The effects of nonelectrolytes (ureas, amino acids, sugars) on the cloud point (CP) of nonionic surfactant Triton X-114 (TX-114) and tetra-n-butylammonium bromide (TBAB) system were studied. Ureas as well as thioureas...The effects of nonelectrolytes (ureas, amino acids, sugars) on the cloud point (CP) of nonionic surfactant Triton X-114 (TX-114) and tetra-n-butylammonium bromide (TBAB) system were studied. Ureas as well as thioureas increased the CP. Behaviors of amino acids depended upon their nature. Nonpolar and uncharged polar amino acids were less effective in changing the CP. However, tryptophan and phenylalanine increased the CP sharply. Acidic amino acid (aspartic acid) and sugars decreased the CP. The results were explained in terms of their effect on water structure. Amino acids got solubilized either in the micellar interior or in the bulk phase.展开更多
This study deals with the enhanced solubilization of polycyclic aromatic hydrocarbons （PAHs） such as phenanthrene （PHE） and fluorene （FLR） in a pure cationic gemini （G6） and three conventional surfactants [pol...This study deals with the enhanced solubilization of polycyclic aromatic hydrocarbons （PAHs） such as phenanthrene （PHE） and fluorene （FLR） in a pure cationic gemini （G6） and three conventional surfactants [polyethylene glycol dodecyl ether （Brij35）, cetyltrimethyl ammonium bromide （CRAB） and sodium lauryl sulfate （SDS）] as well as in their equimolar binary combinations （G6-Brij35, G6-CTAB and G6-SDS）. Their solubilization efficiency toward PHE and FLR has been quantified in terms of the molar solubilization ratio （MSR） and the micelle-water partition coefficient （Kin）. The ideality/nonideality of the mixed micelles is discussed with the help of Clint, Rubingh and Rosen＇s approaches. These theories determine the deviation of experimental critical micelle concen- tration （CMC） values from ideal critical micelle concentration, which was measured by evaluating the interaction parameters （/3m and/3）. Negative values ofβm were observed in all the equimolar binary systems, which show synergism in the mixed micelles. Whereas at air/liquid interface synergism was observed in the systems G6-CrAB and G6-Brij35; G6-SDS exhibited an antagonistic effect. The order of MSR and Km was G6-CTAB 〉 G6- Brij35 〉 G6-SDS for phenanthrene as well as for fluorene.展开更多
The effect of electrolytes on the micellar behavior of an amphiphilic drug, chlorpromazine (CPZ) hydrochloride, was studied using cloud point (CP) and dye solubilization techniques. In the presence of KBr, increase in...The effect of electrolytes on the micellar behavior of an amphiphilic drug, chlorpromazine (CPZ) hydrochloride, was studied using cloud point (CP) and dye solubilization techniques. In the presence of KBr, increase in pH led to decrease in the CP of 50 mmol·L-1 drug solution (prepared in 10 mmol·L-1 sodium phosphate (SP) buffer) because of deprotonation of drug molecules at high pH. The visible absorbance increased (due to dye solubilization) with the increase in pH from 6.5 to 6.9, which indicated micellar growth. At fixed pH (6.7), addition of inorganic salts (KF, KCl, and KBr) to drug solutions (50 mmol·L-1) caused an increase in the CP as well as in the visible absorbance, with effectiveness being in the order: F-<Cl-<Br-. The results were discussed on the basis of counter-ion binding and their effect toward micellar growth. Cations (co-ions) also led to an increase in the CP (and also the visible absorbance), with their effectiveness order being Li+ >Na+ >K+, which was explained by considering cognizance of their hydrated radii. Compared with anions, their effect was small. Increase in [CPZ] caused micellar growth and hence the CP as well as the visible absorbance increased. The overall behavior was discussed in terms of electrostatic interactions and micellar growth.展开更多
The behavior of the mixed amphiphilic drug promethazine hydrochloride(PMT) and cationic as well as nonionic surfactants was studied by tensiometry.The cmc values of the PMT-surfactant systems decrease at a surfactant ...The behavior of the mixed amphiphilic drug promethazine hydrochloride(PMT) and cationic as well as nonionic surfactants was studied by tensiometry.The cmc values of the PMT-surfactant systems decrease at a surfactant mole fraction of 0.1 and it then becomes constant.The critical micelle concentration(cmc) values are lower than the ideal cmc(cmc*) values for PMT/TX-100,PMT/TX-114,PMT/Tween 20,and PMT/Tween 60 systems.For the PMT/Tween 40,PMT/Tween 80,PMT/CPC,and PMT/CPB systems the cmc values are close to the cmc* values.This indicates that PMT forms mixed micelles with these surfactants by attractive interactions.The surface excess(Γmax) decreases in the presence of surfactants.The rigid structure of the drug makes adsorption easier and the contribution of the surfactant at the interface decreases.The interaction parameters βm(for the mixed micelles) and βσ(for the mixed monolayer) are negative indicating attraction among the mixed components.展开更多
The mixed micelle formation of binary cationic 14-s-14 gemini with conventional single chain surfactants was studied by conductivity measurements.The critical micelle concentration(cmc) and the degree of counterion bi...The mixed micelle formation of binary cationic 14-s-14 gemini with conventional single chain surfactants was studied by conductivity measurements.The critical micelle concentration(cmc) and the degree of counterion binding values(g) of the binary systems were determined.The results were analyzed by applying regular solution theory(RST) to calculate micellar compositions(X),activity coefficients(f1,f2),and the interaction parameters(β).The synergistic interactions of all the investigated cationic gemini+conventional surfactant combinations were found to be dependent upon the length of hydrophobic spacer of the gemini surfactant.The excess Gibbs free energy of mixing was evaluated,and it indicated relatively more stable mixed micelles for the binary combinations.展开更多
The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of chromium dipeptide complex ([Cr(Ⅲ)-Gly-Gly]2+) with ninhydrin under varying conditions has been investigated. The rates o...The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of chromium dipeptide complex ([Cr(Ⅲ)-Gly-Gly]2+) with ninhydrin under varying conditions has been investigated. The rates of the reaction were determined in both water and surfactant micelles in the absence and presence of various organic and inorganic salts at 70 ℃ and pH 5.0. The reaction followed first- and fractional-order kinetics with respect to [Cr(Ⅲ)- Gly-Gly2+] and [ninhydrin]. Increase in the total concentration of CTAB from 0 to 40×10-3 mol·dm-3 resulted in an increase in the pseudo-first-order rate constant (kψ) by a factor of ca 3. Quantitative kinetic analysis of kψ-[CTAB] data was performed on the basis of the pseudo-phase model of the micelles. As added salts induce structural changes in micellar systems that may modify the substrate-surfactant interactions, the effect of some inorganic (NaBr, NaCl, Na2SO4) and organic (NaBenz, NaSal, NaTos) salts on the rate was also explored. It was found that the tightly bound counterions (derived from organic salts) were the most effective.展开更多
In the present study we report the micellization behavior of imipramine hydrochloride(IMP)in absence and presence of different concentrations of inorganic salts(LiCl,NaF,NaCl,NaBr,and KCl)and ureas(urea and thiourea)o...In the present study we report the micellization behavior of imipramine hydrochloride(IMP)in absence and presence of different concentrations of inorganic salts(LiCl,NaF,NaCl,NaBr,and KCl)and ureas(urea and thiourea)over the temperature range from 288.15 to 303.15 K.The critical micellization concentrations(cmc)of drug and drug+additive systems were determined by conductometric technique. With increasing temperature the cmc first increases then decreases.Maximum cmc values were obtained at 293.15 K with or without additives.In presence of inorganic salts the cmc value decreases which is explained on the basis of nature and ion size of the added ion.Urea and thiourea also decrease the cmc at low concentrations(0.2 mmo·lL -1 urea and 0.1 mmo·lL -1 thiourea),but,at higher concentrations,increase in cmc is observed.The related thermodynamic parameters are also evaluated and discussed.展开更多
Kinetics of D-mannose oxidation by cerium (IV) was studied in a sulfuric acid medium at 40 ℃ both in absence and presence of ionic micelles. In both cases, the rate of the reaction was first-order in D-mannose and in...Kinetics of D-mannose oxidation by cerium (IV) was studied in a sulfuric acid medium at 40 ℃ both in absence and presence of ionic micelles. In both cases, the rate of the reaction was first-order in D-mannose and in cerium (IV), which decreased with increasing [H2SO4]. This suggested that the redox reaction followed the same mechanism. The reaction proceeded through formation of an intermediate complex, which was proved by kinetic method. The complex underwent slow unimolecular decomposition to a free radical that reacted with cerium (IV) to afford the product. The catalytic role of cationic cetyltrimethylammonium bromide (CTAB) micelles was best explained by the Menger-Portnoy model. The study of the effect of CTAB also indicated that a negatively charged species was reactive form of cerium (IV). From the kinetic data, micelle-cerium (IV) binding and rate constants in micellar medium were evaluated. The anionic micelle of sodium dodecyl sulfate plays no catalytic role. The oxidation has the rate expression: -d[Ce(IV)]= k1Kc1[D-mannose][Ce(IV)]dt Different activation parameters for micelle catalyzed and uncatalyzed paths were also calculated and discussed.展开更多
文摘The effects of nonelectrolytes (ureas, amino acids, sugars) on the cloud point (CP) of nonionic surfactant Triton X-114 (TX-114) and tetra-n-butylammonium bromide (TBAB) system were studied. Ureas as well as thioureas increased the CP. Behaviors of amino acids depended upon their nature. Nonpolar and uncharged polar amino acids were less effective in changing the CP. However, tryptophan and phenylalanine increased the CP sharply. Acidic amino acid (aspartic acid) and sugars decreased the CP. The results were explained in terms of their effect on water structure. Amino acids got solubilized either in the micellar interior or in the bulk phase.
文摘This study deals with the enhanced solubilization of polycyclic aromatic hydrocarbons （PAHs） such as phenanthrene （PHE） and fluorene （FLR） in a pure cationic gemini （G6） and three conventional surfactants [polyethylene glycol dodecyl ether （Brij35）, cetyltrimethyl ammonium bromide （CRAB） and sodium lauryl sulfate （SDS）] as well as in their equimolar binary combinations （G6-Brij35, G6-CTAB and G6-SDS）. Their solubilization efficiency toward PHE and FLR has been quantified in terms of the molar solubilization ratio （MSR） and the micelle-water partition coefficient （Kin）. The ideality/nonideality of the mixed micelles is discussed with the help of Clint, Rubingh and Rosen＇s approaches. These theories determine the deviation of experimental critical micelle concen- tration （CMC） values from ideal critical micelle concentration, which was measured by evaluating the interaction parameters （/3m and/3）. Negative values ofβm were observed in all the equimolar binary systems, which show synergism in the mixed micelles. Whereas at air/liquid interface synergism was observed in the systems G6-CrAB and G6-Brij35; G6-SDS exhibited an antagonistic effect. The order of MSR and Km was G6-CTAB 〉 G6- Brij35 〉 G6-SDS for phenanthrene as well as for fluorene.
基金The project was supported by the fund of the Council of Scientific and Industrial Research (CSIR), New Delhi, India (9/112 (0389) 2K7-EMR-I).
文摘The effect of electrolytes on the micellar behavior of an amphiphilic drug, chlorpromazine (CPZ) hydrochloride, was studied using cloud point (CP) and dye solubilization techniques. In the presence of KBr, increase in pH led to decrease in the CP of 50 mmol·L-1 drug solution (prepared in 10 mmol·L-1 sodium phosphate (SP) buffer) because of deprotonation of drug molecules at high pH. The visible absorbance increased (due to dye solubilization) with the increase in pH from 6.5 to 6.9, which indicated micellar growth. At fixed pH (6.7), addition of inorganic salts (KF, KCl, and KBr) to drug solutions (50 mmol·L-1) caused an increase in the CP as well as in the visible absorbance, with effectiveness being in the order: F-<Cl-<Br-. The results were discussed on the basis of counter-ion binding and their effect toward micellar growth. Cations (co-ions) also led to an increase in the CP (and also the visible absorbance), with their effectiveness order being Li+ >Na+ >K+, which was explained by considering cognizance of their hydrated radii. Compared with anions, their effect was small. Increase in [CPZ] caused micellar growth and hence the CP as well as the visible absorbance increased. The overall behavior was discussed in terms of electrostatic interactions and micellar growth.
基金supported by Department of Science and Technology's Science and Engineering Research Council Scheme of India (SR/FTP/CS-49/2007) for NAQVI Andleeb Z. and fellowship of University Grant Commission of India for KHAN Abbul Bashar
文摘The behavior of the mixed amphiphilic drug promethazine hydrochloride(PMT) and cationic as well as nonionic surfactants was studied by tensiometry.The cmc values of the PMT-surfactant systems decrease at a surfactant mole fraction of 0.1 and it then becomes constant.The critical micelle concentration(cmc) values are lower than the ideal cmc(cmc*) values for PMT/TX-100,PMT/TX-114,PMT/Tween 20,and PMT/Tween 60 systems.For the PMT/Tween 40,PMT/Tween 80,PMT/CPC,and PMT/CPB systems the cmc values are close to the cmc* values.This indicates that PMT forms mixed micelles with these surfactants by attractive interactions.The surface excess(Γmax) decreases in the presence of surfactants.The rigid structure of the drug makes adsorption easier and the contribution of the surfactant at the interface decreases.The interaction parameters βm(for the mixed micelles) and βσ(for the mixed monolayer) are negative indicating attraction among the mixed components.
基金supported by the Council of Scientific and Industrial Research(CSIR) Funds,New Delhi,India(ACK.No.:123075/2K8/1)
文摘The mixed micelle formation of binary cationic 14-s-14 gemini with conventional single chain surfactants was studied by conductivity measurements.The critical micelle concentration(cmc) and the degree of counterion binding values(g) of the binary systems were determined.The results were analyzed by applying regular solution theory(RST) to calculate micellar compositions(X),activity coefficients(f1,f2),and the interaction parameters(β).The synergistic interactions of all the investigated cationic gemini+conventional surfactant combinations were found to be dependent upon the length of hydrophobic spacer of the gemini surfactant.The excess Gibbs free energy of mixing was evaluated,and it indicated relatively more stable mixed micelles for the binary combinations.
文摘The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of chromium dipeptide complex ([Cr(Ⅲ)-Gly-Gly]2+) with ninhydrin under varying conditions has been investigated. The rates of the reaction were determined in both water and surfactant micelles in the absence and presence of various organic and inorganic salts at 70 ℃ and pH 5.0. The reaction followed first- and fractional-order kinetics with respect to [Cr(Ⅲ)- Gly-Gly2+] and [ninhydrin]. Increase in the total concentration of CTAB from 0 to 40×10-3 mol·dm-3 resulted in an increase in the pseudo-first-order rate constant (kψ) by a factor of ca 3. Quantitative kinetic analysis of kψ-[CTAB] data was performed on the basis of the pseudo-phase model of the micelles. As added salts induce structural changes in micellar systems that may modify the substrate-surfactant interactions, the effect of some inorganic (NaBr, NaCl, Na2SO4) and organic (NaBenz, NaSal, NaTos) salts on the rate was also explored. It was found that the tightly bound counterions (derived from organic salts) were the most effective.
基金supported by the Council of Scientific and Industrial Research,New Delhi,India(01(2208)/08/EMR-II)
文摘In the present study we report the micellization behavior of imipramine hydrochloride(IMP)in absence and presence of different concentrations of inorganic salts(LiCl,NaF,NaCl,NaBr,and KCl)and ureas(urea and thiourea)over the temperature range from 288.15 to 303.15 K.The critical micellization concentrations(cmc)of drug and drug+additive systems were determined by conductometric technique. With increasing temperature the cmc first increases then decreases.Maximum cmc values were obtained at 293.15 K with or without additives.In presence of inorganic salts the cmc value decreases which is explained on the basis of nature and ion size of the added ion.Urea and thiourea also decrease the cmc at low concentrations(0.2 mmo·lL -1 urea and 0.1 mmo·lL -1 thiourea),but,at higher concentrations,increase in cmc is observed.The related thermodynamic parameters are also evaluated and discussed.
文摘Kinetics of D-mannose oxidation by cerium (IV) was studied in a sulfuric acid medium at 40 ℃ both in absence and presence of ionic micelles. In both cases, the rate of the reaction was first-order in D-mannose and in cerium (IV), which decreased with increasing [H2SO4]. This suggested that the redox reaction followed the same mechanism. The reaction proceeded through formation of an intermediate complex, which was proved by kinetic method. The complex underwent slow unimolecular decomposition to a free radical that reacted with cerium (IV) to afford the product. The catalytic role of cationic cetyltrimethylammonium bromide (CTAB) micelles was best explained by the Menger-Portnoy model. The study of the effect of CTAB also indicated that a negatively charged species was reactive form of cerium (IV). From the kinetic data, micelle-cerium (IV) binding and rate constants in micellar medium were evaluated. The anionic micelle of sodium dodecyl sulfate plays no catalytic role. The oxidation has the rate expression: -d[Ce(IV)]= k1Kc1[D-mannose][Ce(IV)]dt Different activation parameters for micelle catalyzed and uncatalyzed paths were also calculated and discussed.
