• Journal of the Korean Chemical Society
• /
• v.23 no.5
• /
• pp.314-319
• /
• 1979

The electronic spectrum of marine dinoflagellate antenna pigment, peridinin, has been described in terms of PPP SCF MO CI computations and fluorescence polarization of the peridinin component in photosynthetic pigment complex of Amphidinium carterae. The main absorption band at 470 nm, $^1B{\leftarrow}A$, is polarized nearly along the long molecular axis. There appear to be two ${\pi}{\rightarrow}{\pi}^*$ transitions (C and $D{\leftarrow}A$) in the socalled "cis" peak region, and they are polarized roughly parallel to the main $B{\leftarrow}A$ absorption. In addition, we have found that the carbonyl group undergoes very 1ittle reorganization of the electronic structure in going from the ground to the $^1B$ excited states of peridinin, while the allenic group shows a strong charge transfer tendency in producing an electron-deficient allente allene group in the excited state.

• Journal of the Korean Chemical Society
• /
• v.37 no.9
• /
• pp.787-792
• /
• 1993

Semiempirical MNDO calculations are employed to study relation properties on bridging OH group with Al-O(P-O) bond length and Al-O-P bond angle of structural characteristics using birdging $(OH)_3AlOP(OH)_3$ and $(OH)_3AlOHP(OH)_3^+$ model culster. We know that the O-H bond dissociation energy of bridging OH group is increased with increasing Al-O(P-O) bond length and decreasing Al-O-P bond angle. The bridging OH group is formed into enlarged Al-O(P-O) bond length and shortened Al-O-P bond angle in bridging oxygen atom by a hydrogen migration. The negative net charge of bridging oxygen atom is increased with longer Al-O-P bond angle, while the positive net charge is decreased with longer Al-O-P bond angle.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.9
• /
• pp.1297-1304
• /
• 2006

A systematic study of the structure, energetics and spectral characteristics of substituted aminoketenes $R(NH_2)$C=C=O (R = H, $CH_3$, $NH_2$, OH, $OCH_3$, CH=$CH_2$, C$\equiv$CH, CN, CHO, NO, $NO_2$) which are highly reactive and transient intermediates in synthesis has been conducted by ab initio calculations at the MP2/6- 31G*//MP2/6-31G* level. Twenty four stable isomers of the eleven substituted aminoketenes having dihedral angles $\phi NH_2\sim120{^{\circ}}$ and $60^{\circ}$ have been identified and their optimized geometries and energies obtained. Electrostatic and steric effects on the molecular geometries have been analyzed. While the $\pi$-acceptor groups lead to planar conformations, the electron-donor groups give rise to non-planar conformations. Isodesmic substituent stabilization energies relative to alkenes have been calculated and correlation with group electronegativities established. Role of induction effect by the substituent groups and resonance effects in charge distribution in the molecules has been analyzed. An analysis of the asymmetric stretching frequencies and intensities of the C=C=O group shows that affect of non-$\pi$ acceptor substituents on the frequency is determined by the field effect (F) and resonance effect (R) parameters, the calculated intensities I (km/mol.) are correlated to group electronegativities $x$ of the substituents by the relationship I = 640.2–100.1 $x$ (r = 0.92). The $\pi$-acceptor substituents increase the intensity which may be explained in terms of their delocalizing effect on the negative charge at the $C_{\beta}$ atom.

• Journal of the Korean Chemical Society
• /
• v.13 no.2
• /
• pp.121-129
• /
• 1969

The apparent and partial molal volumes({\phi}\nu$and $V^{\circ}$) of a series of homologous n-alkylamine hydrochlorides $C_nH_{2n+1}NH_3^+Cl^-$, where n varies from zero to four, have been determined by means of a float method at 30$^{\circ}C$ to the fifth decimal place down to 0.01M in aqueous solutions. The experimental results indicate that the partial molal volumes of the salts are almost additive for successive homologues depending on the increment of molecular weight ($CH_2$). It has been observed that the concentration dependence of the ${\Phi}v$ are linear in general and limiting slopes are positive and relatively close to the theoretical values. Anionic partial molal volume of chlorides anion $V^{\circ}_{Cl^-}$ is found to be 18.6 ml $mole^{-1}$, which is in good agreement with the results of other workers. {\phi}\nu$ data also show that in solution the hydrophobic effect of ions are in competition with the charge effect, but the latter, that is, electrostriction seemed to be considerably predominant.

• Journal of Microbiology and Biotechnology
• /
• v.8 no.4
• /
• pp.341-346
• /
• 1998

Optimization for the production of Pest an was followed by the Plackett-Burman Design, using modified Czapek-dox medium as the starting point. At the flask level, $K_2HPO_4$, $MgSO_4{\cdot}7H_2O$, and aeration variables positively affected the Pestan production, DCW (dry cell weight), apparent viscosity, and flocculating activity response. KCI and $FeSO_4{\cdot}7H_2O$ negatively affected the Pestan production, DCW, apparent viscosity, and flocculating activity response. Aeration variable was shown to have a positive effect on only the flocculating activity response among Pestan production, DCW, and apparent viscosity responses. In comparison of the positive and negative variables media conditions, Pestan production and flocculating activity differed by about 9 and 125 times, respectively. In particular, at the jar fermentor level, the aeration variable was the most important factor of the all responses (pestan production, DCW, apparent viscosity, flocculating activity, and anionic charge density). The flocculating activity and apparent viscosity of Pestan were closely related to the molecular chain length and charge density.

• Journal of the Korean Chemical Society
• /
• v.48 no.2
• /
• pp.123-128
• /
• 2004

Quantum chemical quantities, enthalpy of formation(${\Delta}H_f$), HOMO and LUMO energy, and dipole moment(${\mu}_D$) were acquired by AM1, PM3, and ZINDO/1 methods for polyamines and imidazole derivatives. The investigation of the inhibitory activity on some Ni(II) complexes with polyamines and imidazole derivatives is performed by ZINDO/1 calculations. It was found that experimental inhibitory activity(IA) appeared when the value of net charge and enthalpy of formation were over 0.03 and -300 eV, respectively for Ni(II) complexes. These results showed that the Ni(II) complexes have exception on the following very unstable compounds: square pyramidal [Ni(dpt)(tn)])]$^{2+}$(dpt=3,3'-diaminodipropylamine)(tn=1,3-diaminopropane) and distorted tetrahedral [Ni(N-PropIm))$_2$(NCS))$_2$](N-PropIm=N-Propylimidazole).

• Membrane Journal
• /
• v.27 no.5
• /
• pp.406-414
• /
• 2017

In this study, we have developed pore-filled ion-exchange membranes (PFIEMs) filled with ionomer in a thin polyethylene porous film (thickness = $25{\mu}m$) and investigated the charge-discharge characteristics of the all vanadium redox flow battery (VRFB) employing them. Especially, the degree of crosslinking and free volume of the PFIEMs were appropriately controlled to produce ion-exchange membranes exhibiting both the low membrane resistance and low vanadium permeability by mixing crosslinking agents having different molecular size. As a result, the prepared PFIEMs exhibited excellent electrochemical properties which are comparable to those of the commercial membranes. Also, it was confirmed through the experiments of vanadium ion permeability and VRFB performance evaluation that the PFIEMs showed low vanadium ion permeability and high charge-discharge efficiency in comparison with the commercial membrane despite their thin film thickness.

• Applied Chemistry for Engineering
• /
• v.21 no.3
• /
• pp.278-283
• /
• 2010

The cationic polymerization of oxolane high explosives which have pendant explosive groups such as azido, nitrato and hydrazino is investigated theoretically using the semiempirical MINDO/3, MNDO and AM1 methods. The nucleophilicity and basicity of oxolane high explosives can be explained by the negative charge on oxygen atom of oxolane. The reactivity of propagation in the polymerization of oxolane can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxolane. The reaction of the oxolane high explosives in oxonium ion form to the open chain carbenium ion form is expected by computational stability energy (17.950~30.197 kcal/mol) of the oxonium ion and carbenium ion favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium ion and carbenium ion is found to be a major determinant of mechanism, owing to the rapid equilibrium of these catoinic forms. Based on calculation, in the prepolymer propagation step, $S_N1$ mechanism will be at least as fast as that for $S_N2$ mechanism.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.3
• /
• pp.981-987
• /
• 2011

The anomalous spectroscopic properties of quercetin-3-O-rhamnoside (QCRM) and quercetin-3-O-rutinoside (QCRT) in AOT reverse micelle were studied. The excited state intramolecular proton transfer (ESIPT) occurs through the strong hydrogen bond between the -OH at position 5 and the carbonyl oxygen. Because the ESIPT can only happens in the $S_1$ state and the Franck-Condon factor involved in the $S_2\;{\rightarrow}\;S_1$ internal conversion is small, the $S_2\;{\rightarrow}\;S_o$ emission alone appears. Because the molecular planarity is improved at the interior of the micelle, the excited state intramolecular charge transfer in the $S_1$ state is extended, and the excited state is more tolerable for any quenching effects in the micelle. Therefore, an $S_1\;{\rightarrow}\;S_o$ emission was newly discovered under this micelle microenvironment. For the $S_2\;{\rightarrow}\;S_o$ emission, the quantum yields increase but the quantum yield of the $S_1\;{\rightarrow}\;S_o$ emission approximately decreases as the water concentration in the micelle increases.

• Analytical Science and Technology
• /
• v.20 no.1
• /
• pp.61-69
• /
• 2007

The geometrical parameters, total and relative energies, vibrational frequencies, the HOMO-LUMO energy gap, and reorganization energies for the neutral molecule, anion, and cation of $C_{16}H_{16}O_3$ have been determined using density functional method (DFT). The highest level of theory employed in this study is $B3LYP/6-311G^{**}$. Harmonic vibrational frequencies were determined at the $B3LYP/6-311G^{**}$ level of theory. All positive vibrational frequencies were obtained to confirm minimum structures. The HOMO-LUMO energy gap and reorganization energies were calculated to predict the charge transport property of liquid-crystal.