• Bulletin of the Korean Chemical Society
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• v.24 no.2
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• pp.205-208
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• 2003

Laser-induced Raman spectroscopy has been utilized to demonstrate its feasibility for studying the kinetics of imine formation in chloroform solvent. The imine formation, by the nucleophilic addition of primary amine to the carbonyl group of ketone, has been monitored at ten minute intervals for eight hours. The intensity of the C=O stretching mode at 1684 $cm^{-1}$ was measured to determine the rate constant of the reaction. In order to correct the sample-to-sample fluctuations in Raman peak area, this peak was normalized to the C-Cl bending peak at 666 $cm^{-1}$. By the peak area change during the course of reaction, the second order rates at three different temperatures have been determined. The substituent effects on the π conjugations of imine product have also been investigated. On the basis of Raman frequency shifts, the delocalization properties of the aromatic system modified by substitution of a hydrogen atom with -Cl and $-CH_3O$ groups could be clearly understood.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4347-4351
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (2) with X-pyridines are investigated kinetically in acetonitrile at $-20.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. Unusual positive ${\rho}_X$ (= +2.49) and negative ${\beta}_X$ (= -0.41) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=6.6^{\circ}C$. The pyridinolysis rate of 2 with a cyclic five-membered ring is forty thousand times faster than its acyclic counterpart (3: diethyl chlorophosphate) because of great positive value of the entropy of activation of 2 (${\Delta}S^{\neq}$ = +49.2 eu) compared to negative value of 3 (${\Delta}S^{\neq}$ = -44.1 eu) over considerably unfavorable enthalpy of activation of 2 (${\Delta}H^{\neq}=28.4\;kcal\;mol^{-1}$) compared to 3 (${\Delta}H^{\neq}=6.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed.

• Bulletin of the Korean Chemical Society
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• v.22 no.8
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• pp.837-841
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• 2001

The electronic absorption and Raman spectra of $\alpha\omega-diphenylpolyenyl$, anions Ph(CH)nPh- (DPn- , n = 3, 5, 7, 9, and 13), with odd number of carbons at the polyene part, have been studied in the tetrahydrofuran (THF) solutions and in their solid film states, respectively. In the case of Raman spectra for DPn- , the frequencies and relative intensities of some Raman peaks regularly change with the increase of polyene chain length. The spectral patterns of anions (DPn- ) are very similar with those of radical anion (DPn${\cdot}$- ). However, the C=C stretching peaks of DPn- anions are observed in the 25-35 cm-1 higher frequency region than those of DPn${\cdot}$- radical anions. In the case of long chain models such as DP9- and DP13- , the C=C stretching peaks are observed in even higher frequency region than those of the corresponding neutral polyenes such as DP8, DP10, and DP12. The Raman patterns of DPn- anions in the THF solutions are similar with those in their solid film states. On the other hand, their electronic absorption spectra show a considerable difference each other. The n- ${\pi}*$ electronic absorption bands of DPn- anions in the THF solutions have been observed in the 0.27-0.39 eV lower energy region than those in their solid film states due to the solvent effects on polyene anions.

• Korean Journal of Materials Research
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• v.14 no.10
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• pp.737-742
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• 2004

$CuInSe_2$ (CIS) nanoparticles of chalcopyrite structure were directly synthesized by a solvothemal method in an autoclave with diethylamine as a solvent. A morphology change of the nanoparticles was observed as a function of reaction temperatures and times. Dense rod-type CIS nanoparticles with width of $5\sim10mm$ and length in the range of 30-80 nm were obtained at $180^{\circ}C$ for 36 hrs whereas spherical particles with diameter in the range of 5-10 nm were observed at $250^{\circ}C$ for 36 hrs. The formation of the rod-like nanoparticles in diethylamine, without double N-chelation, was explained by the Solution-Liquid-Solid (SLS) mechanism.

• Carbon letters
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• v.1 no.3_4
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• pp.148-153
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• 2001

The initial irreversible capacity, $Q_i$, is one of the parameters to express the material balancing of the cathode to anode. We introduced new terms, which are the initial intercalation Ah efficiency (IIE) and the initial irreversible specific capacity at the surface ($Q_{is}$), to express precisely the irreversibility of an electrode/electrolyte system. Two terms depended on kinds of active-materials and compositions of the electrode, but did not change with charging state. MPCF had the highest value of IIE and the lowest value of $Q_{is}$ in 1M $LiPE_6$/EC + DEC (1 : 1 volume ratio) electrolyte. IIE value of $LiCoO_2$ electrode was 97-98%, although the preparation condition of the material and the electrolyte were different. $Q_{is}$ value of $LiCoO_2$ was 0~1 mAh/g. MPCF-$LiCoO_2$ cell system had the lowest of the latent capacity. $Q_{is}$ value increased slightly by adding conductive material. IIE and $Q_{is}$ value varied with the electrolyte. By introducing PC to EC+DEC mixed solvent, IIE values were retained, but $Q_{is}$ increased. In case of addition of MP, IIE value increased and $Q_{is}$ value also increased a little.

• Journal of the Korean Society of Manufacturing Technology Engineers
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• v.24 no.1
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• pp.38-42
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• 2015

Polydimethylsiloxane (PDMS) is a widely used material for replicating micro-structures because of its transparency, deformability, and easy fabrication. At the nanoscale, however, it is hard to fill a nanohole template with uncured PDMS. This paper introduces several simple methods by changing the surface energy of a nanohole template and PDMS elastomer for replicating 100nm-scale structures. In the case of template, pristine anodic aluminum oxide (AAO), hydrophobically treated AAO, and hydrophillically treated AAO are used. For the surface energy change of the PDMS elastomer, a hydrophilic additive and dilution solvent are added in the PDMS prepolymer. During the molding process, a simple casting method is used for all combinations of the treated template and modified PDMS. The nanostructured PDMS surface was investigated with a scanning electron microscope after the molding process for verification.

• Macromolecular Research
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• v.12 no.1
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• pp.22-25
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• 2004

We have synthesized aniline oligomer composites by using heteropoly acid (H$_4$SiW$_{12}$O$_{40}$ ) as a dopant. The doping and dedoping processes of the aniline oligomer composites were investigated with the aid of UV- Vis spectra. The bands of the aniline oligomer at 572 nm weakened or disappeared, and the bands at 268, 412, and 771 nm appeared, after the aniline oligomer was doped. When the solution of the aniline oligomer doped with H$_4$SiW$_{12}$O$_{40}$ was kept at lower values of pH, the aniline oligomer could not be dedoped by dilution. The turning point of doping and dedoping occurred at pH 5.5. The band at 771 nm shifted towards longer wavelengths when the aniline oligomer composites were synthesized using acetone as the solvent. This observation indicates that the molecular chain became stretched. In addition, we also investigated the change of the electronic absorption spectra of the composites with respect to the time laid up.id up.

• Journal of the Korean Magnetic Resonance Society
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• v.12 no.1
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• pp.51-59
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• 2008

Convection effect in liquids has been one of the main targets to be overcome in pulsed-field-gradient NMR measurements of self-diffusion coefficients since the temperature gradient along the sample tube generated by the heating and/or cooling process causes the effect, resulting in additional diffusion. It is known that the capillary is the most appropriate tube type for diffusion experiments at variable temperatures since the narrower tube suppresses convection effectively. For evaluating the properties of hydrogen bonding, diffusion coefficients of the $K^+$-complexed and free valinomycin in a micro tube have been determined at various temperatures. From the analysis of the obtained diffusion coefficient values, we could conclude that the intramolecular hydrogen bonding in both of the $K^+$ complexed and free valinomycin in a non-polar solvent is preserved over the observed temperature range, and the temperature dependence of hydrogen bonding is more pronounced in free valinomycin. It is also thought that there is no big change in the radius of the $K^+$-complexed as temperature is varied, and the ratio of overall radius, $r_{complex}/r_{free}$ is slightly decreased as temperature rises.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.588-594
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• 1997

Gelation time, gel structure and volatility of by-products during gelation of PZT sol-gel processing were investigated by FT-IR spectroscopy. FT-IR spectroscopic study was performed on PZT gels with the various H₂O contents (1, 2 and 3 mol) and the several types (HNO₃, NH₄OH) and amounts (0.1, 0.2 mol) of catalysts, monitoring temporal (0, 1, 3, 10 weeks, 3 months and 3 years) and thermal (100-700 ℃) changes of FT-IR spectra. The interpretation of temporal change of the spectra revealed two trends. One is under the condition of 1 mol H₂O, 1 mol H₂O+0.1 mol HNO₃, 3 mol H₂O and the other is for 1 mol H₂O+0.1 mol NH₄OH, 2 mol H₂O, 1 mol H₂O+0.2 mol HNO₃. The gel structures and the gelation times for these conditions were discussed in comparison with the reported results of SiO₂, and we suggested the reaction mechanisms for these structural characteristics. Thermal variation of FT-IR spectra was interpreted as the evolution processes of gel by investigating the evaporation of solvent and the decomposition of organic residues.

• Journal of the Korean Chemical Society
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• v.59 no.3
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• pp.238-245
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• 2015

The crystallization and morphology change of amorphous titanias by hydrothermal treatment have been investigated. The amorphous titanias were prepared by pure water hydrolysis of two different precursors, titanium tetraisopropoxide (TTIP) and TTIP modified with acetic acid (HOAc) and characterized prior to hydrothermal treatment. In order to avoid complicate situation, the hydrothermal treatment was performed in a single solvent water with and without strong acids at various temperatures. The effects of strong acid, temperature and time were systematically investigated on the transformation of amorphous titania to crystalline TiO₂ under simple hydrothermal condition. Without strong acid the titanias were transformed into only anatase phase nanoparticle regardless of precursor type, temperature and time herein used (up to 250 ℃ and 48 hours). The treatment temperature and time effected only on the crystalline size, not on the crystal phase et al. However, it was clearly revealed that the strong acids such as HNO₃ and HCl catalyzed the formation of rutile phase depending on temperature. HCl was slightly better than HNO₃ in this catalytic activity. The morphology of rutile TiO₂ formed was also a little affected by the type of acid. The precursor modifier, HOAc slightly reduced the catalytic activity of the strong acids in rutile phase formation.