[Show abstract][Hide abstract] ABSTRACT: Antioxidant (AO) efficiencies are reported to go through maxima with increasing chain length (hydrophobicity) in emulsions. The so-called "cutoff" after the maxima indicating a decrease in efficiency remains unexplained. Here we show, for gallic acid, GA, and propyl, octyl and lauryl gallates (PG, OG and LG, respectively), that at any given volume fraction of emulsifier, the concentrations of antioxidants in the interfacial region of stripped corn oil emulsions and their efficiency order follow: PG > GA > OG > LG. These results provide clear evidence that an AO's efficiency correlates with its fraction in the interfacial region. AO distributions were obtained in intact emulsions by using the pseudophase kinetic model to interpret changes in observed rate constants of the AOs with a chemical probe and their efficiencies were measured by employing the Schaal oven test. The model provides a natural explanation for the maxima with increasing AO hydrophobicity.
Journal of Agricultural and Food Chemistry 05/2013; · 3.11 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Specific salt effects on the reduction of an amphiphilic arenediazonium ion, 16-ArN2+, by TBHQ in opaque, stirred and kinetically stable emulsions prepared with a zwitterionic sulfobetaine surfactant are consistent with chameleon effect: selective anion binding/induced cation binding in the interfacial region of the emulsions. Added NaX salts with different anions decrease the observed first order rate constant, kobs, for the reduction in the order: X- = ClO4- > Br- ≈ CCl3CO2- > Cl- > MeSO3-. Added MCln salts of increasing cation valence at constant total Cl- concentration increase kobs in the order: Mn+ = Cs+ < Ca2+ < Al3+ in the same emulsions. These results, combined with recent results in nonionic and ionic emulsions demonstrate that pseudophase kinetic models provide general, coherent explanations for chemical reactivity in homogeneous micelles, microemulsions, vesicles and now biphasic emulsions and with all types of basic surfactant structures: nonionic, cationic, anionic, and now zwitterionic.
[Show abstract][Hide abstract] ABSTRACT: Kinetic results obtained in cationic and anionic emulsions show for the first time that pseudophase kinetic models give reasonable estimates of the partition constants of reactants, here t-butylhydroquinone (TBHQ) between the oil and interfacial region, PO(I), and the water and interfacial region, PW(I), and of the interfacial rate constant, kI, for the reaction with an arenediazonium ion in emulsions containing a 1:1 volume ratio of a medium chain length triglyceride, MCT, and aqueous acid or buffer. The results provide: (a) an explanation for the large difference in pH, >4 pH units, required to run the reaction in CTAB (pH 1.54, added HBr) and SDS (pH 5.71, acetate buffer) emulsions; (b) reasonable estimates of PO(I) and kI in the CTAB emulsions; (c) a sensible interpretation of added counterion effects based on ion exchange in SDS emulsions (Na(+)/H3O(+) ion exchange in the interfacial region) and Donnan equilibrium in CTAB emulsions (Br(-) increasing the interfacial H3O(+)); and (d) the significance of the effect of the much greater solubility of TBHQ in MCT versus octane, 1000/1, as the oil. These results should aid in interpreting the effects of ionic surfactants on chemical reactivity in emulsions in general and in selecting the most efficient antioxidant for particular food applications.
Journal of Colloid and Interface Science 03/2013; · 3.55 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Until relatively recently, modeling chemical reactivity in emulsions has proved refractory. The problem lies in developing good methods for determining the distributions of reactants because classical separation of the phases by physical methods do not work, which prevents measurement of the distributions of reactants and components between the oil, interfacial and aqueous regions in emulsions. Without this understanding, they cannot be used efficiently as reaction media. We are using a physical-organic chemistry approach grounded in thermodynamics and inspired by the prior success of pseudophase kinetic models developed for association colloids such as micelles microemulsions, and vesicles. In emulsions, as in association colloids, the observed rate constant depends on the concentrations of reactants in each region and on medium effects. The medium effects reflect the solvent properties of a reaction region and the distributions of reactants depend on their solubilities in each region. Here we introduce: (a) the current concepts and basic assumptions employed to interpret chemical reactivity in nonionic and ionic emulsions; (b) several approaches for estimating the partition constants for substrates between the oil-interfacial, POI, and water-interfacial, PWI, regions of the emulsions; and (c) methods for determining the rate constant in the interfacial region, kI. The results demonstrate that pseudophase kinetic analyses provide a unique, versatile, and robust solution to interpreting chemical reactivity in emulsions. The approach permits identifying the relative importance of various emulsion properties such as oil hydrophobicity, emulsifier structure and HLB, temperature, and acidity on reactant distributions. Representative results for antioxidants are included. The approach offers a new route for identifying most efficient antioxidant for a particular food application.
Current Opinion in Colloid & Interface Science 02/2013; 18(1):3–14. · 6.63 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Chemical trapping is a powerful approach for obtaining experimental estimates of interfacial molarities of weakly basic nucleophiles in the interfacial regions of amphiphile aggregates. Here we demonstrate that the chemical probe, 4-hexadecyl-2,6-dimethylbenzenediazonium ion, 16-ArN2+, reacts competitively with interfacial water, with the amide carbonyl followed by cleavage of the headgroups from the tail at the amide oxygen, and with the terminal carboxylate groups in micelles of two N-acyl amino acid amphiphiles, sodium N-lauroylsarcosinate, SLS, and sodium N-lauroylglycinate, SLG, simple peptide bond model amphiphiles. Interfacial molarities, moles/liter of interfacial volume, of these three groups were obtained from product yields and by assuming that selectivity toward a particular nucleophile compared to water is the same in an aqueous reference solution and in the interfacial region. Interfacial carboxylate group molarities are ~1.5 M in both SLS and SLG micelles, but the concentration of the amide carbonyl for SLS micelles is ~4.6-5 times less (ca. 0.7 M) than that of SLG micelles (~3 M). The proton on the secondary N of SLG helps solubilize the amide bond in the aqueous region, but the methyl on the tertiary N of SLS helps solubilize the amide bond in the micellar core, reducing its reaction with 16-ArN2+. Application of chemical trapping to proteins in membrane mimetic interfaces should provide insight into the topology of the protein within the interface because trapping of the amide carbonyl and cleavage at the C-N bond occurs only within the interface, and fragment characterization marks those peptide bonds located within the interface.
[Show abstract][Hide abstract] ABSTRACT: We determined the effects of emulsifier concentration and temperature on the distribution of gallic acid (GA) in a food-grade emulsion composed of 1:9 vol:vol stripped corn oil, acidic water and Tween 20. The distribution of GA can be defined by the partition constant between the aqueous and the interfacial regions, P(W)(I), which was determined by using a kinetic method and the pseudophase kinetic model. Once P(W)(I) is known, determining the distribution of GA is straightforward. Our results show that at least 40% of the total GA is located in the interfacial region of the emulsion at 0.005 volume fraction of Tween 20, and this percentage increases to ca. 85% of the total GA at 0.04 volume fraction of Tween 20. The variation of P(W)(I) with the temperature was used to estimate the thermodynamic parameters for the GA transfer from the aqueous to the interfacial region of the emulsion and the activation parameters for the reaction between 16-ArN(2)(+) and GA in the interfacial region. The free energy of transfer from the aqueous to the interfacial region, ΔG(T)(0,W→I), is negative, the enthalpy of transfer is small and negative, but the entropy of transfer is large and positive. Our results demonstrate that the partitioning of GA in acidic emulsions between aqueous and interfacial regions depends primarily on droplet concentration and is only slightly dependent on temperature.
Journal of Colloid and Interface Science 03/2012; 370(1):73-9. · 3.55 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: We have determined the distribution of the antioxidant tert-butylhydroquinone, TBHQ, between the oil and interfacial regions
of an emulsion composed of stripped corn oil, acidic water and hexaethyleneglycol monododecyl ether, C12E6, by employing a kinetic method based on the reaction between the hydrophobic 16-hexadecylbenzenediazonium ions, 16-ArN2
+, and TBHQ. The kinetic data are interpreted under the light of the pseudophase kinetic model and provide estimates of the
partition constant, and hence the distribution, of TBHQ between the oil and the interfacial region of the emulsion. Our results
show that more than 80% of TBHQ is located in the interfacial region even at low emulsifier volume fractions, and the fraction
of TBHQ in that region increases upon increasing [C12E6].
[Show abstract][Hide abstract] ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
[Show abstract][Hide abstract] ABSTRACT: The combined linear sweep voltammetry (LSV)/pseudophase kinetic model method was used to obtain the first estimates of the free energies, enthalpy, and entropies of transfer of alpha-tocopherol (TOC) between the oil and interfacial regions of fluid, opaque, emulsions of n-octane, acidic water, and the nonionic surfactant hexaethyleneglycol mono dodecyl ether (C12E6) from the temperature dependence of TOC's partition constant. Determining structure-reactivity relationships for chemical reactions in emulsions is difficult because traditional methods for monitoring reactions are unsuitable and because the partitioning of reactive components between the oil, interfacial, and aqueous regions of opaque emulsions are difficult to measure. The dependence of the observed rate constant, k(obs), for the reaction of an arenediazonium probe, 16-ArN2+, with TOC was determined as a function of C12E6 volume fraction. The pseudophase kinetic model was used to estimate the interfacial rate constant, k1, and the partition constants of antioxidants between the oil and interfacial, Po(I), regions in the emulsion from k(obs) versus phiI profiles. The thermodynamic parameters of transfer from the oil to the interfacial region at a series of temperatures were respectively obtained from the PoI values (deltaGT0,O-->I), by the van't Hoff method (deltaHT0,O-->I), and from the Gibbs equation (deltaST0,O-->I). The free energy of transfer is spontaneous, and a large positive entropy of transfer dominates a positive enthalpy of transfer, indicating that the TOC headgroup disrupts the structure of the interfacial region in its immediate vicinity upon transfer from n-octane. The methods described here are applicable to any bimolecular reaction in emulsions in which one of the reactants is restricted to the interfacial region and the rate of its reaction with a second component can be monitored electrochemically.
[Show abstract][Hide abstract] ABSTRACT: Understanding ion specific effects on the solution properties of association colloids is a major unsolved problem, and we are studying the chemistry of gemini surfactants in the gas-phase by mass spectrometry and density functional theory (DFT) to probe ion specific effects in the absence of water. Products from gas-phase fragmentation chemistry of dication-monoanion pairs, M2+X(-), of C16H33(CH3)2N+-(CH2)(n-) +N(CH3)2C16H33.2X(-) gemini surfactants were determined by using sequential collision induced dissociation mass spectrometry. The spacer length "n" was systematically varied (n = 2, 3, 4, and 6) for each counterion investigated (X(-) = F(-), Br(-), Cl(-), I(-), NO3(-), CF3CO2(-), and PF6(-)). The M2+X(-) pairs fragment into monocationic products from competing E2 and S N2 pathways that are readily quantified by tandem MS. The dominant reaction pathway depends on dication and anion structure because it switches from E2 to S N2 with decreasing anion basicity and increasing spacer length. For spacer lengths n = 4 and 6, the major S N2 product shifts from attack at methylene to methyl on the quaternary ammonium group. DFT calculations of gemini headgroup model bolaform salts, CH3(CH3)2N+-(CH2)(n-)+N(CH3)2CH3.2X(-) (X(-) = F(-), Cl(-), Br(-), and I(-), n = 2-4), primarily of activation enthalpies, DeltaH, but also of free energies and entropies for the dication-monoanion pairs, M2+X(-), provide qualitative explanations for the MS structure-reactivity patterns. DeltaH values for S N2 reactions are independent of X(-) type and spacer length, while E2 reactions show a significant increase in DeltaH with decreasing anion basicity and a modest increase with spacer length. Comparisons with the DeltaH values of model CH3CH2(CH3)3N+X(-) halides show that the second charge on the dicationic ion pairs does not significantly affect DeltaH and that the change in distance between the nucleophile and leaving group in the ground and transition states structures in S N2 reactions is approximately constant indicating that DeltaH is governed primarily by electrostatic interactions.
The Journal of Physical Chemistry B 12/2008; 112(46):14435-45. · 3.61 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Until recently, determining the distribution of antioxidants, AOs, between the oil, interfacial and aqueous regions of opaque emulsions has not worked well because the concentrations of AOs in interfacial regions cannot be determined separately from their concentrations in the oil and water phases. However, our novel kinetic method based on the reaction between an arenediazonium ion and vitamin E, or alpha-tocopherol, provides the first good estimates for the two partition constants that describe alpha-tocopherol distribution between the oil/interfacial and water/interfacial regions of tributyrin/Brij 30/water emulsions without physical isolation of any phase. The reaction is monitored by a new derivatization method based on trapping unreacted arenediazonium ion as an azo dye and confirmed by linear sweep voltammetry, LSV. The results by both derivatization and LSV methods are in good agreement and show that alpha-tocopherol distributes strongly in favor of the interfacial region when the oil is tributyrin, e.g., ca. 90% when the surfactant volume fraction is Phi I=0.01. The second-order rate constant for reaction in the interfacial region is also obtained from the results. Our kinetic method provides a robust approach for determining antioxidant distributions in emulsions and should help develop a quantitative interpretation of antioxidant efficiency in emulsions.
Journal of Colloid and Interface Science 05/2008; 320(1):1-8. · 3.55 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: N,N,N',N'-Tetramethylimidazolidinium dichloride (1-Im-1 2Cl) has been studied as a model system for cation-anion interactions in the interfacial regions of gemini micelles by X-ray crystallography, density functional theory (DFT) calculations, and infrared spectroscopy. Single crystals of 1-Im-1 2Cl contain 1-Im-1 dications, whose five-membered rings adopt a distorted envelope conformation. Eight chloride anions surround each dication, two of which are cradled above and below the five-membered ring (apical) and six of which are dispersed about the periphery of the ring (equatorial). The cations and anions are linked in the solid state by an extensive network of weak C-H...Cl hydrogen bonds that involve all of the H atoms of the dication. The calculated (DFT at the 6-31+G(d) level) structure of the asymmetric unit, which consists of a dication and two apical chloride ions, closely resembles the equivalent unit in the crystal structure with respect to bond distances and angles, the conformation of the 1-Im-1 ring, and the nature and location of the C-H...Cl hydrogen bonds. The calculated IR spectrum predicts a number of absorptions in the 3000 cm(-1) region, assigned as C-H...Cl stretching modes, which are consistent with the presence of an intense band in the observed IR spectrum of the crystals. Over all, this study supports the notion that apical chloride ions interact more strongly with gemini surfactant headgroups by forming multiple hydrogen bonds in ion pairs of a type that cannot be present in the corresponding ion pairs of quaternary headgroups with counterions of single-chain surfactants.
The Journal of Physical Chemistry B 01/2008; 111(49):13668-74. · 3.61 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: High field (800 MHz) (1)H NMR was used to monitor the two-step consecutive reaction of excess SO(3)(2-) with symmetrical bifunctional alpha,omega-dibromoalkanes with butane (DBB), hexane (DBH), octane (DBO), and decane (DBD) chains in CTAB micelles at 25 degrees C. The first-order rate constant for the first substitution step for DBB and DBH is about 5 times faster than for the second, but the kinetics for DBO and DBD were not cleanly first-order. After 40 min, the solution contained about 80% of the intermediate bromoalkanesulfonate from DBB and DBH and the remainder is alkanedisulfonate and unreacted starting material. The same reactions were carried out in homogeneous MeOH/D(2)O solutions at 50 degrees C. The rate constants for all four alpha,omega-dibromoalkanes were first-order throughout the time course of the reaction and the same within +/-10%. However, because micellar solutions are organized on the nanoscale and bring together lipophilic and hydrophilic reactants into a small reaction volume at the micellar interface, they speed this substitution reaction considerably compared to reaction in MeOH/D(2)O. The CTAB micelles also induce a significant regioselectivity in product formation by speeding the first step of the consecutive reaction more than the second. The results are consistent with the bromoalkanesulfonate intermediates having a radial orientation within the micelles with the -CH(2)SO(3)(-) group in the interfacial region and the -CH(2)Br group directed into the micellar core such that the concentration of -CH(2)Br groups in the reactive zone, i.e., the micellar interface, is significantly reduced. These results provide the first example of self-assembled surfactant system altering the relative rates of the reaction steps of a consecutive reaction and, in doing so, enhancing monosubstitution of a symmetrically disubstituted species.
Journal of Colloid and Interface Science 09/2007; 312(2):453-459. · 3.55 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Surface-active amphiphiles aggregate spontaneously in water to form association colloids such as micelles, microemulsions, and vesicles. The hydrophobic effect drives aggregation, but the opposing forces that provide balance and determine equilibrium morphologies are not understood, in particular, how specific ion effects, which often follow a Hofmeister series, affect the properties of association colloids. We have harnessed the competitive trapping of arenediazonium ions by weakly basic nucleophiles such as halide counterions, anionic headgroups, alcohols, urea, and water, to estimate their concentrations in the interfacial regions of association colloids from reaction product yields. In the chemical trapping method, product yields are proportional to the concentrations of water and other nucleophiles within the interfacial region, not their stoichiometric concentrations in solution. Changes in the balance of forces controlling aggregate structure are reflected in changes in interfacial concentrations of water and other components in association colloids as reported by the chemical trapping method. Significant changes in interfacial water and counterion concentrations are observed during structural transitions. Specific ion effects on sphere-to-rod transitions of cationic amphiphiles are interpreted in terms of the strengths of headgroup and counterion pairing and ion hydration interactions. Trapping results also provide important information on interfacial compositions of microemulsions, vesicles, nonionic micelles and macroemulsions, reverse micelles, micelles in aqueous urea, and anionic polyelectrolytes. Identifying relationships between aggregate morphology and interfacial composition by chemical trapping has just begun.
[Show abstract][Hide abstract] ABSTRACT: The assumptions of the pseudophase model for chemical reactivity in homogeneous microemulsions are used to determine the distribution of alpha-tocopherol (TOC) in macroemulsions from changes in the observed rate constant (k(obs)) for reaction between 4-hexadecylarenediazonium ion (16-ArN2+) probe and TOC with increasing surfactant concentration. Two partition constants are needed to describe the distribution of TOC or other antioxidant (AO) or polar uncharged molecule between the oil and interfacial (P(O)(I)) and the water and interfacial (P(W)(I)) regions of stirred fluid emulsions. The observed rate constants are measured electrochemically. Here we report values of P(O)(I) and P(W)(I) for the distribution of TOC in octane/acidic water/C12E6 (hexaethylene glycol monododecyl ether) and octane/acidic water/C12E4 (Brij 30, tetraethylene glycol dodecyl ether) emulsions obtained by fitting two kinetic data sets with an equation based on the pseudophase model and solving two equations in two unknowns. The partition constants were used to estimate the %TOC in each region of the emulsions. In 1:1 oil:water C12E6 emulsions, at 2% volume fraction of C12E6, 73% of TOC is in the interfacial region, 26% in the octane and about 1% in the water. The distributions of TOC in C12E4 emulsions are similar. The combined electrochemical-pseudophase model approach is applicable to any AO or other compound that reacts with 16-ArN2+. The second-order rate constant, k(I), for reaction in the interfacial region of the emulsions is also estimated from the kinetic data and is about the same for both surfactants (k(I) approximately 0.1-0.2 M(-1)s(-1)) showing that the medium properties of the interfacial regions of C12E6 and C12E4 emulsions are similar. Comparison of these rate constants for a variety of AOs may provide a scale of AO efficiency that is independent of AO distribution between the oil, interfacial and aqueous regions of emulsions.
Advances in Colloid and Interface Science 12/2006; 123-126:303-11. · 8.64 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Results from chemical trapping experiments in micellar solutions containing 1.5-5 mM aqueous solutions of three didodecyl dicationic dibromide gemini surfactants with different methylene spacer lengths (12-n-12 2Br where n = 2-4 CH(2) groups) gave quantitative estimates of the molarities of interfacial bromide (Br(m)) and water (H(2)O(m)), the fractions of free and paired headgroups and counterions, and the net headgroup charge. These results are one of the most detailed compositional studies of an association colloid interface to date. Br(m) increases and H(2)O(m) decreases as n decreases and the two cationic charges are closer together. The 12-2-12 2Br gemini (the only one of the three geminis known to form threadlike micelles) shows a marked increase in Br(m) (from 2.3 to 3.6 M) and a decrease in H(2)O(m) (from 35 to 17 M) at the exceptionally low surfactant concentration in the vicinity of the previously reported sphere-to-rod transition or second cmc concentration. Rod formation occurs because of an increase in headgroup-counterion association and dehydration at the micelle surface that depend on both the free energies of hydration and specific ion interactions and surfactant and counterion concentrations. These and other recent chemical trapping results support a new model for the balance of forces controlling morphological transitions of association colloids. The hydrophobic effect drives the formation of headgroup-counterion pairs, which have a lower demand for water of hydration. Release of water permits tighter packing and formation of cylindrical aggregates.
Journal of the American Chemical Society 02/2006; 128(2):492-501. · 10.68 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The first and second association constants, K1 and K2, for ion pair formation in aqueous 0.02-3.5 M solutions of bis(trimethyl)-alpha,omega-alkanediammonium halides with variable spacer lengths, 1-n-1 2X (n = 2-4, X = Cl, Br) and bolaform salts and for tetramethylammonium halides (TMAX, X = Cl, Br), K(TMAX), were determined by the chemical trapping method. Values for K(TMAX) are small, K(TMABr) = 0.83 M(-1) and K(TMACl) = 0.29 M(-1), in agreement with literature values. For the bolaform salts, K1 depends on spacer length and counterion type, ranges from 0.4 to 17 M(-1), is 2-10 times larger than K2, is larger for Br- than Cl-, and decreases by a factor of approximately 3 for Cl- and approximately 10 for Br- as n increases from 2 to 4. K2, for the formation of bolaform dihalide pair, is essentially the same as that for ion pair formation in TMAX solutions, i.e., K2 approximately K(TMAX). Values of K1 and K(TMABr) obtained from changes in 79Br line widths are in good agreement with those obtained by chemical trapping. The results are consistent with a thermodynamic model in which the ion association depends on the balance of the ion specific hydration free energies of cations and anions and their ion specific and hydration interactions in ion pairs. Spacer length dependent ion pairing by bolaform electrolytes, which are analogues of the headgroups and counterions of gemini amphiphiles, suggests a new model for the spacer length dependent sphere-to-rod transitions of gemini micelles. Neutral, but polar, headgroup-counterion pairs have a lower demand for hydration that free headgroups and counterions, and headgroup-counterion pair formation releases interfacial water into the bulk aqueous phase, permitting tighter amphiphile packing in rodlike micelles.
The Journal of Physical Chemistry B 01/2006; 109(49):23629-37. · 3.61 Impact Factor