• Electrical & Electronic Materials
• /
• v.7 no.4
• /
• pp.341-346
• /
• 1994

• Bulletin of the Korean Chemical Society
• /
• v.24 no.6
• /
• pp.792-796
• /
• 2003

Polychlorinated dibenzo-p-dioxins (PCDDs) are extremely toxic and persistent environmental pollutants. Their chemical reactivities and other physicochemical/biological properties show a strong dependence on the chlorination pattern. With increasing the number of chlorines, dioxin congeners become more electronegative and gain higher electron affinities. The vertical electron affinities (VEA) are related with the LUMO energies of neutral molecules. LUMO energies of all PCDD congeners were calculated at the B3LYP/6-31G** level and those of some selected congeners at the level of B3LYP/6-311G**//B3LYP/6-31G** and B3LYP/cc-pvtz/ /B3LYP/6-31G**. The total energies of neutral and anionic species for dibenzo-p-dioxins (DD), 1469-TCDD, 2378-TCDD, and OCDD were calculated at the level of B3LYP/6-31G**, B3LYP/aug-cc-pvdz, and B3LYP/ aug-cc-pvtz//B3LYP/6-31G**. By using the four congeners with D2h symmetry as reference molecules, we could estimate VEA (B3LYP/aug-cc-pvdz) of 75 PCDD congeners based on the linear correlations between LUMO energy and VEA (B3LYP/6-31G**) and between VEA (B3LYP/6-31G**) and VEA (B3LYP/aug-ccpvtz// B3LYP/6-31G**). Results show that all PCDDs with the number of Cl ≥ 3 have positive electron affinities. The PCDD electron affinity values provided in this work can be a useful data set in understanding the congener-specific reactivities of dioxins in various environmental media.

• Applied Biological Chemistry
• /
• v.38 no.1
• /
• pp.90-94
• /
• 1995

Post emergence herbicidal activities$(pI_{50})$ of X-substituted phenylvinylsulfone derivatives(S) in-vivo against rice(Oryza sativa L.), Barnyard grass(Echinochloa crus-galli) and Pickerelweed(Monochoria vaginalis Presl) were measured by the pot test under paddy conditions. The (S) showed herbicidal symptom rapidly with lower activity(average $pI_{50}=2.0$) as proherbicide, which was excellent tolerance to rice. The structure activity relationships(SAR) were analyzed using such a physicochemical parameters as hydrophobic$({\pi})$ and molecular orbital(MO) quantity by the multiple regression technique, and discussed with quantum pharmacology. The herbicidal activities were related to the hydrophobic$({\pi})$ effect of X-substituent and orbital(HOMO & LUMO) energy. In case of Pickerelweed, the effect was rationalized by parabolic function of ${\pi}$ constant, where the optimal value of ${\pi}$ was 1.10. An increase in hydrophobicity and negative orbital energy by the electron attracting X-substituent may contribute to the herbicidal activity. Based on results proposed from SAR analysis, the mode of herbicidal action could be assumed.

• Journal of the Korean Chemical Society
• /
• v.26 no.1
• /
• pp.7-17
• /
• 1982

In order to predict substituent and Lewis acid effects on the regiospecificity of the Diels-Alder reaction, and to investigate the competition for the complexation of Lewis acid between diene and dienophile, frontier orbital theory has been applied to thermal and catalyzed Diels-Alder reaction by means of CNDO/2 MO method. It has been found that: (1) Lewis acid coordinated preferentially with diene rather than dienophile when carbonyl oxygen of acetoxy substituted diene had larger negative atomic charges than that of dienophile. (2) Most of the reaction were neutral electron demand type, and hence 4-C, 2-C and quantitative secondary orbital interacion methods were generally in good accord with experiments. (3) Sulfur activated the adjacent terminal carbon atom greatly to increase diene LUMO-dienophile HOMO interaction through vacant-d-orbital participation, and played an important role in controlling regioselectivity of neutral electron demand reaction type.

• Analytical Science and Technology
• /
• v.20 no.4
• /
• pp.339-346
• /
• 2007

To search the ninhydrin derivatives that have high chromogenic and fluorogenic properties, molecular holographic quantitative structure property relationship (HQSPR) models on the reactivity between glycine and ninhydrin analogues as latent fingerprint detector were derived and investigated quantitatively. The ${\varepsilon}LUMO$ (e.v.) energy of ninhydrin molecule was an important factor to reactivity of ninhydrin. And, it is suggested that the nucleophilic reaction by orbital-controlled reaction from the frontier molecular orbital (FMO) interaction between glycine and ninhydrin derivatives was more superior than that of electrophilic reaction by charged controlled reaction. The analytical results in atomic contribution maps also shows that the reactivity of ninhydrin was increased by meta-substituents as strong electron withdrawing groups on the benzo ring. Therefore, it is sugested by HQSPR and QSPR model that the 5,6-dinitroninhydrin molecule would increase the reactivity as much as three times as compared to none substituted ninhydrin molecule.

• Journal of the Korean Chemical Society
• /
• v.54 no.3
• /
• pp.291-294
• /
• 2010

In this study, we demonstrated high-efficiency blue organic light-emitting diodes (OLEDs) employing BCzVBi as a blue fluorescent dye doped into blue host material, DPVBi with various concentration. The optimized blue OLED device having high-efficiency was constructed with structure of NPB (500 ${\AA}$) / DPVBi:BCzVBi-6% (150 ${\AA}$)/$Alq_3$(300 ${\AA}$) / Liq (20 ${\AA}$) / Al (1000 ${\AA}$). The maximum luminescence of blue OLED was 13200 cd/$m^2$ at 13.8 V and current density and maximum efficiency were 26.4 mA/$cm^2$ at 1000 cd/$m^2$ and 4.24 cd/A at 3.9 V, respectively. Luminous efficiency shows two times higher than comparing with non-doped BCzVBi blue OLED whereas $CIE_{x,y}$ coordinate was similar with bare DPVBi blue OLED such as (0.16, 0.19). Electroluminescence of BCzVBi-6% doped blue OLED has two major peaks at 445 nm and 470 nm whereas pure DPVBi's blue peak appears at 456 nm and it is happened through endothermic Forster energy transfer by molecule's vibration between LUMO of DPVBi as host material and LUMO of BCzVBi as dopant in device.

• Applied Chemistry for Engineering
• /
• v.24 no.4
• /
• pp.396-401
• /
• 2013

Alternating copolymers, poly[9-(2-octyl-dodecyl)-9H-carbazole-alt-4,7-di-thiophen-2-yl-benzo[1,2,5]thiadiazole] (PCD20TBT) and poly[9,10-bis-(2-octyl-dodecyloxy)-phenanthrene-alt-4,7-di-thiophen-2-yl-benzo[1,2,5]thiadiazole] (PN40TBT), were synthesized by the Suzuki coupling reaction. The copolymers were soluble in common organic solvents such as chloroform, chlorobenzene, 1,2-dichlorobenzene, tetrahydrofuran and toluene. The maximum absorption wavelength and the band gap of PCD20TBT were 535 nm and 1.75 eV, respectively. The maximum absorption wavelength and the band gap of PN40TBT were 560 nm and 1.97 eV, respectively. The HOMO and the LUMO energy level of PCD20TBT were -5.11 eV and -3.36 eV, respectively. As for PN40TBT, the HOMO and the LUMO energy level of PCD20TBT were -5.31 eV and -3.34 eV, respectively. The polymer solar cells (PSCs) based on the blend of copolymer and PCBM (1 : 2 by weight ratio) were fabricated. The power conversion efficiencies of PSCs based on PCD20TBT and PN40TBT were 0.52% and 0.60%, respectively. The short circuit current density ($J_{SC}$), fill factor (FF) and open circuit voltage ($V_{OC}$) of the device with PCD20TBT were $-1.97mA/cm^2$, 38.2% and 0.69 V. For PN40TBT, the $J_{SC}$, FF, and $V_{OC}$ were $-1.77mA/cm^2$, 42.9%, and 0.79 V, respectively.

• The Korean Journal of Pesticide Science
• /
• v.11 no.2
• /
• pp.72-81
• /
• 2007

Quantitative structure-activity relationships (QSARs) on the pre-emergency herbicidal activity and reactivity of a series of new O,O-dialkyl-1-phenoxyacetoxy-1-methylphosphonates (S) analogues against seed of cucumber (Cucumus Sativa) were discussed quantitatively using 2D-QSAR and HQSAR methods. The statistical values of HQSAR model were better than that of 2D-QSAR model. From the frontier molecular orbital (FMO) interaction between substrate molecule (S) and $BH^+$ ion (I) in PDH enzyme, the electrophilic reaction was superior in reactivity. From the effect of substituents, $R_2$-groups in substrate molecule (S) contributed to electrophilic reaction with carbonyl oxygen atom while X, Y-groups contributed to nucleophilic reaction with carbonyl carbon atom. And the influence of X,Y-groups was more effective than that of $R_2$-groups. As a results of 2D-QSAR model (I & II) and atomic contribution maps with HQSAR model, the more length of X, Y-groups is longer, the more herbicidal activity tends to increased. And also, the optimal ${\epsilon}LUMO$ energy, $({\epsilon}LUMO)_{opt.}$=-0.479 (e.v.) of substrate molecule is important factor in determining the herbicidal activity. It is predicted that the herbicidal activity proceeds through a nucleophilic reaction. From the analytical results of 2D-QSAR and HQSAR model, it is suggested that the structural distinctions and descriptors that contribute to herbicidal activities will be able to applied new herbicide design.

• Journal of the Korean Chemical Society
• /
• v.23 no.5
• /
• pp.277-285
• /
• 1979

CNDO/2 calculations on $XC_6H_4CH_2Cl,\;where\;X = H,\;p-CH_3,\;p-NH_2\;and\;p-NO_2$, and on benzyl radicals, cations and anions have been carried out in order to investigate nonlinear Hammett behavior. Main conclusions reached are: 1. Benzyl chloride exhibits borderline behavior due to ${\sigma}-{\pi}$ conjugation between C-Cl bond and the ring-system. 2. The extent of mutual conjugation can be judged by $\pi$-charge and bond alternation and interfrontier level separation narrowing effects. 3.The electron donating para substituent reduces the HOMO AO coefficient of the benzylic carbon, while the electron withdrawing para substituent reduces the LUMO AO coefficient of the benzylic carbon.

• Journal of the Korean Chemical Society
• /
• v.55 no.3
• /
• pp.364-372
• /
• 2011

The corrosion inhibition of imatinib mesylate (IMT) on mild steel in 0.25 M sulphuric acid has been studied using gravimetric and potentiodynamic polarization techniques at various concentrations of inhibitor, temperature and fluid velocities. The results obtained showed that, inhibition efficiency (% IE) increases with increasing concentration of the inhibitor. The adsorption process on mild steel surface follows Langmuir adsorption isotherm. The values of Gibbs free energies of adsorption obtained suggest that, the adsorption process of IMT on mild steel is chemisorption. Thermodynamic parameters were evaluated and discussed. The electron orbital density distribution of HOMO and LUMO of IMT was used to discuss the inhibition mechanism. FT-IR spectroscopy and SEM images were used to analyze the surface adsorbed film.