• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.987-992
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• 2012

Magnetic nanoparticles (MNPs) treated with phosphoric acid were used to improve sequence coverage in protein identification by matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). Sample solution of tryptic peptides from proteins was mixed with the MNPs, and the MNPs were separated from the supernatant using a magnet. MALDI mass spectra obtained separately from the supernatant and the MNPs were distinctly different and complementary to each other. Combination of the two spectra led to a significantly increased sequence coverage.

• Bulletin of the Korean Chemical Society
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• 제23권2호
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• pp.315-319
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• 2002

Visible surface-assisted desorption/ionization mass spectrometry (SALDI-MS) has been investigated for several small macromolecules deposited on the graphite plate using laser radiation at 532 nm where most of the macromolecules are transparent. The graphite surface functioned well as a photon absorbing material and an energy transfer mediator for visible light. The results show that visible SALDI is a much softer ionization technique than UV-MALDI and FAB-MS in our results with synthetic macromolecules, PPG, PPGMBE and cavitand molecules. For the SALDI of biomolecules, glycerol as a proton source was essential with the graphite plate. As in visible SALDI, the role division of the photon absorbing material and the cationization agent can provide a generality in mass spectrometric analysis of macromolecules compared with MALDI using the dual functional matrix.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3366-3370
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• 2010

The specific rates of solvolysis of t-butyl fluoroformate (1) have been measured at $40.0^{\circ}C$ in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation, with incorporation of the solvent nucleophilicity and the solvent ionizing power, is applied. The actual values are very similar to those obtained in earlier studies of the solvolyses of isopropyl chloroformate and ethyl chlorothioformate in the more ionizing and least nucleophilic solvents, which are believed to proceed by an ionization pathway. The small negative values for the entropies of activation are consistent with the ionization nature of the proposed rate-determining step. These observations are also compared with those previously reported for the corresponding primary and secondary alkyl haloformate esters.

• Bulletin of the Korean Chemical Society
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• 제31권1호
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• pp.35-40
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• 2010

A comprehensive comparative investigation of small carbohydrates in laser desorption ionization was performed on supporting materials composed of sodiated 2,5-dihydroxybenzoic acid (DHB), carbon nanotubes, an ionic liquid matrix of DHB-pyridine, a binary matrix of DHB-aminopyrazine, zinc oxide nanoparticles, and gold nanoparticles. The abundance of $[M+Na]^+$ ions, where M is glucose or sucrose, was compared for each supporting material. The highest sensitivity for both glucose and sucrose, with a detection limit of 3 pmol, was observed with carbon nanotubes. Both carbon nanotubes and the ionic liquid matrix exhibited the highest reproducibility.

• Macromolecular Research
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• 제17권6호
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• pp.397-402
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• 2009

In emulsifier-free, emulsion polymerization with ionizable comonomer, the ionization of the comonomer is critical in determining the size of the final polymerie particles at sub-micrometer scale. In this study, polystyrene latex beads with carboxylates on the surface were synthesized using acrylic acid as a comonomer. Specifically, ammonium hydroxide was added to the emulsifier-free polymerization system to promote the ionization of acrylic acid by increasing pH. Smaller polystyrene latex particles were produced by increasing the ammonium hydroxide concentration in the reaction system, due to the enhanced stability promoted by the ionization of acrylic acid during the nucleation step. In addition, the surface morphology of the polystyrene latex particles was controlled by the concentration of acrylic acid, the dissociation of which was influenced by the ammonium hydroxide concentration.

• Bulletin of the Korean Chemical Society
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• 제17권9호
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• pp.814-819
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• 1996

In search of simple host molecules for uranyl ion which form 1: 1-type complexes with high formation constants that can be used either in extraction of uranium from seawater or in catalysis of biologically important organic reactions, the uranophile activities of dihydroxyazobenzene derivative 1 were studied. Uranyl ion and 1 form a 1: 1-type complex with a very large formation constant. The formation constant was measured at pH 7-11.6 by competition experiments with carbonate ion. From the resulting pH dependence, ionization constants of the two aquo ligands coordinated to the uranium of the uranyl complex of 1 were calculated. The ionization constants were also measured by potentiometric titration of the uranyl complex of 1. Based on these results, the pKa values of the two aquo ligands were estimated as 7.1 and 11.0, respectively. At pH 7.5-9.5, therefore, the complex exists mostly as monohydroxo species. Under the conditions of seawater, 1 possesses greater affinity toward uranyl ion compared with other uranophiles such as carbonate ion, calixarene derivatives, or a macrocyclic octacarboxylate. In addition, complexation of 1 with uranyl ion is much faster than that of the calixarene or octacarboxylate uranophiles.

• Bulletin of the Korean Chemical Society
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• 제17권11호
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• pp.1036-1039
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• 1996

Synthetic lipoidal peptides based on viral protein sequences have been prepared. These peptides contain an N-palmitoyl group at the N-terminal residue, which is a modified cysteine, containing a S-[2,3-bis(acyloxy)-(2-R,S)-propyl] moiety. When this residue (Pam3Cys) is at the N-terminus of a synthetic peptide, it acts as potent immunoadjuvant to enhance both IgM and IgG antibody responses to the attached peptide. Conventional analytical procedures (e.g., Edman degradation and amino acid analysis) are either not applicable due to the N-terminal modification, or do not provide confirmation of the intact structure. Chromatographic analysis is also hindered by the tendency of these lipoidal Pam3Cys peptides to form large aggregates, and in some cases to be permanently adsorbed on reversed phase columns. We have applied several mass spectrometric techniques, including fast atom bombardment (FAB), electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) to characterize the intact structures of a number of different Pam3Cys synthetic peptides. The MALDI-MS has been found to be the most sensitive for the analysis of the structure of Pam3Cys peptides.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1963-1967
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• 2010

The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.

• Bulletin of the Korean Chemical Society
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• 제34권3호
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• pp.907-911
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• 2013

Numbers of matrix- and analyte-derived ions and their sum in matrix-assisted laser desorption ionization (MALDI) of a peptide were measured using 2,5-dihydroxybenzoic acid (DHB) as matrix. As for MALDI with ${\alpha}$-cyano-4-hydroxy cinnamic acid as matrix, the sum was independent of the peptide concentration in the solid sample, or was the same as that of pure DHB. This suggested that the matrix ion was the primary ion and that the peptide ion was generated by matrix-to-peptide proton transfer. Experimental ionization efficiencies of $10^{-5}-10^{-4}$ for peptides and $10^{-8}-10^{-7}$ for matrices are far smaller than $10^{-3}-10^{-1}$ for peptides and $10^{-5}-10^{-3}$ for matrices speculated by Hillenkamp and Karas. Number of gas-phase ions generated by MALDI was unaffected by laser wavelength or pulse energy. This suggests that the main role of photo-absorption in MALDI is not in generating ions via a multi-photon process but in ablating materials in a solid sample to the gas phase.

• 분석과학
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• 제6권1호
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• pp.77-82
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• 1993

음이온 화학적 이온화 질량분석법은 아미노산 분석에 있어서 sensitivity를 향상시킬 수 있는 좋은 방법이 될 수 있다. 강한 전자 포획성 분자들에 대해서 이 방법은 femtomole에서 attomole($10^{18}$)까지 측정한계가 내려가는 것이 보고되고 있다. 이 논문에서는 아미노산을 전자 포획성 물질인 dinitro-phenyl(DNP) 유도체를 만들어 음이온 화학적 이온화 질량 분석법으로 스펙트럼을 얻어 이를 전자 이온화법으로 얻은 질량 스펙트럼과 비교하였다. 그 결과 음이온 질량분석법의 경우 이온화 과정의 선택성 때문에 background noise가 훨씬 줄어들어 깨끗한 스펙트럼이 얻어졌다.