• Bulletin of the Korean Chemical Society
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• 제31권1호
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• pp.92-99
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• 2010

Photoexcitation of a precursor ion inside a cell floated at high voltage installed in a tandem time-of-flight (TOF) mass spectrometer provides triple tandem mass spectrometric information and allows kinetic and mechanistic studies. In this work, the factors affecting, or downgrading, the performance of the technique were identified. Ion-optical and computational analyses showed that an optimum instrument could be designed by utilizing a reflectron with linear-plus-quadratic potential inside. Theoretical predictions were confirmed by tests with instruments built with different ion-optical layout. With optimized instruments, masses of intermediate ions in the consecutive dissociation of a precursor ion could be determined with the maximum error of $\pm5$ Da. We also observed excellent agreement in dynamical parameters (critical energy and entropy) for the dissociation of a model peptide ion determined by instruments with different ion-optical layout operated under optimum conditions. This suggests that these parameters can be determined reliably by the kinetic method developed previously when properly designed and operated tandem TOF instruments are used.

• 대한화학회지
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• 제10권3호
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• pp.114-118
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• 1966

The glass electrode was empirically calibrated in dioxane-and ethanol-water mixed solvents, by means of which the pH-meter reading could be converted to stoichiometric hydrogen ion concentration. By the potentiometric titration method, the thermodynamic dissociation constants of hydrogen cupferrate (HCup) with variations of ionic concentration in aqueous solution were determined, and by the extrapolation of the constants the new thermodynamic $pK_a$ value, 3.980${\pm}$0.006, at zero ional concentration was obtained. The thermodynamic dissociation constants of HCup in dioxane-and ethanol-water solution were also potentiometrically determined with the changes in composition of organic solvents at 0.01 and 0.05 of the ionic strength(${mu}$) and 25 $^{\circ}C$. The empirical formula of the constants with mole fraction(n) of the organic solvent are as follow: Dioxane-water solution. $pK_a$= 12.96n + 4.10 at ${\mu}$ = 0.01, n = 0.0228∼0.171 $pK_a$= 12.05n + 4.23 at ${\mu}$ = 0.05, n= 0.0228∼0.171 Ethanol-water solution, $pK_a$= 4.0ln + 4.26 at ${\mu}$= 0.01, n= 0.0395∼0.262 $pK_a$= 3.83n + 4.34 at ${\mu}$= 0.05, n= 0.0395∼0.262

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1401-1406
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• 2013

This study tested the feasibility of observing H/D exchange of intact protein by top-down electron capture dissociation (ECD) mass spectrometry for the investigation of protein structure. Ubiquitin is selected as a model system. Local structural information was obtained from the deuteration levels of c and $z^{\cdot}$ ions generated from ECD. Our results showed that ${\alpha}$-helix region has the lowest deuteration level and the C-terminal fraction containing a highly mobile tail has the highest deuteration level, which correlates well with previous X-Ray and HDX/NMR analyses. We studied site-specific H/D exchange kinetics by monitoring H/D exchange rate of several structural motives of ubiquitin. Two hydrogen bonded ${\beta}$-strands showed similar HDX rates. However, the outer ${\beta}$-strand always has higher deuteration level than the inner ${\beta}$-strand. The HDX rate of the turn structure (residues 8-11) is lower than that of ${\beta}$-strands (residues 1-7 and residues 12-17) it connects. Although isotopic distribution gets broader after H/D exchange which results in a limited number of backbone cleavage sites detected, our results demonstrate that this method can provide valuable detailed structural information of proteins. This approach should also be suitable for the structural investigation of other unknown proteins, protein conformational changes, as well as protein-protein interactions and dynamics.

• 전기학회논문지
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• 제60권11호
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• pp.2097-2102
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• 2011

Discharge analysis technique for dielectric liquid was presented by using the Finite Element Analysis (FEA) under a lightning impulse incorporating two-phase flow phenomena which described gas and liquid phases in discharge space. Until now, the response of step voltage has been extensively explored, but that of lightning impulse voltage was rarely viewed in the literature. We, therefore, developed an analyzing technique for dielectric liquid in a tip-sphere electrode stressed by a high electric field. To capture the bubble phase, the Heaviside function was introduced mathematically and the material functions for the ionization, dissociation, recombination, and attachment were defined in liquid and bubble, respectively. By using this numerical setup, the molecular dissociation and ionization mechanisms were tested under low and high electric fields resulted from the lightning impulse voltage of 1.2/50 ${\mu}s$. To verify our numerical results, the velocity of electric field wave was measured and compared to the previous experimental results which can be viewed in many papers. Those results had good agreement with each other.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2000년도 제18회 학술발표회 논문개요집
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• pp.147-147
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• 2000

Chemisorption of oxygen molecules on the Si(111)-(7x7) surface has been studied extensively as a model for the initial-stage oxidation of the surface. The basic step to the surface oxidation is the dissociation of the adsorbed O2 molecules, but the dissociation procedure and the atomic structure of the reaction products still remains as a subject of debates. We present here density-functional theory calculations on the initial-stage oxidation states of the Si adatom site for all possible dissociation configurations that can be generated by multiple O2 reactions. We determine the equilibrium structures and analyze their electronic and vibrational properties in comparison with measured UPS, XPS, and EELS spectra. The O(ad) atom bonded on top of the Si adatom is always less stable than the O(ins) atom inserted into one of the adatom backbonds. Our electronic and vibrational analysis demonstrates further that the O(ad) and O(ins) atoms account well for the metastable and stable features in previous experiments, respectively. Moreover, the calculated decay pathways of the metastable structures and the comparison of the calculated O ls core-level shifts with XPS data provides a convincing argument in unambiguously identifying the experimental metastable and stable structures, thereby making it possible to build a correct atomic-scale picture of the initial-stage oxidation process on this surface.

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.593-595
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• 1992

To improve the lifetime and output power in a sealed-off $CO_2$ laser, a series of Nd$_{1-x}$Sr$_x$CoO$_3$(x = 0.0, 0.25, 0.40, 0.50, 0.60, 0.75) perovskite-type compounds has been synthesized and used for a cathode material. Using a typical method samples were sintered at 1150$^{\circ}$C and their structures were determined as a cubic form by means of XRD analysis. The degrees of $CO_2$ dissociation were measured by PAS (photoacoustic spectroscopy) with the lapse of time. In the case of $Nd_{0.4}$Sr$_{0.6}$$CoO_3$, which showed the highest catalytic cathode effect, only 7% of the initial $CO_2$ concentration were dissociated at 30 torr of gas mixture and 5 mA of discharge current. The more the gas pressure decreased and the discharge current increased, the more the degree of dissociation occurred. The ability of catalytic cathode to regenerate CO$_2$ in the laser cavity lies in order for x, 0.60 > 0.50 > 0.40 > 0.75 > 0.25 ${\gg}$ 0.0. Except for the case of x = 0.0 the amounts of $CO_2$ dissociation were found to be within 7-15% of the initial $CO_2$ concentration.

• Mass Spectrometry Letters
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• 제12권4호
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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.

• Mass Spectrometry Letters
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• 제9권4호
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• pp.91-94
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• 2018

Bilin tetrapyrroles are metabolic products of the breakdown of porphyrins within a species. In the case of mammals, these bilins are formed by the catabolism of heme and can be utilized as either biomarkers in disease or as an indicator of human waste contamination. Although a small subset of bilin tandem mass spectrometry reports exist, limited data is available in online databases for their fragmentation. The use of fragmentation data is important for metabolomics analyses to determine the identity of compounds detected within a sample. Therefore, in this study, the fragmentation of bilins generated by positive ion mode electrospray ionization is examined by collision-induced dissociation (CID) as a function of collision energy on an FT-ICR MS. The use of the FT-ICR MS allows for high mass accuracy measurements, and thus the formulas of resultant product ions can be ascertained. Based on our observations, fragmentation behavior for hemin, biliverdin and its dimethyl ester, phycocyanobilin, bilirubin, bilirubin conjugate, mesobilirubin, urobilin, and stercobilin are discussed in the context of the molecular structure and collision energy. This report provides insight into the identification of structures within this class of molecules for untargeted analyses.

• Mass Spectrometry Letters
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• 제12권2호
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• pp.41-46
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• 2021

Collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) are the widely used fragmentation technique in mass spectrometry-based proteomics studies. Understanding the fragmentation pattern from the tandem mass spectra using statistical methods helps to implement efficient spectrum analysis algorithms. The study characterizes the frequency of occurrence of multi-charged fragment ions and their neutral loss events of doubly and triply charged peptides in the CID and HCD spectrum. The dependency of the length of the fragment ion on the occurrence of multi-charged fragment ion is characterized here. Study shows that the singly charged fragment ions are generally dominated in the doubly charged peptide spectrum. However, as the length of the product ion increases, the frequency of occurrence of charge 2 fragment ions increases. The y- ions have more tendencies to generate charge 2 fragment ions than b- ions, both in CID and HCD spectrum. The frequency of occurrence of charge 2 fragment ion peaks is prominent upon the dissociation of the triply charged peptides. For triply charged peptides, product ion of higher length occurred in multiple charge states in CID spectrum. The neutral loss peaks mostly exist in charge 2 states in the triply charged peptide spectrum. The b-ions peaks are observed in much less frequency than y-ions in HCD spectrum as the length of the fragment increases. Isotopic peaks are occurred in charge 2 state both in doubly and triply charged peptide's HCD spectrum.

• 마케팅과학연구
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• 제17권4호
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• pp.201-221
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• 2007

인터넷 쇼핑에 있어 가격은 제품에 대한 정보단서로서 중요해지고 있으며 가격에 대한 의존성 역시 점차 높아지고 있다. 본 연구는 이러한 가격민감도와 플로우에 관한 문헌고찰을 토대로 인터넷 쇼핑에서 소비자들이 경험하는 플로우가 재방문의도에 중요한 역할을 하고 있지만, 인터넷 쇼핑 행동의 또 다른 특성인 가격민감도는 오히려 플로우를 감소시킬 가능성이 있음을 제안한다. 인터넷 쇼핑에서의 가격민감도, 플로우, 재방문의도의 관계 검증과 함께 쇼핑몰의 유형에 따른 차이도 살펴본다. 연구결과, 인터넷 쇼핑몰에서의 플로우 경험은 재방문의도를 높이지만, 가격민감도 차원 중 가격탐색차원은 플로우의 각 차원에 부정적인 영향을 미치고 있는 것으로 나타났으며, 또한 이러한 영향은 가격비교쇼핑몰, 경매쇼핑몰, 종합쇼핑몰에 따라 다른 결과를 보이고 있다.