• Journal of Pharmaceutical Investigation
• /
• v.22 no.3
• /
• pp.65-76
• /
• 1992

The superoxide dismutase (SOD)-mimetic activities of copper complexes of a series of salicylic acid (SA) analogs were tested and compared to the activity of bovine erythrocyte SOD using ferricytochrome c reduction assay. Stability constants of copper complexes were measured potentiometrically using SCOGS2 program. In the presence of 10 g/l albumin, all the copper complexes lost their SOD mimetic activities. Multiple regression analysis was employed for the statistical comparisons between the SOD mimetic activity and their physicochemical properties. Correlation exists for the SOD mimetic activity and steric parameter $(E_s)$ and/or electronic parameter $({\Sigma}{\sigma})$ in xanthine/xanthine oxidase (XOD) system, demonstrating that E, plays a key role in SOD activity whereas ${\Sigma}{\sigma}$ influences it to a lesser extent. The protective effect of copper complexes against membrane damage was measured by counting D-glucose released frm $EG_s$. D-glucose and XOD were entrapped within $EG_s$ and acetaldehyde was used as a substrate for XOD. In this membrane model system using $EG_s$, hydrophobic parameter $({\Sigma}{\pi})$ is of most importance, producing parabolic equation while $E_s$, and ${\Sigma}{\sigma}$ appear to playa minor role in protection against D-glucose release. In summary, to design an efficient SOD mimetic, stability, steric factor, lipophilicity and redox potential should be considered.

• Korea-Australia Rheology Journal
• /
• v.11 no.3
• /
• pp.241-246
• /
• 1999

In this study, we consider the effect of nonionic surfactants on the rheological responses of emulsion systems under the action of a uniform do electric field. The model emulsions consist of a less conducting dispersed phase and a more conducting continuous phase. When the shear flow is weak, the positive viscosity effect is produced due to the formation of chain-like morphology. The nonionic surfactants used here generate two distinctively different effects. Specifically, first, the steric hindrance induced by the surfactant molecules renders the structure unstable, and thereby reduces the degree of positive viscosity effect. Secondly, the presence of surfactant molecules also prevents the rotation of the dispersed droplets by anchoring across the interface or by decreasing the size of dispersed phase. The second effect suppresses the negative viscosity effect.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.10
• /
• pp.1915-1919
• /
• 2008

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl benzoates (5b) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The kinetic data have been compared with the data reported previously for the corresponding reactions of 2,4- dinitrophenyl benzoates (5a) to investigate the effect of changing the nucleofuge from 2,4-dinitrophenoxide to 3,4-dinitrophenoxide on reactivity and mechanism. The kinetic results show that aminolyses of 5a and 5b proceed through the same mechanism, i.e., a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step (RDS). Substrate 5a is more reactive than 5b when breakdown of $T^{\pm}$ is the RDS but less reactive when formation of $T^{\pm}$ is the RDS. Dissection of kN values into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1 }$ ratio) has revealed that 5a results in larger $k_2/k_{-1}$ ratios but smaller k1 values than 5b for all the amines studied. Since 2,4-dinitrophenoxide is less basic and a better nucleofuge than 3,4-dinitrophenoxide, the larger $k_2/k_{-1}$ ratios determined for the reactions of 5a than for those of 5b are as expected. The steric hindrance exerted by the ortho-nitro group on 5a contributes to the smaller k1 values found for the reactions of 5a than for those of 5b.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.7
• /
• pp.2081-2085
• /
• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of phenyl 2- pyridyl carbonate (6) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 6 is linear with ${\beta}_{nuc}$ = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Substrate 6 is over $10^3$ times more reactive than 2-pyridyl benzoate (5), although the reactions of 6 and 5 proceed through the same mechanism. A combination of steric hindrance, inductive effect and resonance contribution is responsible for the kinetic results. The reactions of 6 and 5 proceed through a cyclic transition state (TS) in which H-bonding interactions increase the nucleofugality of the leaving group (i.e., 2-pyridiniumoxide). The enhanced nucleofugality forces the reactions of 6 and 5 to proceed through a concerted mechanism. In contrast, the corresponding reaction of 4-nitrophenyl 2-pyridyl carbonate (7) proceeds through a stepwise mechanism with quantitative liberation of 4-nitrophenoxide ion as the leaving group, indicating that replacement of the 4-nitrophenoxy group in 7 by the PhO group in 6 changes the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as the leaving group (i.e., from 4-nitrophenoxide to 2-pyridiniumoxide). The strong electron-withdrawing ability of the 4-nitrophenoxy group in 7 inhibits formation of a H-bonded cyclic TS. The presence or absence of a H-bonded cyclic TS governs the reaction mechanism (i.e., a concerted or stepwise mechanism) as well as the leaving group (i.e., 2-pyridiniumoxide or 4-nitrophenoxide).

• Textile Coloration and Finishing
• /
• v.15 no.5
• /
• pp.321-326
• /
• 2003

In order for disperse dye based ink to be fitted with the critical requirements of ink jet printing, this study was undertaken to investigate the effects of 6 different dispersants on the milling efficiency of insoluble dye particles and dispersion stability of the final ink. It was found that a polystyrene dispersant with high molecular weight exerted relatively better dispersion stability which may be associated with its steric stabilization effect in the ink solution.

• Nuclear Engineering and Technology
• /
• v.5 no.1
• /
• pp.26-29
• /
• 1973

Halongen exchange reactions of phenylethyl bromides have been studied in acetone at 25$^{\circ}$and 35$^{\circ}C$. Results show that the reaction proceeds by a typical S$_{N}$2 path, and steric crowding effect in 1-phenylethyl bromide gives large variation in the activation parameters for chloride exchange.

• Bulletin of the Korean Chemical Society
• /
• v.17 no.10
• /
• pp.892-899
• /
• 1996

In order to elucidate the effect of alkoxy substituent in thexylborane and hence establish their usefulness as hydroborating agent, reactions of alkenes and alkynes with thexylalkoxyborane (ThxBHOR; R=Et, i-Pr, i-Bu, sec-Bu, t-Bu, Ph) were investigated in detail. The reagents readily hydroborated alkenes and alkynes of various structural types at 25 ℃ in excellent regioselectivity. The selectivity increases consistently with increasing steric size of alkoxy substituent. Especially, the selectivity achieved by the sec-butoxy derivative is comparable to that previously achieved by thexylhaloborane-methyl sulfide (ThxBHX·SMe2), the most selective hydroborating agent known.

• Bulletin of the Korean Chemical Society
• /
• v.5 no.6
• /
• pp.226-230
• /
• 1984

LIS's of cis and trans-methyl-2-phenylcyclopropanecarboxylate, cis and trans-t-butyl-2-phenylcyclopropanecarboxylate, cis and trans-N,N-dimethylcyclopropanecarboxamide, trans-2-phenylcyclopropyl methyl ketone and trans-2-phenylcyclopropyl t-butyl ketone have been studied. The LIS's hold the McConnell-Robertson relation and are mainly influenced by the steric effect. LIS's of trans isomers are larger than those of cis isomers. In trans isomers, the LIS's decrease in the following order: methyl ketone > methyl ester > N,N-dimethyl amide > t-butyl ketone${\sim}$t-butyl ester.

• Membrane Journal
• /
• v.20 no.2
• /
• pp.135-141
• /
• 2010

Various asymmetric Polysulfone membranes were prepared for a MBR process. Ether-typed alcohols (co-solvent) were added into a dope solution in order to control the pore size of membrane, whose effect on water permeability were investigated. Pore size of the prepared membranes were more affected by molecular-structure of co-solvent than by boiling point of theirs. With the increasing order of methoxy ($CH_3$-O-) < secondary propanol ($-CH_2$-CH(OH)$-CH_3$) < ethoxy ($CH_3-CH_2$-O-), water permeability of the prepared membrane increased. The phenomenon might attribute to the difference of molecularly steric hinderance of co-solvent (eg, Methoxy propanol, Ethoxy ethanol, Methoxy ethanol) in dope solution during the phase inversion. By the addition of ether typed alcohol into a dope solution, the pore size of MF (microfiltration) could be controlled. Also, Membrane prepared was applied to a MBR process and the system was stably operated for 2 months.

• YAKHAK HOEJI
• /
• v.42 no.2
• /
• pp.159-164
• /
• 1998

The secondary hydroxy group at side chain of shikonin structure was selectively acylated with various haloacetic acids in presence of dicyclohexylcarbodiimide and 4-dimethylamin opyridine to produce haloacetylshikonin derivatives. The cytotoxicity of monohaloacetylshikonin derivatives against L1210 cells increased in the following order; monochloroacetylshikonin ($ED_{50}$, 0.142${\mu}$g/ml) > monobromoacetylshikonin ($ED_{50}$. 0.158${\mu}$g/ml) > monoiodoacetylshikonin ($ED_{50}$, 0.173${\mu}$g/ml). Introduction of larger halogen atoms decreased the cytotoxic activity, presumably due to steric hinderance. The cytotoxicity of chloroacetylshikonin derivatives was dependent on the number of chlorine atom, thus increasing in the following order; trichloroacetylshikonin (0.032${\mu}$g/ml) > dichloroacetylshikonin (0.059${\mu}$g/ml) > monochloroacetylshikonin ($ED_{50}$, 0.142${\mu}$g/ml). Thus, the electron withdrawing effect seems to be important for the cytotoxicity of chloroacetylshikonin derivatives. Consistent with the above, dichloroacetylshikonin (T/C. 182%) and trifluoroacetylshikonin (195%) showed higher T/C values than monochloroacetyl-(T/C, 122%), monobromoacetyl-(T/C, 154%) and monoiodoacetylshikonin (T/C, 117%) derivatives. Haloacetylshikonin derivatives showing lower cytoxic activities against L1210 cells exhibited lower T/C values. It seems that there is a relationship between the cytoxicity of haloacetylshikonin and their antitumor activity.