• 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.

• 분석과학
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• 제18권4호
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• pp.278-286
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• 2005

The crystal structure of ($Tl_{71}$-Y ($Tl_{71}Si_{121}Al_{71}O_{384}$), ${\alpha}=24.706(3){\AA}$, dehydrated at 653 K and $8{\times}10^{-6}$ torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group $Fd\bar{3}m$ at 294(1) K. The structure was refined using all intensities to the final error indices (using only the 302 reflection for which $F_{\circ}$ > $4{\sigma}(F_0)$) $R_1=0.0602$ (based on F) and $R_w=0.1744$ (based on $F_2$). The 71 $Tl^+$ ions per unit cell are found at four crystallographically distinct positions. Site I' position in the sodalite cavity opposite D6Rs are each occupied by eighteen $Tl^+$ ions per unit cell; these $Tl^+$ ions are recessed ca. $1.45{\AA}$ into the sodalite cavity from their O(3) plane (Tl-O=2.701(15), $3.163(16){\AA}$ and O-Tl-O=$92.1(4)^{\circ}$). The 23 $T1^+$ ions fill site II in the supercage; these $T1^+$ ions are recessed ca. $1.58{\AA}$ into the supercage from their O(2) plane (Tl-O = 2.850(16), $3.156(16){\AA}$ and O-T1-O = $85.1(5)^{\circ}$). The 19 $Tl^+$ ions lie at site III' in the supercage near a triple 4-ring (Tl-O = 3.10(7), $3.39(5){\AA}$ and O-Tl-O = 47.8(9), $95.3(18)^{\circ}$) and the remaining II ions occupy another site III' near a triple 4-ring in the supercage (Tl-O = 2.81(4), $2.71(4){\AA}$ and O-Tl-O = $57.3(8)^{\circ}$).

• 한국광물학회지
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• 제11권2호
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• pp.106-116
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• 1998

The adsorption of Cs-137 and Sr-90 onto kaolinite in prescence of major groundwater cations (Ca2+, K+, Na+) with different concentrations was simulated by using triple-layer surface complexation model (TL-SCM). The site density (8.73 sites/nm2) of kaolinite used for TL-SCM was calculated from it's CEC and specific surface area. TL-SCM modeling results indicate that concentrations dependence on 137Cs and 90Sr adsorption onto kaolinite as a function of pH is best modeled as an outer-sphere surface reaction. This suggests that Cs+ and Sr2+ are adsorbed at the $\beta$-layer in kaolinite-water interface where the electrolytes, Nacl, KCl and CaCl2, bind. However, TL-SCM results on Sr adsorption show a discrepancy between batch data and fitting data in alkaline condition. This may be due to precipitation of SrCO3 and complexation such as SrOH+. Intrinsic reaction constants of ions obtained from model fit are as follows: Kintcs=10-2.10, KintSr=10-2.30, KintK=10-2.80, KintCa=10-3.10 and KintNa=10-3.32. The results are in the agreement with competition order among groundwater ions (K+>Ca2+>Na+) and sorption reference of nuclides (Cs-137>Sr-90) at kaolinite-water interface showed in batch test.

• Mass Spectrometry Letters
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• 제12권4호
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• pp.152-158
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• 2021

Electrospray ionization (ESI) and ion mobility spectrometry-mass spectrometry (IMS-MS) were employed to investigate the solvated structures of ionic species in the lithium iodide electrolyte solution in the gas phase. The Li⁺I^-Li⁺ triple ion and single standalone Li+ ions solvated by 1,4-dioxane were successfully generated and observed by ESI-MS under the influence of dioxane vapor at the inlet region. Under the present experimental condition, (1,4-dioxane)_m·Li⁺ complex ions (m = 1, 2, and 3) and a (1,4-dioxane)·Li⁺I^-Li⁺ complex ion were observed, which were further examined by IMS to investigate their structures. The presence of multiple structural isomers was confirmed, which accounts for the endothermic conformational transition of 1,4-dioxane from a chair to a boat to achieve bidentate O-donor binding to Li⁺ and Li⁺I^-Li⁺. Further structural details critical for the ion-solvent interactions were also examined and discussed with the help of density functional theory calculations.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.2031-2035
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• 2010

A triple-probe channel type chemosensor based on an $NO_2S_2$-macrocycle functionalized with phenyltricyanovinyl group was synthesized and its sensing characteristics were examined. The pink-red solution of L changed selectively to pale yellow upon addition of $Hg^{2+}$. The selective fluorometric response of L to all the tested metal ions was studied. The results showed that a large enhancement of the fluorescence of L was observed only in the case of $Hg^{2+}$. In addition, L showed large anodic shift (~ 0.3 V) for the addition of excess $Hg^{2+}$. Through above three observed results by the different techniques, we confirmed that the proposed chemosensor acts as the multiple-probe channel sensing material. The crystal structure of mercury(II) nitrate complexs of L which shows a 1-D polymer network with a formula $[Hg_2(L)_2(NO_3)_2({\mu}-NO_3)_2]_n$ was also reported.

• Bulletin of the Korean Chemical Society
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• 제21권8호
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• pp.823-827
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• 2000

Gas-Phase reactions of methyl and ethyl nitrites with anionic nucleophiles of SH-, F- and OH- are investigated theoretically at the MP2/6-311+G* level. The SN2 processes are all highly exothermic and proceed with a typ-icaI double-weIl reaction coordinate profile. The elimination reactions of methyl nitrite with SH- and F- are double-well energy surface processes,with stabilizedproduct complexes of NO-...H2S and NO-...HF, pro-ceeding by an E1 cb-like E2 mechanism. The $\beta-elimination$ of ethyl nitrite is an E2 type process. The $\alpha-elimi-nation$ reactions of methyl and ethyl nitrites with OH- have triple-well energy profiles of Elcb pathway with an $\alpha-carbanion$ intermediate which is stabilized bythe vicinal $nc\alpha-{\sigma}*o-N$ charge transfer interactions. CompIex-ation ofmethyl carbanion with HF seems to provide a stable intermediate within a triple-well energy profile of El cb channel in the reaction of F- with methyl nitrite.

• Biotechnology and Bioprocess Engineering:BBE
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• 제10권3호
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• pp.205-211
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• 2005

Water-soluble polyethyleneimine (PE) derivatives containing nucleic acid bases and hydrophilic amino acids such as homoserine (Hse) and serine were prepared by the activated ester method as nucleic acid models. From spectroscopic measurements, the polymers were found to interact with DNA accompanied by an induction of conformational change. Hypochromicity in UV spectra indicated that a stable polymer complex was formed between poly (A) with PEI­Hse-Ura by complementary hydrogen bonding with equimolar nucleic base units (adenine:uracil=1:1). The induced conformation of DNA by the interaction with the polymer containing uracil and homoserine (PEI-Hse-Ura) was concluded to be a super triple helical structure. The formation of the polymer complex, DNA: PEI-Hse-Ura, was found to be affected by the presence of metal ions such as $Ca^{2+}\;and\;Cu^{2+}$.

• 한국재료학회지
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• 제29권12호
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• pp.741-746
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• 2019

New triple tungstate phosphors NaPbLa(WO₄)₃:Yb³⁺/Ho³⁺ (x = Yb³⁺/Ho³⁺ = 7, 8, 9, 10) are successfully fabricated by microwave assisted sol-gel synthesis and their structural and frequency upconversion (UC) characteristics are investigated. The compounds crystallized in the tetragonal space group I4₁/a and the NaPbLa(WO₄)₃ host have unit cell parameters a = 5.3927(1) and c = 11.7961(3) Å, V = 343.05(2) ų, Z = 4. Under excitation at 980 nm, the phosphors have yellowish green emissions, which are derived from the intense ⁵S₂/⁵F₄→⁵I₈ transitions of Ho³⁺ ions in the green spectral range and strong ⁵F₅→⁵I₈ transitions in the red spectral range. The optimal Yb³⁺:Ho³⁺ ratio is revealed to be x = 9, which is attributed to the quenching effect of Ho³⁺ ions, as indicated by the composition dependence. The UC characteristics are evaluated in detail under consideration of the pump power dependence and Commission Internationale de L'Eclairage chromaticity. The spectroscopic features of Raman spectra are discussed in terms of the superposition of Ho³⁺ luminescence and vibrational lines. The possibility of controlling the spectral distribution of UC luminescence by the chemical content of tungstate hosts is demonstrated.

• Bulletin of the Korean Chemical Society
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• 제28권1호
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• pp.41-48
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• 2007

Large colorless single crystals of sodium zeolite X, stoichiometry |Na80 |[Si112Al80O384]-FAU, with diameters up to 200 μm and Si/Al = 1.41 have been synthesized from gels with the composition of 2.40SiO2 : 2.00NaAlO2 : 7.52NaOH : 454H2O : 5.00TEA. One of these, a colorless octahedron about 200 μm in cross-section has been treated with aqueous 0.1 M KNO3 for the preparation of K+-exchanged zeolite X. The crystal structure of |K80|[Si112Al80O384]-FAU per unit cell, a = 24.838(4) A, dehydrated at 673 K and 1 × 10-6 Torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd at 294 K. The structure was refined using all intensities to the final error indices (using only the 707 reflections for which Fo > 4σ (Fo)) R1 = 0.075 (based on F) and R2 = 0.236 (based on F2). About 80 K+ ions per unit cell are found at an unusually large number of crystallographically distinct positions, eight. Eleven K+ ions are at the centers of double 6-rings (D6Rs, site I; K-O = 2.492(6) A and O-K-O (octahedral) = 88.45(22)o and 91.55(22)o). Site-I' position (in the sodalite cavities opposite D6Rs) is occupied by five K+ ions per unit cell; these K+ ions are recessed 1.92 A into the sodalite cavities from their 3-oxygen planes (K-O = 2.820(19) A, and O-K-O = 78.6(6)o). Twety-three K+ ions are found at three nonequivalent site II (in the supercage) with occupancies of 5, 9, and 9 ions; these K+ ions are recessed 0.43 A, 0.75 A, and 1.55 A, respectively, into the supercage from the three oxygens to which it is bound (K-O = 2.36(13) A, 2.45(13) A, and 2.710(13) A, O-K-O = 116.5(20)o, 110.1(17)o, and 90.4(6)o, respectively). The remaining sixteen, thirteen, and twelve K+ ions occupy three sites III' near triple 4-rings in the supercage (K-O = 2.64(3) A, 2.94(3) A, 2.73(5) A, 2.96(6) A, 3.06(4) A, and 3.08(3) A).

• Bulletin of the Korean Chemical Society
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• 제30권11호
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• pp.2691-2696
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• 2009

Effects of representative group II and transition metal ions on the stability of the $poly(dA){\cdot}[poly(dT)]_2$ triplex were investigated by the van’t Hoff plot constructed from a thermal melting curve. The transition, $poly(dA){\cdot}[poly(dT)]_2\;{\rightarrow}\;poly(dA){\cdot}poly(dT)\;+\;poly(dT)$, was non-spontaneous with a positive Gibb’s free energy, endothermic (${\Delta}H^{\circ}$ > 0), and had a favorable entropy change (${\Delta}S^{\circ}$ > 0), as seen from the negative slope and positive y-intercept in the van’t Hoff plot. Therefore, the transition is driven by entropy change. The $Mg^{2+}$ ion was the most effective at stabilization of the triplex, with the effect decreasing in the order of $Mg^{2+}\;>\;Ca^{2+}\;>\;Sr^{2+}\;>\;Ba^{2+}$. A similar stabilization effect was found for the duplex to single strand transition: $poly(dA){\cdot}poly(dT)\;+\;poly(dT)\;→\;poly(dA)\;+\;2poly(dT)$, with a larger positive free energy. The transition metal ions, namely $Ni_{2+},\;Cu_{2+},\;and\;Zn_{2+}$, did not exhibit any effect on triplex stabilization, while showing little effect on duplex stabilization. The different effects on triplex stabilization between group II metal ions and the transition metal ions may be attributed to their difference in binding to DNA; transition metals are known to coordinate with DNA components, including phosphate groups, while group II metal ions conceivably bind DNA via electrostatic interactions. The $Cd_{2+}$ ion was an exception, effectively stabilizing the triplex and melting temperature of the third strand dissociation was higher than that observed in the presence of $Mg_{2+}$, even though it is in the same group with $Zn_{2+}$. The detailed behavior of the $Cd_{2+}$ ion is currently under investigation.