• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2571-2574
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• 2010

We investigate the mechanism of $S_NAr$ fluorination reactions under the influence of protic solvents and ions. We find that counterion or protic solvent alone retards the $S_NAr$ reactions, but together they may promote the reaction. In this mechanism, the protic solvent acts on the counterion as a Lewis base, and the nucleophile reacts as an ion pair. We also show that an anion (mesylate) may exhibit catalytic effects, suggesting the role of ionic liquids for accelerating the $S_NAr$ reactions.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1535-1538
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• 2009

We present calculations for $S_N$2/E2 reactions in protic solvents (t-butyl alcohol, ethylene glycol). We focus on the role of the hydroxyl (-OH) groups in determining the $S_N$2/E2 rate constants. We predict that the ion pair E2 mechanism is more favorable than the naked ion E2 reaction in ethylene glycol. E2 barriers are calculated to be much larger (~ 9 kcal/mol) than $S_N$2 reaction barriers in protic solvents, in agreement with the experimental observation [Kim, D. W. et al. J. Am. Chem. Soc. 2006, 128, 16394] of no E2 products in the reaction of CsF in t-butyl alcohol.

• 한국전기화학회:학술대회논문집
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• 1998.12a
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• pp.153-166
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• 1998

Lithium ion Batteries commercially available since the early nineties in Japan are going to be more and more important for portable electronic devices and even EV applications. Today several companies around the world are working hard to join to market for Lithium secondary batteries. Based on the growing interest for commercial use of batteries also the materials have to be reviewed in order to meet large scale production needs. The requirements especially for electrolytes for lithium batteries are extremely high. The solvents and the lithium salts should be of highest purity. So the supply of these chemicals including packaging, transportation and storage but also the handling in production are critical items in this field. Frolic impurities are very critical for LiPF6 based electrolytes. The influence of water is tremendous. But also the other protic impurities like alcoholes are playing an Important role for the electrolyte quality. The reaction of these species with LiPF6 leads to formation of HF which further reacts with cathode materials (spinel) and anode. To understand the role of the protic impurities more clearly the electrolyte was doped with such compounds and was analyzed for protic impurities and HF. These results which directly show the relation between impurities and quality will be presented and discussed. In addition several investigations on different packaging materials as well as methods to analyze and handle the sensititive material will be addressed. These questions which are only partly discussed in literature so far and never been investigated systematically cover some of the key parameters for understanding of the battery chemicals. This investigation and understanding however is of major importance for scientist and engineers in the field of Lithium ion and Lithium polymer batteries.

• Analytical Science and Technology
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• v.22 no.2
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• pp.159-165
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• 2009

The thermochromism of fluoran has been examined. The DCF exists as a colorless lactone in aprotic solvents. However, the DCF exists in the form of an equilibrium mixture of a colored zwitter-ion and a colorless lactone in protic solvents. When an acid is added to the solution, the DCF exists an equilibrium mixture as a colorless lactone and a colored cation even in aprotic solvents. In order to understand the interaction between the DCF and the solvent, absorption spectra of the DCF in various solvents were measured. The thermodynamic parameters of the DCF have also been investigated. From the variation of absorbance with temperature, the standard enthalpy changes ${\Delta}H^0$ of the equilibrium between the lactone and the zwitter-ion in various solvents have been determined. The standard enthalpy change ${\Delta}H^0$ is approximately -2.0 kJ/mol in protic solvents. In acidic solution, the standard enthalpy change is measured to be to zero in protic solvents within the experimental error. When the carboxylic group is protonated in acidic solution, a poor interaction between the dye and the solvent is expected.

• Bulletin of the Korean Chemical Society
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• v.8 no.6
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• pp.441-444
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• 1987

The circular dichroism(CD) spectra of the optically active [$Co(acac)_2(diamine)]^+$ complexes were measured in the several protic and aprotic solvents, where acac = acetylacetonate anion and diamine = ethylenediamine and trimethylenediamine. The degree of the CD variation in protic solvents was enhanced as the dielectric constant decreases except n-butanol and benzylalcohol. And the degree of the CD variation in aprotic solvents was roughly increased as both dipole moment and dielectric constant decrease except aromatic solvents and the solvents having no dipole moment. It was deduced that the CD variations of the complexes have been due to the conformational change of acetylacetonate ligands coordinated to Co(III) ion.

• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.664-672
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• 2011

A series of hydrophilic chromophores was synthesized through introduction of dendritic sulfonate anions using click chemistry. A dendron structure bearing several sulfonate groups enhances hydrophilicity of attached chromophores. A click triazole formation connects chromophores with hydrophilic groups. A neutral trichloroethyl sulfonate has versatile features such as easy introduction, chemical endurance for isolation or storage, and convenient transformation to a hydrophilic anion. Zinc and OH mediated cleavage of trichloroethyl group from the neutral sulfonate undergoes to generate a water-soluble sulfonate anion. The solubility was examined with different counter cations and in different pH media and thus increased with the number of attached sulfonate ion. Two hydrophilic chromophores of stilbene-derived and azobenzene-derived dipolar structures exhibit clear negative and positive solvatochromism in protic solvents, respectively.

• Journal of Electrochemical Science and Technology
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• v.13 no.2
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• pp.254-260
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• 2022

Trimethylammonium tetrafluoroborate (TriMA BF₄), consisting of the smallest trialkylammonium ion, was investigated for use in electrochemical double-layer capacitors. Despite the presence of a proton in TriMA⁺, cycle life tests in acetonitrile (AN) and -butyrolactone (GBL) showed a good capacity retention with a 1.8 V cut-off voltage. The rate of electrolysis of TriMA BF₄ in GBL was lower than that in AN because of the lower conductivity in GBL. As a consequence, the cells based on GBL achieved a higher capacitance and longer life than those with AN. TriMA BF₄ had a higher conductivity and lower viscosity than the quaternary salt tetraethylammonium tetrafluoroborate in GBL, as well as higher ionic mobility, these factors resulted in a higher rate capability.

• Journal of the Korean Chemical Society
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• v.13 no.2
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• pp.109-114
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• 1969

Halogen exchange reactions of benzyl halides have been studied in absolute acetone. Rate constants were calculated using an integrated rate expression derived for the reaction involving ion-pair association. The order of nucleophilicity of halide ions in acetone was found to be a reverse of the order in 90% aqueous enthanol solvent. This was interpreted by means of HSAB principle and solvation of halide ions. Net increase in rate of reaction in acetone compared with the rate in protic solvent resulted from large increase in ${\Delta}S^\neq$ rather than decrease in ${\Delta}H^\neq$. The solvation of the transition state also contribute to the net increase in rate.

• Mass Spectrometry Letters
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• v.8 no.2
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• pp.29-33
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• 2017

Understanding the mechanisms that control and concentrate the observed electrospray ionisation (ESI) response from peptides is important. Controlling these mechanisms can improve signal-to-noise ratio in the mass spectrum, and enhances the generation of intact ions, and thus, improves the detection of peptides when analysing mixtures. The effects of different mixtures of aqueous: organic solvents (25, 50, 75%; v/v): formic acid solution (at pH 3.26) compositions on the ESI response and charge-state distribution (CSD) during mass spectrometry (MS) were determined in a group of biologically active peptides (molecular wt range 1.3 - 3.3 kDa). The ESI response is dependent on type of organic solvent in the mobile phase mixture and therefore, solvent choice affects optimal ion intensities. As expected, intact peptide ions gave a more intense ESI signal in polar protic solvent mixtures than in the low polarity solvent. However, for four out of the five analysed peptides, neither the ESI response nor the CSD were affected by the volatility of the solvent mixture. Therefore, in solvent mixtures, as the composition changes during the evaporation processes, the $pK_b$ of the amino acid composition is a better predictor of multiple charging of the peptides.

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.250-257
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• 1987

The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$