• Bulletin of the Korean Chemical Society
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• v.26 no.9
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• pp.1339-1343
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• 2005

The N-inversion energies and nucleophilic ring-opening reactions of N-substituted aziridine compounds are investigated using B3LYP/6-31+$G^*$ methods, where substituents (R) on the nitrogen atom has been H (1), Me (2), Ph (3), Bn (4), CHMePh (5), $CO_2Me$ (6), COPh (7) and $SO_2Ph$ (8). The N-inversion energy with X group are decreased as the following order: R = CHMePh (17.06 kcal/mol) $\gt$ Me (16.97) $\gt$ Bn (16.70) $\gt$ H (16.64) $\gt$ $SO_2Ph$ (12.18) $\gt$ Ph (8.91) $\gt$ COPh (5.75) $\gt$ $CO_2Me$ (5.48). For reactivity of the ring opening toward cyanide ion, the aziridine 6 (R=$CO_2Me$) is shown to be the most reactive one. During the ring opening of aziridine 6 by CN$^{\ominus}$, the torsional OCNC angle becomes near to $180^{\circ}$, where the geometry allows for the effective incorporation of electrons of the nitrogen atom to the C=O bond. It would be a possible driving force for nucleophilic ring opening reaction as well as decreasing the N-inversion energy barrier. Regarding to the regioselectivity, the orientation of nucleophile in ring opening reaction appears to be different in the case of 9 and 10. The results are discussed in terms of steric/electronic effect of the $C_2$-substituents.

• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.802-807
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• 1996

Second-order rate constants have been measured spectrophotometrically for the reactions of aryl benzoates (X-C6H4CO2C6H4-Y) with EtO-, Z-C6H4O- and Z-C6H4C(Me)=NO- in absolute ethanol at 25.0 ℃. All the reactions have been performed in the presence of excess 18-crown-6 ether in order to eliminate the catalytic effect shown by alkali metal ion. A good Hammett correlation has been obtained with a large ρ- value (-1.96) when σ- (Z) constant was used for the reaction of p-nitrophenyl benzoate (PNPB) with Z-C6H4O-. Surprisingly, the one for the reaction of PNPB with Z-C6H4C(Me)=NO- gives a small but definitely positive ρ- value (＋0.09). However, for reactions of C6H5CO2C6H4-Y with EtO-, correlation of log k with σ- (Y) constant gives very poor Hammett correlation. A significantly improved linearity has been obtained when σ0 (Y) constant was used, indicating that the leaving group departure is little advanced at the TS of the RDS. For reactions of X-C6H4CO2C6H4-4-NO2 with EtO-, C6H5O- and C6H5C(Me)=NO-, correlations of log k with σ (X) constants for all the three nucleophile systems give good linearity with large positive ρ values, e.g. 2.95, 2.81 and 3.06 for EtO-, C6H5O- and C6H5C(Me)=NO-, respectively. The large ρ values clearly suggest that the present reaction proceeds via a stepwise mechanism in which the formation of the addition intermediate is the RDS.

• Journal of the Korean institute of surface engineering
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• v.34 no.5
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• pp.414-420
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• 2001

A 30-kV plasma immersion ion implantation setup (P $I^3$) has been equipped with a self-developed 6'-magnetron to perform hard coatings with enhanced adhesion by P $I^3$D(P $I^3$ assisted deposition) process. Using ICP source with immersed Ti antenna and reactive magnetron sputtering of Ti target in $N_2$/Ar ambient gas mixture, the TiN films were prepared on Si substrates at different pulse bias and ion-to-atom arrival ratio ( $J_{i}$ $J_{Me}$ ). Prior to TiN film formation the nitrogen implantation was performed followed by deposition of Ti buffer layer under A $r^{+}$ irradiation. Films grown at $J_{i}$ $J_{Me}$ =0.003 and $V_{pulse}$=-20kV showed columnar grain morphology and (200) preferred orientation while those prepared at $J_{i}$ $J_{Me}$ =0.08 and $V_{pulse}$=-5 kV had dense and eqiaxed structure with (111) and (220) main peaks. X-ray diffraction patterns revealed some amount of $Ti_{x}$ $N_{y}$ in the films. The maximum microhardness of $H_{v}$ =35 GN/ $M^2$ was at the pulse bias of -5 kV. The P $I^3$D technique was applied to enhance wear properties of commercial tools of HSS (SKH51) and WC-Co alloy (P30). The specimens were 25-kV PII nitrogen implanted to the dose 4.10$^{17}$ c $m^{-2}$ and then coated with 4-$\mu\textrm{m}$ TiN film on $Ti_{x}$ $N_{y}$ buffer layer. Wear resistance was compared by measuring weight loss under sliding test (6-mm $Al_2$ $O_3$ counter ball, 500-gf applied load). After 30000 cycles at 500 rpm the untreated P30 specimen lost 3.10$^{-4}$ g, and HSS specimens lost 9.10$^{-4}$ g after 40000 cycles while quite zero losses were demonstrated by TiN coated specimens.s.

• Journal of Sensor Science and Technology
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• v.24 no.3
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• pp.181-187
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• 2015

The magnetoelectric characteristics on layered $Fe_{78}B_{13}Si_9/PZT$ and $Fe_{78}B_{13}Si_9/PZT/Fe_{78}B_{13}Si_9$($t_m=0.017$, 0.034mm) composites by epoxy bonding for magnetic field sensor were investigated in the low-frequency range and resonance frequency range. The optimal bias magnetic field $H_{dc}$ of these samples was about 23~63 Oe range. The Me coefficient of $Fe_{78}B_{13}Si_9/PZT/Fe_{78}B_{13}Si_9(t_m=0.034mm)$ composites reaches a maximum of $186mV/cm{\cdot}Oe$ at $H_{dc}=63Oe$, f=50 Hz and a maximum of $1280mV/cm{\cdot}Oe$ at $H_{dc}=63Oe$, resonance frequency $f_r=95.5KHz$. The output voltage shows linearity proportional to ac fields $H_{ac}$ and is about U=0~130.6 mV at $H_{ac}=0{\sim}7Oe$, f=50 Hz, U=0~12.4 V at $H_{ac}=0{\sim}10Oe$, $f_r=95.5KHz$(resonance frequency). The optimal frequency(f=50 Hz) of this sample is around the utility ac frequency(f=60 Hz). Therefore, this sample will allow for ac magnetic field sensor at utility frequency and low bias magnetic fields $H_{dc}$.

• Korean Journal of Agricultural Science
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• v.24 no.1
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• pp.11-15
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• 1997

The importance value and volume growth percentage, based on the data obtained from 33 quadrats by $relev{\acute{e}}$ method of Mueller-Dombois and Ellenberg, were applied to investigate Pinus thunbergii forests in Taean Haean National Park. The investigation was done from July till September 1996. 1. The dominant species of tree were found in the order of Pinus thunbergii, Quercus dentata, Robinia pseudcacacia, Platycarya strobilacea, Carpinus coreana, Albizzia julibrissin, Pinus densi-thunbergii, and Quercus serrata 2. The volume growth percentage of Pinus thunbergii was about 0.6%~10.5% and the mean of it's was 3.8%. 3. Chemical properties of forest soil showed ranging pH 4.8~6.3, organic matter 1.51~11.79%, $P_2O_5$ 2.5~14.5ppm, $Ca^{{+}{+}}$ 1.3~6.6(me/100g), $Mg^{{+}{+}}$ 0.4~2.6(me/100g), and $K^+$ 0.23~1.89(me/100g).

• Journal of the Korean Chemical Society
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• v.47 no.6
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• pp.547-552
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• 2003

Separation and determinations of Co(II) and Ni(II) ions as their 4-(2-pyridylazo)resorcinol(PAR) chelates by reversed-phase capillary high-performance liquid chromatography(RP-CpHPLC) were performed. Among many capillary columns, Vydac C4 column was selected and acetonitrile solution was used as mobile phase. The effect of pH and MeCN concentration(%) on the retention factor, k and peak intensity was examined and discussed. As a results, it was found that 22.5% MeCN and pH 5.60 was adequate as mobile phase for the separation of the two metal ions and determination of Co(II) ion, but the mobile phase condition for Ni(II) ion determination was 22.5% MeCN of pH 7.20. Detection limit(D.L., S/N=3) of Co(II) and Ni(II) ions were $2.0{\times}10{-7}$ M(14.9 ppb) and $1.0{\times}10{-6}$ M(59.2 ppb), respectively.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4161-4164
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• 2012

Density functional MO calculations for the methylsilole anion of $[C_4H_4SiMe]^-$ and methylgermole anion of $[C_4H_4SiMe]^-$ at the B3LYP (full)/6-311+$G^*$ level (GAUSSIAN 94) were carried out and characterized by frequency analysis. The ground state structure for the methylsilole anion and methylgermole anion is that the methyl group is pyramidalized with highly localized structure. The difference between the calculated $C_{\alpha}-C_{\beta}$ and $C_{\beta}-C_{\beta}$ distances are 9.4 and 11.5 pm, respectively. The E-Me vector forms an angle of $67.9^{\circ}$ and $78.2^{\circ}$ with the $C_4E$ plane, respectively. The optimized structures of the saddle point state for the methylsilole anion and methylgermole anion have been also found as a planar with highly delocalized structure. The optimized $C_{\alpha}-C_{\beta}$ and $C_{\beta}-C_{\beta}$ distances are nearly equal for both cases. The methyl group is located in the plane of $C_4E$ ring and the angle between the E-Me vector and the $C_4E$ plane for the methylsilole anion and methylgermole anion is $2.0^{\circ}$ and $2.3^{\circ}$, respectively. The energy difference between the ground state structure and the transition state structure is only 5.1 kcal $mol^{-1}$ for the methylsilole anion. However, the energy difference of the methylgermole anion is 14.9 kcal $mol^{-1}$, which is much higher than that for the corresponding methylsilole monoanion by 9.8 kcal $mol^{-1}$. Based on MO calculations, we suggest that the head-to-tail dimer compound, 4, result from [2+2] cycloaddition of silicon-carbon double bond character in the highly delocalized transition state of 1. However, the inversion barrier for the methylgermole anion is too high to dimerize.

• Natural Product Sciences
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• v.9 no.4
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• pp.241-244
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• 2003

A new (2) and a known (1) acylated taurine derivatives were isolated from MeOH extract of the starfish Certonardoa semiregularis. Another new acylated taurine derivative (3) was isolated from the MeOH extract of the sponge Erylus nobilis. The structures were determined on the basis of spectral analysis.

• Asian-Australasian Journal of Animal Sciences
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• v.13 no.5
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• pp.605-612
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• 2000

Four young swamp buffalo cows of similar age ranging in weight between 280 to 380 kg and trained to do physical work were used in a study to determine energy and protein requirements for draught using a $4{\times}4$ Latin square designed experiment. The experiment consisted of field trials employing 4 levels of work load, e.g. no work as control, and loads amounting 450 to 500 Newton (N) pulled continuously for 1, 2 and 3 h daily for 14 consecutive days. Cows were fed king grass (Penisetum purpuroides) ad libitum and were subjected to materials balance trials. Body composition was estimated in vivo by the body density method and daily energy expenditure (EE) was calculated from ME minus retained energy (RE). The results show that EE while not working ($EE_{resting}$) was $0.42kgW^{0.75}MJ/d$ and maintenance ME ($ME_m$) was $0.37kgW^{0.75}MJ/d$. ME requirement increased to 1.65 times maintenance for the work of 3 hours. The energy expended for doing exercise ($E_{exercise}$) was 9.56, 20.0 and 25.86 MJ/cow for treatments 1, 2 and 3 II, respectively. Fat retention was absent in all groups of working cows, but protein retention was only negative for cows undertaking 3 h work. The relationship between $E_{exercise}$ (MJ), work load (F, kN), work duration (t, h) and body mass (W, kg) was found to be: $E_{exercise}=(0.003F^{1.43}t^{0.93})/W^{0.09}MJ$. The maintenance requirement for digestible protein was $2.51kgW^{0.75}g/d$, whereas digestible protein for growth ($DP_{growth}$) and for work ($DP_{work}$) followed the equations: $DP_{growth}=[(258+1.25W^{0.75}){\Delta}Wkg/d]g$ and $DP_{work}=[12.59e^{0.95t}]g$, respectively The coefficients a, b and c for the calculation of $E_{exercise}$ components according to the Lawrence equation were found to be 2.56 J/kgW.m, 5.2 J/kg load carried.m and 0.29, respectively, thus efficiencies to convert ME into work were 0, 16.09, 27.3 and 32.44% for control, 1, 2 and 3 h/d work, respectively. ME and DP requirements for a 250 to 400 kg working buffalo cow allowing to growth up to 0.5 kg/d are presented.

• Korean Chemical Engineering Research
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• v.48 no.5
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• pp.643-648
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• 2010

Production of biodiesel from soybean oil catalyzed by Lewis acidic ionic liquids(ILs) containing metal chloride salts was investigated in this study. Metal chloride salts, such as $SnCl_2$, $ZnCl_2$, $AlCl_3$, $FeCl_3$ and CuCl, were screened for oil transesterification in the range of 363-423 K. Among these metal chlorides, tin chloride showed particularly high catalytic property for the oil transesterification. Similarly, among these Lewis acidic ionic liquid catalysts, $[Me_3NC_2H_4OH]Cl-2SnCl_2$ resulted in a high fatty acid methyl esters(FAMEs) content of 91.1% under the following reaction conditions: 403 K, 14 h, and a molar ratio of 1:12:0.9 (oil:methanol:catalyst). Unlike the pure tin chloride catalysts, Lewis acidic ILs containing tin chloride $[Me_3NC_2H_4OH]Cl-2SnCl_2$ catalyst could be recycled up to five times without any significant loss of activity by separating from the FAMEs with simple decantation. The Lewis acidity and high moisture-stability of this catalyst appeared to be responsible for the excellent catalytic performance. The effects of reaction time and the molar ratio of methanol/catalyst to oil on the FAMEs production were also studied in this work.