A new method, based upon semi-empirical kinetic approach, for the determination of ion exchange constant for ion exchange processes occurring between counterions at the cationic micellar surface is described in this review article. Basically, the method involves a reaction kinetic probe which gives observed pseudo-first-order rate constants (k(obs)) for a nucleophilic substitution reaction between the nonionic and anionic reactants (R and S) in the presence of a constant concentration of both reactants as well as cationic micelles and varying concentrations of an inert inorganic or organic salt (MX). The observed data (k(obs), versus [MX]) fit satisfactorily (in terms of residual errors) to an empirical equation which could be derived from an equation explaining the mechanism of the reaction of the kinetic probe in terms of pseudophase micellar (PM) model coupled with another empirical equation. This (another) empirical equation explains the effect of [MX] on cationic micellar binding constant (K(S)) of the anionic reactant (say S) and gives an empirical constant, K(X/S). The magnitude of K(X/S) is the measure of the ability of X(-) to expel S(-) from a cationic micellar pseudophase to the bulk aqueous phase through ion exchange X(-)/S(-). The values of K(X/S) and K(Y/S) (where Y(-) is another inert counterion) give the ion exchange constant, K(X)(Y) (=K(X)/K(Y) where K(X) and K(Y) represent cationic micellar binding constants of X(-) and Y(-), respectively). The suitability of this method is demonstrated by the use of three different reaction kinetic probes and various MX.
A slight modification of the Gabriel synthesis of primary amines is suggested on the basis of the observed and reported values of rate constants for the alkaline and acid hydrolyses of phthalimide, phthalamic acid, benzamide, and their N-substituted derivatives. The suggested procedure requires shorter reactions time and milder acid-base reaction conditions compared with the conventional acid-base hydrolysis in the Gabriel synthesis. A slight modification in the Ing-Manske procedure is also suggested. Pseudo-first-order rate constants, k(obs), for hydrolysis of N-phthaloylglycine, NPG, decrease from 24.1 x 10(-3) to 7.72 x 10(-3) and 6.12 x 10(-3) s(-1) with increasing acetonitrile and 1,4-dioxan contents, respectively, from 2 to 50% v/v (all the percentages given in the paper are vol %), while increasing the organic cosolvents content from 50 to 80% increases k(obs) from 7.72 x 10(-3) to 19.7 x 10(-3) s(-1) for acetonitrile and from 6.12 x 10(-3) to 52.8 x 10(-3) s(-1) for 1,4-dioxan, in aqueous organic solvents containing 0.004 M NaOH at 35 degrees C. The rate constants for NPG hydrolysis decrease from 2.11 x 10(-2) to 1.19 x 10(-4) s(-1) with increasing MeOH content from 2 to 84%, in aqueous organic solvents containing 2% MeCN and 0.004 M NaOH at 35 degrees C.
Pseudo-first-order rate constants obtained for methanolysis of ionized phenyl salicylate (PS(-)) at constant [MeOH], [MeCN], [NaOH] or [KOH], and [KBr] and at 35 degrees C show a decrease with the increase in [CTABr] (where CTABr represents cetyltrimethylammonium bromide) from 0.0-0.01 M. These observed data obey a pseudophase model of the micelle. The micellar binding constants (K(S)) of PS(-), pseudo-first-order rate constants (k(M)) for methanolysis of PS(-) in the micellar pseudophase and cmc are almost unchanged with the change in [NaOH] from 0.005-0.050 M. The increase in [KBr] from 0.0 to 0.3 M at 0.01 M KOH decreases K(S) from 5140 to 653 M(-)(1) and cmc from 1.9 x 10(-)(4) to 0.2 x 10(-)(4) M. Pseudo-first-order rate constants, k(M), are almost independent of [KBr] at 0.01 M KOH.
A kinetic probe, which involves the determination of pseudo-first-order rate constants (k(obs)) for the nucleophilic reaction of piperidine (Pip) with ionized phenyl salicylate (S(-)) at constant [Pip](T) (= 0.1 M), [S(-)](T) (= 2 x 10(-4) M), [CTABr](T), < or = 0.10 M NaOH and varying concentration of MX (= 3-ClC(6)H(4)CO(2)Na and C(6)H(5)CH=CHCO(2)Na), gives the following information. The nonlinear plots of k(obs) versus [MX] reveal indirectly the occurrence of more than one independent ion-exchange processes at the CTABr micellar surface. These observed data fit to a kinetic relationship derived from an empirical equation coupled with pseudophase micellar (PM) model. This relationship gives an empirical constant (K(X/S)) that is used to determine the usual ion-exchange constant (K(X)(Y)). The values of K(X)(Br) (Y = Br) have been calculated for X = 3-ClC(6)H(4)CO(2)(-) and C(6)H(5)CH=CHCO(2)(-). More than 12-fold larger value of K(X)(Br) for X = 3-ClC(6)H(4)CO(2)(-) than that for X = 2-ClC(6)H(4)CO(2)(-) is attributed to the presence and absence of viscoelasticity in the respective presence of 3-ClC(6)H(4)CO(2)(-) and 2-ClC(6)H(4)CO(2)(-).
Pseudo-first-order rate constants (k(obs)) for alkaline hydrolysis of 4-nitrophthalimide show a monotonic decrease with increase in [C(12)E(23)](T) (total concentration of Brij 35) at constant [CH(3)CN] and [NaOH]. This micellar effect is explained in terms of a pseudophase micelle model. The rate of hydrolysis becomes too slow to monitor at [C(12)E(23)](T)>/=0.03 M in the absence of cetyltrimethylammonium bromide (CTABr) and at [C(12)E(23)](T)>/=0.04 M in the presence of 0.006-0.02 M CTABr at 0.01 M NaOH. The plots of k(obs) versus [C(12)E(23)](T) show minima at 0.006 and 0.01 M CTABr, while such a minimum is not visible at 0.02 M CTABr. Copyright 2001 Academic Press.
The rate of formation and disappearance of phthalic anhydride (PAn) intermediate in the aqueous cleavage of N-methoxyphthalamic acid (NMPA) under acidic pH was studied spectrophotometrically in mixed CH3CN-H2O solvents. The rate of formation of PAn from NMPA is almost independent of the change in acetonitrile content from 20 to 70% v/v in mixed aqueous solvents. The rate constants for the formation of PAn from NMPA are approximately 10-fold smaller than the corresponding rate constants for the formation of PAn from o-carboxybenzohydroxamic acid (OCBA). These observations are ascribed to the consequence of the occurrence of slightly different mechanisms in these reactions.
The fascinating and serendipitous discovery, in 1976, of the characteristic viscoelastic behavior of wormlike micelles of cetyltrimethylammonium salicylate (CTASa) surfactant solution at ~2×10(-4) M CTASa became a catalyst for an increasing interest in both industrial application and mechanism of the origin of micellar growth of this and related wormlike micellar systems. It has been perceived for more than three decades, based upon qualitative evidence, that the extent of the strength of the counterion (X) binding to ionic micelles determines the counterion-induced micellar structural transition from spherical-to-small rodlike-to-linear long stiff/flexible rodlike/wormlike-to-entangled wormlike micelles. This perception predicts the presence of a possible quantitative correlation of counterionic micellar binding constants (KX) with counterion-induced micellar growth. The quantitative estimation of counterion binding affinity to cationic micelles, in terms of the values of the degree of counterion binding (βX), is concluded to be either inefficient or unreliable for moderately hydrophobic counterions (such as substituted benzoate ions). The values of KX, measured in terms of conventional ion exchange constants (KX(Y)), can provide a quantitative correlation between KX or KX(Y) (with a reference counterion Y=Cl(-) or Br(-)) and counterion-induced ionic micellar growth. A recent new semi-empirical kinetic (SEK) method provides the estimation of KX(Y) for Y=Br as well as ratio of counterionic micellar binding constants KX/KBr (= RX(Br)) where the values of KBr and KX have been derived from the kinetic parameters in the presence of cationic spherical and nonspherical micelles, respectively. The SEK method has been used to determine the values of KX(Br) or RX(Br) for X=2-, 3- and 4-ClC6H4CO2(-). Rheometric measurements on aqueous CTABr/MX (MX=2-,3- and 4-ClBzNa) solutions containing 0.015 M CTABr and varying values of [MX] reveal the presence of spherical micelles for MX=2-ClBzNa and long linear as well as entangled wormlike micelles for MX=3- and 4-ClBzNa. The respective values of KX(Br) or RX(Br) of 5.7, 50 and 48 for X=2-, 3- and 4-ClBz(-) give a quantitative correlation with the rheometric measurements of the structural features of micelles of 0.015 M CTABr solutions containing 2-, 3- and 4 ClBzNa.
The semiempirical kinetic method has been used to determine the ratio of cetyltrimethylammonium bromide, CTABr, micellar binding constants of counterions X (K(X)) and Br (K(Br)), i.e., K(X)/K(Br) (= R(X)(Br)) for X = dianionic 5-methyl- and 5-methoxysalicylate ions. The values of K(X) and K(Br) have been derived from the kinetic parameters obtained in the presence of spherical/nonspherical and spherical micelles, respectively. The values of R(X)(Br) remain essentially independent of [CTABr] within its range 0.005-0.015 M for both dianionic 5-methyl- and 5-methoxysalicylate ions. The increase in temperature from 35 to 55 °C decreases the values of R(X)(Br) from 796 to 53 for 5-methylsalicylate ions and from 89 to 7.0 for 5-methoxysalicylate ions. Rheological properties of 0.015 M CTABr solutions containing ≥0.01 M counterionic salt, M(2)X, show indirectly the presence of unilamellar vesicles, ULV, and long linear, entangled, and branched wormlike micelles, WM, at, respectively, 35 and 55 °C for X = dianionic 5-methylsalicylate ion. However, such studies show WM and probable spherical micelles, SM, at, respectively, 35 and 55 °C for X = dianionic 5-methoxysalicylate ions. It has been shown that, at a constant [CTABr], the micellar structural transitions from SM-to-WM-to-vesicles may be correlated quantitatively with the values of R(X)(Br) regardless of whether such micellar structural transitions occur due to variation in the values of [M(2)X] at a constant temperature or due to variation in temperature at a constant [M(2)X].
The effects of the concentration of inert organic salts, [MX], (MX=2-, 3- and 4-BrBzNa with BrBzNa=BrC(6)H(4)CO(2)Na) on the rate of piperidinolysis of ionized phenyl salicylate (PS(-)) have been rationalized in terms of pseudophase micellar (PM) coupled with an empirical equation. The appearance of induction concentration in the plots of k(obs) versus [MX] (where k(obs) is pseudo-first-order rate constants for the reaction of piperidine (Pip) with PS(-)) is attributed to the occurrence of two or more than two independent ion exchange processes between different counterions at the cationic micellar surface. The derived kinetic equation, in terms of PM model coupled with an empirical equation, gives empirical parameters F(X/S) and K(X/S) whose magnitudes lead to the calculation of usual ion exchange constant K(X)(Br) (=K(X)/K(Br) with K(X) and K(Br) representing cationic micellar binding constants of counterions X(-) and Br(-), respectively). The value of F(X/S) measures the fraction of S(-) (=PS(-)) ions transferred from the cationic micellar pseudophase to the aqueous phase by the optimum value of [MX] due to ion exchange X(-)/S(-). Similarly, the value of K(X/S) measures the ability of X(-) ions to expel S(-) ions from cationic micellar pseudophase to aqueous phase through ion exchange X(-)/S(-). This rather new technique gives the respective values of K(X)(Br) as 8.8±0.3, 71±6 and 62±5 for X(-)=2-, 3- and 4-BrBz(-). Rheological measurements reveal the shear thinning behavior of all the surfactant solutions at 15mM CTABr (cetyltrimethylammonium bromide) indicating indirectly the presence of rodlike micelles. The plots of shear viscosity (η) at a constant shear rate (γ), i.e. η(γ), versus [MX] at 15 mM CTABr exhibit maxima for MX=3-BrBzNa and 4-BrBzNa while for MX=2-BrBzNa, the viscosity maximum appears to be missing. Such viscosity maxima are generally formed in surfactant solutions containing long stiff and flexible rodlike micelles with entangled and branched/multiconnected networks. Thus, 15 mM CTABr solutions at different [MX] contain long stiff and flexible rodlike micelles for MX=3- and 4-BrBzNa and short rodlike micelles for MX=2-BrBzNa.
Pseudofirst-order rate constants for aqueous cleavage of N-(2'-hydroxyphenyl)phthalimide (1), obtained at 0.001 M NaOH, 2 x 10(-4) M 1, 2% v/v CH(3)CN, and 30 degrees C, show a nonmonotonic decrease with the increase in the total concentration of cetyltrimethylammonium bromide ([CTABr](T)) within its range >/=9 x 10(-5)-M. Similar observations have been obtained in the presence of the constant concentration of NaBr at M. The values of k(obs) become independent of [CTABr](T) at >or=0.04 M CTABr and within a [NaBr] range of 0.0-0.005 M. These observations, in view of the pseudophase (PP) model of the micelle, reveal the presence of presumably spherical micelles at M CTABr in the presence of a constant concentration of NaBr within its range of 0.0-0.01 M. The average value of the CTABr micellar binding constant (K(S)) of ionized 1 (i.e., 1(-)), under these conditions, is (1.88 +/- 0.62) x 10(3) M(-1). The increase in [CTABr](T) at >or=4 x 10(-4) M causes a micellar structural transition from most likely spherical to cylindrical, which is evident from the increase in K(S) values from 3.46 x 10(3) to 11.4 x 10(3) M(-1) with the increase in [CTABr](T) from 4 x 10(-4) to approximately 1 x 10(-3) M in the absence of NaBr. The values of k(obs) at different [NaBr] and at a constant [CTABr](T) follow a kinetic relationship derived from an empirical equation coupled with a PP model of micelle. This relationship gives the value of a kinetic parameter, F(X/S), which represents the fraction of micellized S(-) (S(-) = 1(-)) transferred to the aqueous phase by the limiting concentration of X(-) (X(-) = Br(-)) through ion exchange X(-)/S(-). The value of F(Br/1) is 0.65 +/- 0.12.
Pseudo-first-order rate constants (k(obs)) for the nucleophilic substitution reaction of piperidine (Pip) with ionized phenyl salicylate (PS(-)), obtained at a constant [Pip](T) (= 0.1 M), [PS(-)](T) (= 2 x 10(-4) M), [CTABr](T) (cetyltrimethylammonium bromide), < or = 0.06 M NaOH, and a varying concentration of MX (= 3-FC(6)H(4)CO(2)Na, 3-FBzNa and 4-FC(6)H(4)CO(2)Na, 4-FBzNa), follow the kinetic relationship k(obs) = (k(0) + thetaK(X/S)[MX])/(1 + K(X/S)[MX]) which is derived by the use of the pseudophase micellar (PM) model coupled with an empirical equation. The empirical equation explains the effects of [MX] on CTABr micellar binding constant (K(S)) of PS(-) that occur through X(-)/PS(-) ion exchange. Empirical constants theta and K(X/S) give the parameters F(X/S) and K(X/S), respectively. The magnitude of F(X/S) gives the measure of the fraction of micellized PS(-) transferred to the aqueous phase by the limiting concentration of X(-) through X(-)/PS(-) ion exchange. The values of F(X/S) and K(X/S) have been used to determine the usual thermodynamic ion exchange constant (K(X)(Y)) for ion exchange process X(-)/Y(-) on the CTABr micellar surface. The values of K(X)(Br) (where Br = Y) have been calculated for X = 3-FBzNa and 4-FBzNa. The mean values of K(X)(Br) are 12.8 +/- 0.9 and 13.4 +/- 0.6 for X(-) = 3-FBz(-) and 4-FBz(-), respectively. Nearly 3-fold-larger values of K(X)(Br) for X = 3-FBz(-) and 4-FBz(-) than those for X = Bz(-), 2-ClBz(-), 2-CH(3)Bz(-), and the 2,6-dichlorobenzoate ion (2,6-Cl(2)Bz(-)) are attributed to the presence of wormlike micelles in the presence of > 50 mM 3-FBz(-) and 4-FBz(-) in the [CTABr](T) range of 5-15 mM. Rheological properties such as shear thinning behavior of plots of shear viscosity versus the shear rate at a constant [3-FBz(-)] or [4-FBz(-)] as well as shear viscosity (at a constant shear rate) maxima as a function of the concentrations of 3-FBz(-) and 4-FBz(-) support the conclusion, derived from the values of K(X)(Br), for the probable presence of wormlike/viscoelastic micellar solutions under the conditions of the present study.
The values of the relative counterion (X) binding constant R(X)(Br) (=K(X)/K(Br), where K(X) and K(Br) represent cetyltrimethylammonium bromide, CTABr, micellar binding constants of X(v-) (in non-spherical micelles), v = 1,2, and Br(-) (in spherical micelles)) are 58, 68, 127, and 125 for X(v-) = 1(-), 1(2-), 2(-), and 2(2-), respectively. The values of 15 mM CTABr/[Na(v)X] nanoparticles-catalyzed apparent second-order rate constants for piperidinolysis of ionized phenyl salicylate at 35 °C are 0.417, 0.488, 0.926, and 0.891 M(-1) s(-1) for Na(v)X = Na1, Na2 1, Na2, and Na2 2, respectively. Almost entire catalytic effect of nanoparticles catalyst is due to the ability of nonreactive counterions, X(v-), to expel reactive counterions, 3(-), from nanoparticles to the bulk water phase.
Silver nanoparticles (AgNPs) are among the most widely synthesized and used nanoparticles (NPs). AgNPs have been traditionally synthesized from plant extracts, cobwebs, microorganisms, etc. However, their synthesis from wing extracts of common insect; Mang mao which is abundantly available in most of the Asian countries has not been explored yet. We report the synthesis of AgNPs from M. mao wings extract and its antioxidant and antimicrobial activity. The synthesized AgNPs were spherical, 40-60 nm in size and revealed strong absorption plasmon band around at 430 nm. Highly crystalline nature of these particles as determined by Energy-dispersive X-ray analysis and X-ray diffraction further confirmed the presence of AgNPs. Hydrodynamic size and zeta potential of AgNPs were observed to be 43.9 nm and -7.12 mV, respectively. Fourier-transform infrared spectroscopy analysis revealed the presence of characteristic amide proteins and aromatic functional groups. Thin-layer chromatography (TLC) and Gas chromatography-mass spectroscopy (GC-MS) analysis revealed the presence of fatty acids in the wings extract that may be responsible for biosynthesis and stabilization of AgNPs. Further, SDS-PAGE of the insect wing extract protein showed the molecular weight of 49 kDa. M. mao silver nanoparticles (MMAgNPs) exhibit strong antioxidant, broad-range antibacterial and antifungal activities, (66.8 to 87.0%), broad-range antibacterial and antifungal activities was found with maximum zone of inhibition against Staphylococcus aureus MTCC 96 (35±0.4 mm) and Fusarium oxysporum f. sp. ricini (86.6±0.4) which signifies their biomedical and agricultural potential.
The values of pseudo-first-order rate constants (k(obs)) for alkaline hydrolysis of 1, obtained at 1.0 mM NaOH and within [C(m)E(n)]T (total concentration of C(m)E(n)) range of 3.0-5.0 mM for C(12)E(23) and 10-20 mM for C(18)E(20), fail to obey pseudophase micellar (PM) model. The values of the fraction of near irreversible C m E n micellar trapped 1 molecules (F(IT1)) vary in the range ~0-0.75 for C(12)E(23) and ~0-0.83 for C(18)E(20) under such conditions. The values of F(IT1) become 1.0 at ≥ 10 mM C(12)E(23) and 50 mM C(18)E(20). Kinetic analysis of the observed data at ≥ 10 mM C(12)E(23) shows near irreversible micellar entrapment of 1 molecules under such conditions.
An outdoor soil burial test was carried out to evaluate the degradation of commercially available LDPE carrier bags in natural soil for up to 2 years. Biodegradability of low density polyethylene films in soil was monitored using both optical and scanning electron microscopy (SEM). After 7-9 months of soil exposure, microbial colonization was evident on the film surface. Exposed LDPE samples exhibit progressive changes towards degradation after 17-22 months. SEM images reveal signs of degradation such as exfoliation and formation of cracks on film leading to disintegration. The possible degradation mode and consequences on the use and disposal of LDPE films is discussed.