• Bulletin of the Korean Chemical Society
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• v.16 no.11
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• pp.1015-1019
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• 1995

The electronic structures and properties of the neutral and multiply charged C60n ions (n=2+ to 6-) with spin states have been investigated by semi-empirical MNDO calculations. In the ground state, C601- has the lowest total energy and the highest binding energy. The neutral C60 ion is supposed to have a high ionization potential and a high electron affinity. The HOMO and LUMO positions are lower in the cationic C60 than in the anionic C60. The LUMO energy becomes increasingly positive from C601- to C606- and the HOMO energy becomes increasingly negative from C602+ to C60. The HOMO-LUMO gap of the neutral C60 ion is higher than that of the multiply charged C60 ions. From the HOMO-LUMO gap, it seems reasonable to expect that electrons of the multiply charged C60 ions will be more polarizable than those of the neutral C60 ion. The HOMO and LUMO energies increase as the negative charge increases.

• Bulletin of the Korean Chemical Society
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• v.21 no.4
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• pp.379-382
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• 2000

The temperature dependence of the kinetic parameters of the aspartase-catalyzed reaction has been examined in the direction of deamination. The pK1values at 37$^{\circ}C$, 25$^{\circ}C$, 16$^{\circ}C$ and 7$^{\circ}C$ were 6.2 $\pm$ 0.1, 6.3 $\pm$ 0.1, $6.7{\pm}0.3$ and 6.9 $\pm$ 0.3, respectively. On the other hand, the pK2 values at 37$^{\circ}C$,25$^{\circ}C$, 16$^{\circ}C$ and 7$^{\circ}C$ were 8.1 $\pm0.2$, 8.3 $\pm$ 0.2, 8.2 $\pm$ 0.3 and 8.0 $\pm$ 0.2,respectively. The enthalpy of ionization, DHion, calculated from the slope of pK1, are 6.0 $\pm$ 0.3 kcal/mol. These results validate the prediction that aspartase requires a histidine residue for a general base, and a cysteine (or having a carboxyl functional group) for a general acid.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.482-486
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• 1992

Ion-molecule reactions of acetylene and mixed acetylene-ammonia cluster ions are studied using an electron impact time-of-flight mass spectrometer. The present results clearly demonstrate that $(C_2H_2)_n^+$ cluster ion distribution represents a distinct magic number of n=3. The mass spectroscopic evidence for the enhanced structural stabilities of $[C_6H_4{\cdot}(NH_3)_m]^+$ (m=0-8) ions is also found along with the detection of mixed cluster $[(C_2H_2)_n{\cdot}(NH_3)_m]^+$ ions, which gives insight into the feasible structure of solvated ions. This is rationalized on the basis of the structural stability for acetylene clusters and the dissociation dynamics of the complex ion under the presence of solvent molecules.

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1101-1105
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• 2000

A simultaneous determination method of BTEX (benzene, toluene, ethylbenzene, o,m.p-xylene) and TPH (kerosene, diesel, jet fuel and bunker C) in soil with gas chromatography/flame ionization detection (GC-FID) was described. The effects of extracti on method, extraction solvent, solvent volume and extraction time on the extraction performance were studied. A sonication method was simpler and more efficient than Soxhlet or shaking methods. Sonication with 10 mL of acetone/methylene chloride (1 : 1, v/v) for 10 min was found to be optimal extraction conditions for 20 g of soil. Peak shapes and quantification of BTEX and TPH were excellent, with linear calibration curves over a wide range of 1-500 mg/L for BTEX and 10-5000 mg/L for TPH. Good reproducibilities by sonication were obtained, with the RSD values below 10%. By using about 20 g of soil, detection limits were 0.8 mg/L for BTEX and 10 mg/L for TPH. The advantages of this procedure are the use of simple and common equipment, reduced volumes of organic solvents, rapid extraction periods of less than 20 min, and simultaneous analysis of volatile and semivolatile compounds.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1181-1185
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• 1999

The reaction of FeC5H5+ ion with ferrocene molecule is investigated using FT-ICR mass spectrometry. FeC5H5+ ions are generated by dissociative ionization of ferrocenes using an electron beam. The reaction gives rise to the formation of the adduct ion, Fe2(C5H5)3+, in competition with charge transfer reaction leading to the formation of ferrocene molecular ion, Fe(C5H5)2+·. The branching ratio of the adduct ion increases as the internal energy of the reactant ion decreases and correspondingly the branching ratio for the charge transfer reaction product decreases. The observed rate of the addition reaction channel is slower than that of the charge transfer reaction. The observation of the stable adduct ions in the low-pressure ICR cell is attributed to the radiative cooling of the activated ion-molecule complex. The mechanism of the reaction is presented to account for the observed experimental results.

• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.574-582
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• 1991

The CO molecules adsorbed on Ni(111) surface is studied in the cluster approximation employing EH method with self-consistent charge iteration. The effect of CO coverage is simulated by allowing the variation of valence state ionization potentials of each Ni atom in model cluster according to the self-consistent charge iteration method. The CO coverage dependent C-O stretching frequency shift, adsorption site conversion, and metal work function change are attributed to the charge transfer between metal surface and adsorbate. For CO/Ni(111) system, net charge transfer from Ni surface to chemisorbed CO molecules makes surface Ni atoms be more positive with increasing coverage, and lowers Ni surface valence band. This leads to a weaker interaction between metal surface valence band and Co $2{\pi}^{\ast}$ MO, less charge transfer to a single CO molecule, and the bule shift of C-O stretching frequency. Further increase of coverage induces the conversion of 3-fold site CO to lower coordination site CO as well as the blue shift of C-O stretching frequency. This whole process is accompanied by the continuous increase of metal work function.

• Bulletin of the Korean Chemical Society
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• v.6 no.5
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• pp.266-269
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• 1985

The dissociation constants(K) of m-chloroanilinium ion in water-ethanol mixture, where the volume percentage of water is 89.5%, were evaluated by UV-spectroscopic method at $20{\sim}50^{\circ}C$, up to 1500 bars with changing ionic strength from 0.04 to 0.10 mol $kg^{-1}$ by use of acetate buffer. K values enhance with increasing ionic strength and temperature, but decrease with elevating pressure. From K values, we obtained the partial molar volume change and some other thermodynamic parameters. From the values of enthalpy, entropy and isoequilibrium temperature (649 K), we concluded that the dissociation of m-chloroanilinium ion mentioned above is controlled by enthalpy.

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.292-294
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• 1993

Three derivatives of poly(ethylenimine) (PEI) are prepared by Ni(II)-template condensation with glyoxal(GO): PEI[Ni(II)-GO]$_{0.08}$ (1), PEI[Ni(II)-GO]$_{0.03}$ (2), and lau$_{0.18}$PEI[Ni(II)-GO]$_{0.03}$ (3). The contents of Ni(II)-macrocyclic center of 1-3 are 8%, 3%, or 3%, respectively, of the monomer residues, and 18% of monomer residues for 3 are laurylated. The pH profiles for k$_{cal}$ and k$_m$ for the deacylation of 4-carboxy-2-nitrophenyl acetate are measured. The relative magnitude of the parameters for 1-3 and different shapes of the pH profiles for 1-3 are explained in terms of the electrostatic and the hydrophobic effects exerted by the metal centers and lauryl groups. For the artificial metalloenzymes built on PEI, therefore, the ionization of functional groups and the affinity toward counter-anions can be controlled by adjusting charge density and the content of hydrophobic groups.

• Bulletin of the Korean Chemical Society
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• v.13 no.2
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• pp.162-165
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• 1992

The fine structure branching ratio and Doppler profiles of photofragment Cl ($^{2}P_{j}$) atoms from photodissociation of CINO around 236 nm in the A band have been measured by the two photon resonance enhanced multiphoton ionization technique. The measured branching ratio, $Cl^{\ast} (^{2}P_{1/2})/Cl (^{2}P_{3/2})$ is $0.18{\pm}0.02$. The Doppler profile of Cl is well reproduced assuming that one of the two components in the photofragment translational spectra reported by Haas, Felder, and Huber [Chem. Phys. Lett., 180, 293 (1990)] should correspond to Cl and that an anisotropy parameter $\beta$ for the angular distribution is 0.45. The results suggest that CINO dissociation in the A band should consist of at least two non-crossing electronic states which correlate to the formation of $Cl^* and Cl, respectively.

• KSBB Journal
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• v.19 no.5
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• pp.394-398
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• 2004

A derivatization method in mass spectrometry for small molecular analysis was developed to solve the problems of volatility of many analytes, difficult ionization of analytes, and undiscriminating isobaric analytes. This derivatization method, oximation of $\alpha$-ketoacid, in the transaminase reaction leads to change of mass difference between amine reactants and ketoacid products. In addition, regardless of the kinds of ketoacid, the linear relationship between the peak intensity and its concentration (from 1 mM to 10 mM) shows that quantitative analysis of the conversion of the reaction can be executed by the analysis of peak intensity of the corresponding oximated ketoacids. Furthermore, this method can be used for identifying transaminase as well as determining its substrate specificity