraldine salt form) interacts with metal-oxide particles to generate good connectivity. This material shows good reversibility for Li insertion in discharge cycles when used as the electrode of lithium ion batteries. Therefore, the Pani coating is beneficial for stabilizing the structure and reducing the resistance of the LNCA. In particular, the LNCA/Pani material has advantageous electrochemical properties.

Low temperature wet-chemical synthesis of spherical hydroxyapatite nanoparticles and their in situ cytotoxicity study

  • Mondal, Sudip;Dey, Apurba;Pal, Umapada
    • Advances in nano research
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    • v.4 no.4
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    • pp.295-307
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    • 2016
  • The present research work reports a low temperature ($40^{\circ}C$) chemical precipitation technique for synthesizing hydroxyapatite (HAp) nanoparticles of spherical morphology through a simple reaction of calcium nitrate tetrahydrate and di-ammonium hydrogen phosphate at pH 11. The crystallinity of the single-phase nanoparticles could be improved by calcinating at $600^{\circ}C$ in air. Thermogravimetric and differential thermal analysis (TG-DTA) revealed the synthesized HAp is stable up to $1200^{\circ}C$. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) studies confirmed the formation of spherical nanoparticles with average size of $23.15{\pm}2.56nm$ and Ca/P ratio of 1.70. Brunauer-Emmett-Teller (BET) isotherm of the nanoparticles revealed their porous structure with average pore size of about 24.47 nm and average surface area of $78.4m2g^{-1}$. Fourier transform infrared spectroscopy (FTIR) was used to confirm the formation of P-O, OH, C-O chemical bonds. Cytotoxicity and MTT assay on MG63 osteogenic cell lines revealed nontoxic bioactive nature of the synthesized HAp nanoparticles.

Mono-layer Compositional Analysis of Surface of Mineral Grains by Time-of-Flight Secondary-Ion Mass Spectrometry (TOF-SIMS) (TOF-SIMS를 이용한 광물 표면의 단층조직 분석 연구)

  • Kong Bong Sung;Chryssoulis Stephen;Kim Joo Young
    • Journal of the Mineralogical Society of Korea
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    • v.18 no.2
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    • pp.127-134
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    • 2005
  • Although the bulk composition of materials is one of the major considerations in extractive metallurgy and environmental science, surface composition and topography control surface reactivity, and consequently play a major role in determining metallurgical phenomena and pollution by heavy metals and organics. An understanding of interaction mechanisms of different chemical species at the mineral surface in an aqueous media is very important in natural environment and metallurgical processing. X-ray photoelectron spectroscopy (XPS) has been used as an ex-situ analytical technique, but the material to be analyzed can be any size from $100\;{\mu}m$ up to about 1 cm. It can also measure mixed solids powders, but it is impossible to ascertain the original source of resulting x-ray signals where they were emitted from, since it radiates and scans the macro sample surface area. The study demonstrated the ability of TOF-SIMS to detect individual organic species on the surfaces of mineral particles from plant samples and showed that the TOF-SIMS techniques provides an excellent tool for establishing the surface compositions of mineral grains and relative concentrations of chemicals on mineral species.

Transmission Electron Microscopy on Memristive Devices: An Overview

  • Strobel, Julian;Neelisetty, Krishna Kanth;Chakravadhanula, Venkata Sai Kiran;Kienle, Lorenz
    • Applied Microscopy
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    • v.46 no.4
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    • pp.206-216
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    • 2016
  • This communication is to elucidate the state-of-the-art of techniques necessary to gather information on a new class of nanoelectronic devices known as memristors and related resistive switching devices, respectively. Unlike classical microelectronic devices such as transistors, the chemical and structural variations occurring upon switching of memristive devices require cutting-edge electron microscopy techniques. Depending on the switching mechanism, some memristors call for the acquisition of atomically resolved structural data, while others rely on atomistic chemical phenomena requiring the application of advanced X-ray and electron spectroscopy to correlate the real structure with properties. Additionally, understanding resistive switching phenomena also necessitates the application not only of pre- and post-operation analysis, but also during the process of switching. This highly challenging in situ characterization also requires the aforementioned techniques while simultaneously applying an electrical bias. Through this review we aim to give an overview of the possibilities and challenges as well as an outlook onto future developments in the field of nanoscopic characterization of memristive devices.

Effects of Sputter Parameters on Electrochromic Properties of Tungsten Oxide Thin Films Grown by RF Sputtering

  • Nah, Yoon-Chae
    • Korean Journal of Materials Research
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    • v.21 no.12
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    • pp.703-707
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    • 2011
  • The electrochromic properties of tungsten oxide films grown by RF sputtering were investigated. Among the sputter parameters, first the $Ar:O_2$ ratios were controlled with division into only an $O_2$ environment, 1:1 and 4:1. The structure of each film prepared by these conditions was studied by X-ray diffraction, X-ray photoelectron spectroscopy and Rutherford backscattering spectroscopy. The sputter-deposited tungsten oxide films had an amorphous structure regardless of the $Ar:O_2$ ratios. The chemical compositions, however, were different from each other. The stoichiometric structure and low-density film was obtained at higher $O_2$ contents. Electrochemical tests were performed by cyclic voltammetry and chronoamperometry at 0.05 M $H_2SO_4$ solutions. The current density and charge ratio was estimated during the continuous potential and pulse potential cycling at -0.5 V and 1.8 V, respectively. The film grown in a higher oxygen environment had a higher current density and a reversible charge reaction during intercalation and deintercalation. The in-situ transmittance tests were performed by He-Ne laser (633 nm). At higher oxygen contents, a big transmittance difference was observed but the response speed was too slow. This was likely caused by higher film resistivity. Furthermore, the effect of sputtering pressure was also investigated. The structure and surface morphology of each film was observed by X-ray diffraction and scanning electron microscopy. A rough surface was observed at higher sputtering pressure, and this affected the higher transmittance difference and coloration efficiency.

In Vivo $^{13}C$-NMR Spectroscopic Study of Polyhydroxyalkanoic Acid Degradation Kinetics in Bacteria

  • Oh, Jung-Sook;Choi, Mun-Hwan;Yoon, Sung-Chul
    • Journal of Microbiology and Biotechnology
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    • v.15 no.6
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    • pp.1330-1336
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    • 2005
  • Polyhydroxyalkanoic acid (PHA) inclusion bodies were analyzed in situ by $^{13}C$-nuclear magnetic resonance ($^{13}C$-NMR) spectroscopy. The PHA inclusion bodies studied were composed of poly(3-hydroxybutyrate) or poly(3hydroxybutyrate-co-4-hydroxybutyrate), which was accumulated in Hydrogenophaga pseudoflava, and medium-chain-length PHA (MCL-PHA), which was accumulated in Pseudomonas fluorescens BM07 from octanoic acid or 11-phenoxyundecanoic acid (11-POU). The quantification of the $^{13}C$-NMR signals was conducted against a standard compound, sodium 2,2-dimethyl-2-silapentane-5-sulfonate (DSS). The chemical shift values for the in vivo NMR spectral peaks agreed well with those for the corresponding purified PHA polymers. The intracellular degradation of the PHA inclusions by intracellular PHA depolymerase(s) was monitored by in vivo NMR spectroscopy and analyzed in terms of first-order reaction kinetics. The H. pseudoflava cells were washed for the degradation experiment, transferred to a degradation medium without a carbon source, but containing 1.0 g/l ammonium sulfate, and cultivated at $35^{\circ}C$ for 72 h. The in vivo NMR spectra were obtained at $70^{\circ}C$ for the short-chain-length PHA cells whereas the spectra for the aliphatic and aromatic MCL-PHA cells were obtained at $50^{\circ}C\;and\;80^{\circ}C$, respectively. For the H. pseudoflava cells, the in vivo NMR kinetics analysis of the PHA degradation resulted in a first-order degradation rate constant of 0.075/h ($r^{2}$=0.94) for the initial 24 h of degradation, which was close to the 0.050/h determined when using a gas chromatographic analysis of chloroform extracts of sulfuric acid/methanol reaction mixtures of dried whole cells. Accordingly, it is suggested that in vivo $^{13}C$-NMR spectroscopy is an important tool for studying intracellular PHA degradation in terms of kinetics.