Moment theory for the analytical determination of rate constants for solute permeation at the interface of spherical molecular aggregates

Moment equations were developed on the basis of the Einstein equation for diffusion and the random walk model to analytically determine the rate constant for the interfacial solute permeation from a bulk solvent into molecular aggregates (k_in) and the inverse rate constant from the molecular aggregates to the bulk solvent (k_out). The moment equations were in good agreement with those derived in a different manner. To demonstrate their effectiveness in one concrete example, the moment equations were used to analytically determine the values of k_in and k_out of three electrically neutral solutes, i.e. resorcinol, phenol, and nitrobenzene, from the first absolute (μ_1A) and second central (μ_2C) moments of their elution peaks, as measured by electrokinetic chromatography (EKC), in which the sodium dodecyl sulfate (SDS) micelles were used as a pseudostationary phase. The values of k_in and k_out should be determined with no chemical modifications and no physical action with the molecular aggregates because they are dynamic systems formed through weak interactions between the components. The moment analysis of the elution peak profiles measured by EKC is effective to unambiguously determine k_in, k_out, and the partition equilibrium constant (k_in/k_out) under appropriate experimental conditions.     

Moment equations for partial filling capillary electrophoresis

Moment equations were developed for partial filling CE systems, in which solute dissolution phenomena by spherical molecular assemblies or intermolecular interactions take place. Because experimental conditions of partial filling CE are divided into five categories on the basis of the magnitude relationship between the migration velocity of solute molecules and that of molecular assemblies or ligand molecules, the moment equations were systematically developed for each case by using the Einstein equation for diffusion and the random walk model. In order to demonstrate the effectiveness of the moment equations, they were applied to the analysis of partial filling CE behavior, which is correlated with dissolution phenomena of small solute molecules into spherical molecular assemblies as specific examples. Simulation results only in the case that the migration velocity of solute molecules is faster than that of molecular assemblies were represented in this paper. Detailed explanations about the derivation procedure of the moment equations and the simulation results in other cases can be found in the Supporting Information. The moment equations are theoretical bases for applying partial filling CE to the study on solute permeation kinetics at the interface of spherical molecular assemblies and on reaction kinetics of intermolecular interactions.     

A generalized setchenov approach to the effect of polar additives on ionic micellar solutions

It is shown that the variation of the critical micelle concentration (CMC) of two ionic surfactants (trimethyldodecylammonium bromide and sodium dodecyl sulfate) with the addition of a number of polar solutes in aqueous solutions follows a generalized type of Setchenov equation which allows the definition of a micellization constant K_M specific to each solute. This constant is a sum of a number of terms: the classical salting constant, an electrical term, and a free energy term. Using a precise vapor pressure method, the salting constant k_s was determined for a number of polar solutes in aqueous trimethyldodecylammonium bromide solutions. Using CMC determinations from the literature, it was shown that for solutes such as dimethylformamide, acetamide, urea, and dimethylurea, k_s = K_M, that is, the increase of the CMC is entirely attributable to the change in the medium due to the solute + monomer surfactant interactions; furthermore the change of the electrical terms upon addition of the solutes is negligible. In other cases, like acetone, dioxane, thiourea, or 1-alkanols, a partition coefficient may be easily calculated from a comparison between K_M and k_s.     

Micellar Effects on the Reaction between an Arenediazonium Ion and the Antioxidants Gallic Acid and Octyl Gallate

The effect of sodium dodecyl sulfate (SDS) micelles on the reaction between the 3‐methylbenzenediazonium (3MBD) ion and either the hydrophilic antioxidant gallic acid (GA) or the hydrophobic analogue octyl gallate (OG) have been investigated as a function of pH. Titration of GA in the absence and presence of SDS micelles showed that the micelles do not alter the first ionization equilibrium of GA. Analysis of the dependence of the observed rate constant (k_obs) with pH shows that the reactive species are GA^2? and OG^?. Kinetics results in the absence and presence of SDS micelles suggest that SDS aggregates do not alter the expected reaction pathway. SDS Micelles inhibit the spontaneous decomposition of 3MBD as well as the reaction between 3MBD and either GA or OG, and upon increasing the SDS concentration, with k_obs approaching the value for the thermal decomposition of 3MBD in the presence of SDS. Our results are consistent with the prediction of the pseudophase model and show that the origin of the inhibition for the reaction with GA is different to that for the reaction with OG; in the former case, the observed inhibition can be rationalized in terms of the micelle‐induced electrostatic separation of reactants in the micellar Stern layer, whereas the observed inhibition in the reaction with OG is a consequence of the dilution effect caused by increasing SDS concentration, decreasing the local OG^? concentration in the Stern layer.     

Dediazoniation of 1-naphthalenediazonium tetrafluoroborate in aqueous acid and in micellar solutions

We have measured the rates and product yields of dediazoniation of 1-naphthalenediazonium (1ND) tetrafluoroborate in the presence and absence of sodium dodecyl sulfate (SDS) micellar aggregates by employing a combination of UV–vis spectroscopy and high-performance liquid chromatography (HPLC) measurements. Kinetic data were obtained by a derivatization procedure with product yields were determined by HPLC. HPLC chromatograms show that in aqueous acid and in micellar solutions only one dediazoniation product is formed in significant quantities, 1-naphthol (NOH), and the observed rate constants (k_obs) are the same when 1ND loss is monitored spectrometrically and when NOH formation is monitored by HPLC. Activation parameters were obtained both in the presence and absence of SDS micellar aggregates. In both the systems, the enthalpies of activation are high and the entropies of activation are positive. The enthalpy of activation in the absence of SDS is very similar to that in the presence of SDS micelles, but the entropy of activation is lower by a factor of 4. As a consequence, SDS micelles speed up the thermal decomposition of 1ND and increase k_obs by a factor of 1.5 when [SDS] = 0.02 M. In contrast, results obtained in the presence of complexing systems such as crown ethers and polyethers show significant stabilization of the parent arenediazonium ions. Kinetic and HPLC data are consistent with the heterolytic D_N + A_N mechanism that involves the rate-determining fragmentation of the arenediazonium ion into a very reactive phenyl cation that reacts competitively with available nucleophiles. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 301–309, 2008     

Unusual Rate Enhancement in the Hydroxide-Ion-Catalyzed Cleavage of Acetyl Salicylate Ion (Aspirin Anion) in the Presence of Anionic Micelles

The reaction rate studies on the hydrolytic cleavage of acetyl salicylate ion (AS^-) within the [^-OH] range 0.010-0.025 M reveal AS^- and ^-OH as the reactants. The effects of micelles of sodium dodecyl sulfate (SDS) on observed pseudo-first-order rate constants (k_obs) for the hydrolytic cleavage of AS^- have been studied at different [OH^-]. At a constant [OH^-], the rate constants (k_obs) follow an empirical relationship: k_obs = C + F [SDS]_T where [SDS]_T represents total SDS concentration. The magnitudes of C and F increase with an increase in [OH^-]. These data are explained in terms of the pseudophase model of the micelle.     

Sedimentation transport method for determination of molecular weight distributions

The sedimentation of the system polystyrene-cyclohexane at the Flory temperature has been studied with emphasis on the effects of pressure as well as concentration. The relation between the molecular weight M and the limiting sedimentation coefficient s₀⁰, is found to be s₀⁰ = 1.50 × 10^?15 M^1/2 (sec.) The concentration dependence parameter k_s has the form, k_s = k′M^1/2 = k″s₀⁰ with k′ = 4.5–5.5 × 10^?4. However, a rather unexpected dependence of k_s on the rotor speed is also found. A procedure is proposed for deducing solute molecular weight distributions from boundary spreading data in sedimentation transport experiments, a so-called “single concentration” method, requiring only one sedimentation run. Application to several polystyrenes (in cyclohexane at 35°C) with narrow, broad, and very broad distributions demonstrates the feasibility of the procedure. Comparisons are made with data from elution chromatography and gel permeation chromatography. The GPC method predicts somewhat broader distributions than those obtained by the other two methods.     

Cubic-grid Gaussian basis sets for electron scattering calculations IV

Summary An analytical formula has been derived for averaging the differential cross section for electron scattering with respect to isotropic target molecule orientation. It may be applied to any type ofT-matrix element k ^out|T|k ⁱⁿ in which the plane-wave functionsk ^out andk ⁱⁿ are expanded in a set ofs-type Gaussian functions. The formula for averaging was tested against results obtained by Monte-Carlo-type calculations and against experimental data for elastic electron scattering by the H₂ molecule.     

Characterization of solvation properties of lipid bilayer membranes in liposome electrokinetic chromatography

The nature of solute interactions with biomembrane-like liposomes, made of naturally occurring phospholipids and cholesterol, was characterized using electrokinetic chromatography (EKC). Liposomes were used as a pseudo-stationary phase in EKC that provided sites of interactions for uncharged solutes. The retention factors of uncharged solutes in liposome EKC are directly proportional to their liposome-water partition coefficients. Linear solvation energy relationship (LSER) models were developed to unravel the contributions from various types of interactions for solute partitioning into liposomes. Size and hydrogen bond acceptor strength of solutes are the main factors that determine partitioning into lipid bilayers. This falls within the general behavior of solute partitioning from an aqueous into organic phases such as octanol and micelles. However, there exist subtle differences in the solvation properties of liposomes as compared to those of octanol and various micellar pseudo-phases such as aggregates of sodium dodecyl sulfate (SDS), sodium cholate (SC), and tetradecylammonium bromide (TTAB). Among these phases, the SDS micelles are the least similar to the liposomes, while octanol, SC, and TTAB micelles exhibit closer solvation properties. Subsequently, higher correlations are observed between partitioning into liposomes and the latter three phases than that into SDS.     

Effects of Micellar Aggregates on the Kinetics and Mechanism of the Reaction between 4‐Nitrobenzenediazonium Ions and Some Amino Acids

We have explored the kinetics and mechanism of the reaction between 4‐nitrobenzenediazonium ions (4NBD), and the hydrophilic amino acids (AA) glycine and serine in the presence and absence of sodium dodecyl sulfate (SDS) micellar aggregates by means of UV/VIS spectroscopy. The observed rate constants k_obs were obtained by monitoring the disappearance of 4NBD with time at a suitable wavelength under pseudo‐first‐order conditions. In aqueous acid (buffer‐controlled) solution, in the absence of SDS, the dependence of k_obs on [AA] was obtained from the linear relationship found between the experimental rate constant and [AA]. At a fixed amino acid concentration, k_obs values show an inverse dependence on acidity in the range of pH 5–6, suggesting that the reaction takes place through the nonprotonated amino group of the amino acid. All kinetic evidence is consistent with an irreversible bimolecular reaction with k=2390±16 and 376±7 M ^?1 s^?1 for glycine and serine, respectively. Addition of SDS inhibits the reaction because of the micellar‐induced separation of reactants originated by the electrical barrier imposed by the SDS micelles; k_obs values are depressed by factors of 10 (glycine) and 6 (serine) on going from [SDS]=0 up to [SDS]=0.05M . The hypothesis of a micellar‐induced separation of the reactants was confirmed by ¹H‐NMR spectroscopy, which was employed to investigate the location of 4NBD in the micellar aggregate: the results showed that the aromatic ring of the arenediazonium ion is predominantly located in the vicinity of the C(β) atom of the surfactant chain, and hence the reactive ? N group is located in the Stern layer of the micellar aggregate. The kinetic results can be quantitatively interpreted in terms of the pseudophase kinetic model, allowing estimations of the association constant of 4NBD to the SDS micelles.     

On the Determination of Partial Molar Volumes,Partial Molar Refractions,Mean Electronic Polarizabilities and Effective Molecular Radii from Dilute Multi-component Data alone using Response Surface Models

A quaternary system consisting of three solutes, namely ethanol, diethylene glycol (DEG) and triethylene glycol (TEG) in benzene at 298.15 K and 1.0125 × 10⁵ Pa was studied. An experimental design in the range of concentration 0.006 < x _solute−i < 0.023 was explored, optimizing the metric distance among the solutes to avoid clustering. On-line simultaneous experimental measurements using a densitometer and a refractometer were utilized to measure bulk solution density and bulk refractive index, respectively. Response surface models describing the total molar volume and total molar refraction were employed to determine the partial molar volumes and the partial molar refractions of each solute from the dilute multi-component data alone. Neither densities nor refractive indices of any of the pure components were used and no binary information was required for the analysis. Definitions for the mean electronic polarizability and the effective molecular radius of a solute based on the partial molar refraction were introduced. Subsequently, the mean electronic polarizabilities and the effective molecular radii for each solute in multi-component solutions, as well as the solvent were determined. The results obtained for the partial molar volumes, partial molar refractions, electronic polarizabilities and the effective molecular radii were in good agreement with those obtained from independent binary experiments as well as those from literature binary data.     

Solute exchange between surfactant micelles by micelle fragmentation and fusion

Stopped-flow time-scan experiments on both Triton X-100 (TX100) micelle and sodium dodecylsulfate (SDS) micelles, with the pyrene-containing triglyceride 1 as a probe, establish that there are two distinct solute exchange mechanisms with rates on the time scale of milliseconds to minutes. One process exhibits second order kinetics with a rate proportional to the concentration of empty micelles. For TX100 micelles, this process is rapid (k₂≈10⁶ M⁻¹ s⁻¹ at 24.6°C) and is characterized by an activation energy of 160 kJ mol⁻¹. From the fact that this rate is nearly independent of the structure of the probe we infer that the exchange involves micelle fusion to form a short-lived super-micelle, followed by fragmentation to form two normal (or ‘proper’) micelles. The rate of the first-order process decreases as the size of the probe increases (1-octylpyrene>1-dodecylpyrene>1). For SDS, both rates are very sensitive to the salt (NaCl) concentration. All indications point to this exchange process involving rate-limiting fragmentation of the micelle into two sub-micelles, these in turn grow back to normal micelles by addition of surfactant monomers or by collision with other sub-micelles. We explain the dependence of this rate on the nature of the probe by suggesting that only sub-micelles of a certain size are capable of carrying the probe with them as they separate from the original micelle.     

Kinetics and mechanism of intramolecular general base-catalyzed alkanolysis of phenyl salicylate in the presence of anionic micelles

The alkanolysis of ionized phenyl salicylate, PS^?, has been studied in the presence and absence of micelles of sodium dodecyl sulphate, SDS, at 0.05 M NaOH, 30 or 32°C and within the alkanol, ROH, (ROH = HOCH₂CH₂OH and CH₃OH) contents of 15–74 or 92%, v/v. The alkanolysis of PS^? involves intramolecular general base catalysis. At a constant concentration of SDS, [SDS]_T, the observed pseudo first-order rate constants, k_obs, for the reactions of ROH with PS^? obtained at different concentration of ROH, [ROH]_T, obey the relationship: k_obs = k[ROH]_T/(1 + K_A[ROH]_T) where k is the apparent second-order rate constant and K_A is the association constant for dimerization of ROH molecules. Both k and K_A decrease with increase in [SDS]_T. At a constant [ROH]_T, the rate constants, k_obs, show a decrease of nearly 2-fold with increase in [SDS]_T from 0.0–0.3M. These results are explained in terms of pseudo-phase model of micelle. The rate constants for alkanolysis of PS^? in micellar pseudophase are insignificant compared with the corresponding rate constants in aqueous-alkanol pseudophase. This is attributed largely to considerably low value of [ROH] in the specific micellar environment where micellar bound PS^? molecules exist. The increase in [ROH]_T decrease the value of the binding constant of PS^? with SDS micelle. The effects of anionic micelles on the rates of alkanolysis of PS^? are explained in terms of the porous cluster micellar structure.     

The Impact of Surfactants on FeIII–TAML‐Catalyzed Oxidations by Peroxides: Accelerations,Decelerations, and Loss of Activity

Iron(III) complexes of tetraamidato macrocyclic ligands (TAMLs), [Fe{4‐XC₆H₃‐1,2‐(NCOCMe₂NCO)₂CR₂}(OH₂)]^?, 1 ( 1 a : X=H, R=Me; 1 b : X=COOH, R=Me); 1 c : X=CONH(CH₂)₂COOH, R=Me; 1 d : CONH(CH₂)₂NMe₂, R=Me; 1 e : X=CONH(CH₂)₂NMe₃⁺, R=Me; 1 f : X=H, R=F), have been tested as catalysts for the oxidative decolorization of Orange II and Sudan III dyes by hydrogen peroxide and tert‐butyl hydroperoxide in the presence of micelles that are neutral (Triton X‐100), positively charged (cetyltrimethylammonium bromide, CTAB), and negatively charged (sodium dodecyl sulfate, SDS). The previously reported mechanism of catalysis involves the formation of an oxidized intermediate from 1 and ROOH (k_I) followed by dye bleaching (k_II). The micellar effects on k_I and k_II have been separately studied and analyzed by using the Berezin pseudophase model of micellar catalysis. The largest micellar acceleration in terms of k_I occurs for the 1 a ? tBuOOH? CTAB system. At pH 9.0–10.5 the rate constant k_I increased by approximately five times with increasing CTAB concentration and then gradually decreased. There was no acceleration at higher pH, presumably owing to the deprotonation of the axial water ligand of 1 a in this pH range. The k_I value was only slightly affected by SDS (in the oxidation of Orange II), but was strongly decelerated by Triton X‐100. No oxidation of the water‐insoluble, hydrophobic dye Sudan III was observed in the presence of the SDS micelles. The k_II value was accelerated by cationic CTAB micelles when the hydrophobic primary oxidant tert‐butyl hydroperoxide was used. It is hypothesized that tBuOOH may affect the CTAB micelles and increase the binding of the oxidized catalysts. The tBuOOH? CTAB combination accelerated both of the catalysis steps k_I and k_II.     

Apparent Specific Polarization and Dipole Moment of Some Poly(oxyethylene) Glycols in 1,4-Dioxane and Benzene Solutions at 298.15?K

The electrical permittivity of 1,4-dioxane and benzene solutions of some poly(oxyethylene) glycols up to the average molecular weight of 1590 were measured at 298.15 K. From the experimental data the limiting apparent specific polarization and partial molar polarization were calculated. The electrical dipole moment of the investigated solutes was estimated according to the Debye, Onsager, and Kirkwood theoretical approaches. The calculated dipole moments increase linearly with the square root of the number of monomeric units. The group dipole moment of the polar monomeric unit was calculated from the corresponding limiting partial molar volume, the refraction and polarization of the solute. The factor g, which takes into account the degree of flexibility of the chain, was estimated and found to be greater than 0.92, which means that the lower members of the poly(oxyethylene) glycols possess almost free rotation within the chain backbone of polymer.     

Apparent Specific Polarization and Dipole Moment of Some Poly(oxyethylene) Glycols in 1,4-Dioxane and Benzene Solutions at 298.15 K

Summary. The electrical permittivity of 1,4-dioxane and benzene solutions of some poly(oxyethylene) glycols up to the average molecular weight of 1590 were measured at 298.15 K. From the experimental data the limiting apparent specific polarization and partial molar polarization were calculated. The electrical dipole moment of the investigated solutes was estimated according to the Debye, Onsager, and Kirkwood theoretical approaches. The calculated dipole moments increase linearly with the square root of the number of monomeric units. The group dipole moment of the polar monomeric unit was calculated from the corresponding limiting partial molar volume, the refraction and polarization of the solute. The factor g, which takes into account the degree of flexibility of the chain, was estimated and found to be greater than 0.92, which means that the lower members of the poly(oxyethylene) glycols possess almost free rotation within the chain backbone of polymer.     

New Design of Thiol‐Responsive Degradable Polylactide‐Based Block Copolymer Micelles

A new design to synthesize thiol‐responsive degradable polylactide (PLA)‐based micelles having a disulfide linkage in the middle of triblock copolymers is reported. They were synthesized by a new method that centers on the use of a disulfide‐labeled diol as an initiator for ring‐opening polymerization, followed by controlled radical polymerization. These well‐controlled copolymers with monomodal and narrow molecular weight distribution (M _w/M _n < 1.15) self‐assembled to form aqueous micellar aggregates with disulfide‐containing PLA cores, which is not toxic to cells. Central disulfide linkages were cleaved in response to thiols; such thiol‐triggered degradation enhanced the release of encapsulated anticancer drugs.     

Electrokinetic chromatographic characterization of novel catanionic surfactants vesicle as pseudostationary phase

A novel catanionic surfactants vesicle system composed of octyltriethylammonium bromide/ sodium dodecyl benzene sulfonate (C₈NE₃Br/SDBS) has been developed as pseudostationary phase (PSP) in EKC. The C₈NE₃Br/SDBS system possesses a large vesicle phase region and none of agglomeration phenomena appeared while mixing cationic and anionic surfactants at any molar ratio. Electrophoretic and chromatographic parameters including elution window, hydrophobic selectivity, polar group selectivity, and shape selectivity were characterized using the vesicle at molar ratio of C₈NE₃Br to SDBS of 3:7 as PSP. Compared with SDS micelles, the vesicle PSP possessed a wider elution window and a better selectivity. The retention behavior and selectivity differences between the novel vesicle and SDS micelles were evaluated through linear solvation energy relationship (LSER) analysis. Though the cohesiveness and the hydrogen bond acidity have greatest influences on the solutes retention and selectivity in both the vesicle and SDS micelle, the vesicle PSP demonstrated a higher hydrophobicity and a lower hydrogen bonding donating capability owing to compact bilayer structure of vesicle. Additionally, the vesicle system had a stronger hydrogen bond accepting capability than SDS micelle. Consequently, according to LSER analysis, the bigger coefficients for v, b, and a revealed the vesicle PSP had a better separation selectivity than conventional SDS micelle.     

Catalytic effect of anionic micelles on alkaline hydrolysis of N-hydroxyphthalimide. Evidence for the probable occurrence of the reaction in between Gouy-Chapman and exterior boundary of Stern layers of the micelles

The nucleophilic second-order rate constant (k_OH) for the reaction of ōH with ionized N-hydroxyphthalimide (S^?) appears to follow a reaction mechanism similar to that for reactions of ōH with neutral phthalimide and its N-substituted derivatives. Kinetically indistinguishable terms, k′_w[H₂O][S^?] and k_ōH[ōH][SH] (SH represents nonionized N-hydroxyphthalimide), which constitute the pH-independent rate region of the pH-rate profile, are resolved qualitatively. It is shown that the term k_ōH[ōH][SH], rather than k′_w[H₂O][S^?], is important in these reactions. The rates of ōH-catalyzed cleavage of S^? were studied at 32° in the presence of micelles of sodium dodecyl sulphate (SDS). At a constant [ōH], the observed pseudo first-order rate constants (k_obs) increase linearly with [SDS]_T (total SDS concentration). These data are explained in terms of the pseudophase model of micellar effects on reactivity. The linear dependence of k_obs with [SDS]_T (within [SDS]_T range of 0.0–0.2 or 0.3 M) is attributed to the occurrence of the reaction between the exterior boundary of Stern layer and Gouy-Chapman layer.