• The Korean Journal of Pesticide Science
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• v.6 no.1
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• pp.16-24
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• 2002

Research trends in the measurement of foliar uptake of pesticides and the recently proposed action mechanism of the surfactant-induced uptake of pesticides were reviewed with the related reports and studies. Major techniques used in those fields are bioassay, radiotracer techniques with leaves or cuticular membrane. Recently, a new method using Congo Red as a tracer was proposed. The limiting factor in the pesticides uptake into leaves is the waxy layer which consists of the epicuticular and cuticular wax. Physico-chemical parameters such as molar volume, water solubility and partition coefficient of pesticides have limited influences on the pesticide uptake into leaves. Polydisperse ethoxylated fatty alcohol surfactants are well known as the good activator for many pesticides. It is now generally agreed that uptake activation is not related to the intrinsic surface active properties of surfactants such as surface activity, solvent property, humectancy and critical micelle concentration. Recent studies using ESR-spectroscopy revealed that the surfactants have an unspecific plasticising effect on the molecular structure of the wax and cuticular matrix, leading to increased mobilities of pesticides. Penetration of surfactants into waxy layer altered the pesticide mobility in wax and the partition coefficient of pesticide, and then the pesticides penetration into leaves was enhanced temporally. The enhancing effect of surfactant could be significantly different depending on the carbon number of aliphatic moiety and the number of ethoxy group in polyoxyethylene chain of surfactants. It is suggested that the rate of penetration of surfactants should have a significant relationship with the rate of penetration of pesticides.

• Economic and Environmental Geology
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• v.36 no.5
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• pp.375-380
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• 2003

This study was carried out 1) to investigate the pH effect on solubilization of phenanthrene by biosurfactant in aqueous system and 2) to evaluate the pH effect on the biodegradation rate of phenanthrene in the presence and the absence of the biosurfactant by phenanthrene degraders. Tween 80, which is a chemically synthesized surfactant, showed greater solubilizing capacity than rhamnolipid. The solubilization capacity can be expressed as a MSR(molar solubilization ratio=moles of organic compounds solubilized per mole of surfactant). The calculated MSR of Tween 80 and rhamnolipid were 0.1449 and 0.0425 respectively. The kinetic study of phenanthrene solubilization by rhamnolipid showed that solubilization mechanism could reach equilibrium within 24 hours. Addition of 240 ppm rhamnolipid solution, which concentration is 4.3 times of Critical Micelle Concentration(CMC), caused 9 times solubility enhancement compared to water solubility. The highest solubilities were detected around a pH range of 4.5-5.5. Changes in apparent solubility with the changes in pH are possibly related to the fact that the rhamnolipid, an anionic surfactant, can form different structures depending on the pH. Two biodegradation experiments were performed in the absence and the presence of rhamnolipid, with the cell growth investigated using a spread plate method. The specific growth rates at pH 6 and 7 were higher than at the other pH, and the HPLC analysis data, for the total phenanthrene loss, confirmed the trends in the $\mu$(specific growth rate) values. In presence of rhamnolipid, maximum $\mu$ values shifted from around pH 5 which showed maximum enhancement of solubility in the abiotic experiment, compared to the $\mu$ values obtained without the biosurfactant. In this study, the increase in the observed specific grow rate(1.44 times) was not as high as the increase in solubilization(5 times). This was supported by the fact all the solubilized phenanthrene is not bioavailable to microorganisms.

• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.522-532
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• 1985

The reactions of p-nitrophenyldiphenylphosphate (p-NPDPP) with anions of benzimidazole (BI) and its 2-alkyl derivatives (R-BI) are strongly catalyzed by the micelles of cetyltrimethyl ammonium bromide (CTABr). On the other hand, the first order rate constants $(k'_{R-BI^-})$ and the second order rate constants $(k_{m(R-BI^-)})$ of the reactions mediated by R-$BI^-$in the micellar pseudophase are much smaller than those mediated by $BI^-$. In order to explain the slower rates of the micellar reactions mediated by R-$BI^-$, we compared the concentration-ratios ([R-$BI^-$]/[$BI^-$]) with the first order rate constant-ratios $(k'_{R-BI^-}/k'_{BI^-})$ and the second order constant-ratios $(k_{m(R-BI^-)}/k_{m(BI^-)})$ for the reactions taking place in the micellar pseudophase. The rate constant-ratios were much smaller than the concentration-ratios. For example in a 5 ${\times}10^{-4}$M butyl-BI solution, the two ratios were 0.089 and 0.430 (for the first order) respectively, and in a $10^{-4}$M butyl-BI solution the former was 0.100 (for the second order). This predicts that the reactivities of R-$BI^-$ in the micellar pseudophase are much smaller than that of $BI^-$. Based on the values of several kinetic parameters measured for dephosphorylation of p-NPDPP mediated by R-$BI^-$, a schemetic model is proposed. Due to the hydrophobicity and the steric effect of the alkyl substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long cetyl groups of CTABr. Consequently, the movements of R-$BI^-$ bound to the micelle should be restricted, leading to decreased collison frequencies between the nucleophiles and p-NPDPP. We refer this as an "anchor effect". This effect became more predominent when a larger alky group in R-BI was employed and when a greater concentration of R-BI was used.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.97-105
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• 1989

This study deals with micellar effects on hydrolyses of p-nitrophenyl carboxylic esters(p-NPCE) mediated by 2-alkylbenzimidazole(R-BI) and sodium 2-alkylbenzimidazole-5-sulfonate(R-BISO$_3$Na) in aqueous and CTABr solutions. The reactions mediated by R-BI and R-BISO$_3$Na in micellar solutions are obviously slower than those by benzimidazole(BI) and sodium benzimidazole-5-sulfonate(BISO$_3$Na) respectively, and the reaction rates were decreased with increase of lengths of alkyl groups. This prestents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups for R-BI and R-BISO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(${\Delta}H^{\neq},\;{\Delta}G^{\neq}\;and\;{\Delta}S^{\neq}$) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole(BI) moiety of R-BISO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) which form a micelle of themselves increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr. We measured the isotope effects to elucidate the mechanism of hydrolyses of p-nitrophenyl carboxylic esters, and the relative first order rate constant($k'_{H_2O}/k'_{D_2O}$) are on range of 2.5∼3.2. This range is too high to conclude that the hydrolyses of p-NPA mediated by various R-BISO$_3$Na proceed by nucleophilic mechanism. In other words, the reactions are assumed to proceed in part by general basic one, as compared with the reaction catalyzed by imidazole(IM) in aqueous solution.

• Applied Chemistry for Engineering
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• v.8 no.6
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• pp.914-919
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• 1997

On the basis of theory of Bratsch's electronegativity equalization, the electronegativity equalization, the group electronegativities and the group partial charges for anionic and nonionic surfactants could be calculated by using Pauling's electronegativity parameters. From calculated results, we have investigated how CMC, hydrophilic and hydrophobic groups, group partial charge, electronegativity of hydrophilic and hydrophobic groups, structural stability of micelle for anionic and nonionic surfactants are related. It was fround that CMC depends upon group partial charge and group electronegativity of hydrophilic and hydrophobic groups of surfactants. For the anionic surfactants, negative partial charge in hydrophobic group is delocalized as the carbon number in hydrophobic group increase. So negative partial charge of hydrophilic group has very large electronegativity that is decreased. And CMC decreases as hydration ability of hydrophilic groups which decreases relatively. For the nonionic surfactant, partial charge and electronegativity in hydrophobic group increases with the increment of carbon number in hydrophobic group. And CMC decreases because electronegativity of hydrophilic group is decreased with the increment of electronegativity of hydrophilic group. However, with the increase of repeating units in hydrophilic group, the negative partial charge of hydrophilic group increases. So CMC increases because surfactants hydrate rather than form micelles in aqueous solution by the increase of hydration ability.

• Analytical Science and Technology
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• v.6 no.1
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• pp.1-8
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• 1993

The purpose of this study is to investigate the elution behavior of monosubstituted phenols and benzenes in micellar liquid chromatographic system, $C_{18}$ column-anionic surfactant, sodium dodecyl sulfate(SDS). The partition coefficients between the micellar pseudophase-water and modified stationary phase-water are calculated by the relationship between solute retention and micellar mobile phase(SDS) composition. The free energy of transfer of solute from water to micelle is also calculated from these values. There is a direct correlation between the hydrophobicity parameters in MLC and corresponding partition data for 1-octanol-water, which indicates that the hydrophobicity of molecules plays an important role in the partition for both systems and that quantitative structure activity relationships(QSAR) are available from studies on micellar partition. The other purpose of this study is to investigate methylene selectivity of alkyl homologous series through correlation between retention and the number of carbons. The correlation between hydrophobicity parameters in MLC and 1-octanol-water partition data was also observed when n-propanol was as a modifier in the mobile phase.

• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.629-636
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• 1990

Dephosphorylation of p-nitrophenyldiphenylphosphate(p-NPDPP) mediated by anions of sodium 2-alkylbenzimidazole-5-sulfonate(R-BI-SO$_3$Na) in CTABr micellar solutions are obviously slower than that by anion of sodium benzimidazole-5-sulfonate(BI-SO$_3$Na), and the reation rates were decreased with increase of lengths of alkyl groups. This presents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups of R-BI$^-$SO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(△H$^\neq$/TEX>, △G$^\neq$/TEX> and △S$^\neq$/TEX>) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole moiety of R-BI$^-$SO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) are micellized for themseleves, and increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr.

• Applied Chemistry for Engineering
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• v.19 no.3
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• pp.351-356
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• 2008

Titania nanoparticles were prepared by controlled hydrolysis of titanium tetraisopropoxide (TTIP) in water-in-oil (W/O) and microemulsion stabilized with a nonionic surfactant, N P-10 (Polyoxyethylene Nonylphenol Ether: $C_9H_{19}C_6H_4(OCH_2CH_2)_{10}OH$)). The nanosized particles prepared in W/O microemulsion were characterized by FT-IR, TEM, XRD, TGA, and DTA. In addition, the photocatalytic degradation of p-nitrophenol has been studied by using a batch reactor in the presence of UV light in order to compare the photocatalytic activity of prepared nanosized titania. The nanaosized titania particles calcined at $300{\sim}600^{\circ}C$ showed an anatase structure, but it transformed to a rutile phase above $700^{\circ}C$ of calacination temperature. With an increase of $W_o$ ratio, the crystallite size increased but photocalytic activity decreased. The titania synthesized at $W_o=5$, R = 2, and calcined at $400{\sim}500^{\circ}C$ showed the highest activity on the photocatalytic degradation of p-nitrophenol.

• Applied Chemistry for Engineering
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• v.30 no.3
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• pp.303-307
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• 2019

Sophorolipid is a biological surfactant of the glycolipid structure produced by Candida bombicola, which generally exists as a mixture of acidic and lactonic forms. In this study, we investigated physico-chemical properties, antibacterial activities, and cytotoxicity of the sophorolipid containing more than 96% of the lactonic form, produced by the gene regulation of production strains and application of a metabolic engineering technique. The lactonic sophorolipid showed a weak acidity in the range of pH 3.2~4.6 when diluted in water at the concentrations from 1 to 0.001 wt%. The $pK_a$ value of the lactonic sophorolipid was estimated to be around 4.3 from the acid-base titration curve. The critical micelle concentration (CMC) of the lactonic sophorolipid was $10^{-2}wt%$, at which the surface tension of aqueous solution was reduced to 36 mN/m. The lactonic sophorolipid showed the minimum inhibitory concentrations (MIC) of $1{\times}10^{-3}$ and $5{\times}10^{-3}g/mL$ against Propionibacterium acnes and Corynebacterium xerosis, respectively. The MTT (3-(4,5-Dimethylthiazol-2-yl)-2,5-Diphenyltetrazolium Bromide] assay showed that cytotoxicity of the lactonic sophorolipid was ten times lower than that of triclosan.

• Applied Chemistry for Engineering
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• v.9 no.6
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• pp.822-828
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• 1998

Binary system of water and polyoxyethylene dodecyl ether, $C_{12}H_{25}(OCH_2CH_2)nOH$, have been studied by $^1H$ NMR techniques. For n=5($C_{12}EO_5$) and n=8($C_{12}EO_8$), the self-diffusion coefficients of nonionic surfactants in the isotropic phase($L_1$) have been measured by using pulsed field gradient technique for a range of temperature and concentrations. In addition the line widths of the different proton signals have been monitored, and samples of some liquid crystalline characteristic were also studied. Dramatic Broadening of the methylene signals of the alkyl($C_{12}H_{25}$) chain is observed as the hexagonal liquid crystalline phase is approached in the $C_{12}EO_5-$water system, while only small broadening is observed in the $C_{12}EO_8-$water system. It was shown that there was a growth of $C_{12}EO_5$ micelles to rods with increasing concentrations, while the $C_{12}EO_8-$ micelles at low temperature remain small in the concentration range. The self-diffusion coefficients of the surfactants decrease rapidly with increasing concentration until a minimum is reached after which there is slow increase. The location of the minimum point occurs at lower concentrations the temperature is close to the cloud point, where the system separate into two isotropic phase. In the line width studies, broadening is found at a certain temperature interval when the concentration is increased in the $C_{12}EO_5$ system. The results indicate that the surfactant aggregates grow in size at the cloud point is approached. The aggregates seem to be flexible and probably not to be of a definite shape close to the cloud point. In the $C_{12}EO_8$ system, the micelles are much less affected by an increase in temperature and micellar growth can't be unambiguously established. The methylene signals of the ethylene oxide moieties consistantly show narrower $^1H$ signals, showing that in the aggregates they are less ordered than the chain methylenes. The various changes in aggregate size and shape are correlated with the stability ranges of the isotropic and liquid crystalline phases according to phase diagrams from the literature. Both aggregate size and phase structure are in qualitative agreement with concentration based on the effective shape of the molecules at different temperature and concentration.