Biomedical subjects

I Tucker

Publications and source records attributed to I Tucker.

At least 19 recordsLinked to original sources

PubMed2006

Influence of the polyelectrolyte poly(ethyleneimine) on the adsorption of surfactant mixtures of sodium dodecyl sulfate and monododecyl hexaethylene glycol at the air-solution interface.

The polyelectrolyte poly(ethylenenimine), PEI, is shown to strongly influence the adsorption of the anionic-nonionic surfactant mixture of sodium dodecyl sulfate, SDS, and monododecyl hexaethylene glycol, C(12)E(6), at the air-solution interface. In the presence of PEI, the partitioning of the mixed surfactants to the interface is highly pH-dependent. The adsorption is more strongly biased to the SDS as the pH increases, as the PEI becomes a weaker polyelectrolyte. At surfactant concentrations >10(-4) M, the strong interaction and adsorption result in multilayer formation at the interface, and this covers a more extensive range of surfactant concentrations at higher pH values. The results are consistent with a strong interaction between SDS and PEI at the surface that is not predominantly electrostatic in origin. It provides an attractive route to selectively manipulate the adsorption and composition of surfactant mixtures at interfaces.

Journal Article↗

PubMed2006

pH sensitive adsorption of polypeptide/sodium dodecyl sulfate mixtures.

Neutron reflectivity and surface tension have been used to investigate the pH sensitivity of the adsorption of poly-L-lysine hydrobromide and sodium dodecyl sulfate mixtures at the air-solution interface. The surface tension variation with surfactant concentration is complex, and between the critical aggregation concentration and critical micellar concentration there is a marked increase in the surface tension. The neutron reflectivity results show that this is associated with a depletion of the surface of polypeptide/surfactant complexes. The variations in the adsorption and surface tension with pH are attributed to changes in the polypeptide conformation at the interface and in solution.

Adsorption↗

PubMed2006

Elongational flow induced ordering in surfactant micelles and mesophases.

We have used small angle neutron scattering, SANS, to investigate the elongational flow induced ordering in surfactant micelles and mesophases. Spatially resolved SANS measurements have been used to determine the distribution of orientational ordering over the flow velocity pattern in an elongational flow cell, and comparison with the effects of shear flow are made. Two different surfactant systems have been studied, the charged wormlike mixed micelles of hexaethylene monododecyl ether, C16E6/hexadecyl trimethylammonium bromide, C16TAB (3% C16E(6)/5 mol% C16TAB), and the Lalpha lamellar phase of C16E6 (50.6 wt% C16E6 at 55 degrees C), and a substantially different response is observed. The orientational distribution of the Lalpha lamellar phase of C16E6 reflects the flow velocity pattern distribution within the cell, whereas for the wormlike mixed micelles of C16E6/C16TAB this is not the case, and this is associated with the shear thinning behavior of that system.

Journal Article↗

PubMed2005

Polyelectrolyte modified solid surfaces: the consequences for ionic and mixed ionic/nonionic surfactant adsorption.

This paper describes how the cationic polyelectrolyte, polyDMDAAC (poly(dimethyl diallylammonium chloride)), is used to manipulate the adsorption of the anionic surfactant SDS and the mixed ionic/nonionic surfactant mixture of SDS (sodium dodecyl sulfate)/C(12)E(6) (monododecyl hexaethylene glycol) onto the surface of hydrophilic silica. The deposition of a thin robust polymer layer from a dilute polymer/surfactant solution promotes SDS adsorption and substantially modifies the adsorption of SDS/C(12)E(6) mixtures in favor of a surface relatively rich in SDS compared to the solution composition. Different deposition conditions for the polyDMDAAC layer are discussed. In particular, at higher solution polymer concentrations and in the presence of 1 M NaCl, a thicker polymer layer is deposited and the reversibility of the surfactant adsorption is significantly altered.

Journal Article↗

PubMed2005

Adsorption of polyelectrolyte/surfactant mixtures at the air-solution interface: poly(ethyleneimine)/sodium dodecyl sulfate.

Neutron reflectivity and surface tension have been used to characterize the adsorption of the polyelectrolyte/ionic surfactant mixture of poly(ethyleneimine) (PEI) and sodium dodecyl sulfate (SDS) at the air-water interface. The surface tension behavior and adsorption patterns show a strong dependence upon the solution pH. However, the SDS adsorption at the interface is unexpectedly most pronounced when the pH is high (when the polymer is essentially a neutral polymer) and when the polymer architecture is branched rather than linear. For both the branched and the linear PEI polymer/surfactant complex formation results in a significant enhancement of the amount of SDS at the interface, down to surfactant concentrations approximately 10(-6) M. For the branched PEI a transition from a monolayer to a multilayer adsorption is observed, which depends on surfactant concentration and pH. In contrast, for the linear polymer, only monolayer adsorption is observed. This substantial increase in the surface activity of SDS by complexation with PEI results in spontaneous emulsification of hexadecane in water and the efficient wetting of hydrophobic substrates such as Teflon. In regions close to charge neutralization the multilayer adsorption is accentuated, and more extensively ordered structures, giving rise to Bragg peaks in the reflectivity data, are evident.

Journal Article↗

PubMed2005

The microstructure of di-alkyl chain cationic/nonionic surfactant mixtures: observation of coexisting lamellar and micellar phases and depletion induced phase separation.

The evolution of the microstructure and composition occurring in the aqueous solutions of di-alkyl chain cationic/nonionic surfactant mixtures has been studied in detail using small angle neutron scattering, SANS. For all the systems studied we observe an evolution from a predominantly lamellar phase, for solutions rich in di-alkyl chain cationic surfactant, to mixed cationic/nonionic micelles, for solutions rich in the nonionic surfactant. At intermediate solution compositions there is a region of coexistence of lamellar and micellar phases, where the relative amounts change with solution composition. A number of different di-alkyl chain cationic surfactants, DHDAB, 2HT, DHTAC, DHTA methyl sulfate, and DISDA methyl sulfate, and nonionic surfactants, C12E12 and C12E23, are investigated. For these systems the differences in phase behavior is discussed, and for the mixture DHDAB/C12E12 a direct comparison with theoretical predictions of phase behavior is made. It is shown that the phase separation that can occur in these mixed systems is induced by a depletion force arising from the micellar component, and that the size and volume fraction of the micelles are critical factors.

Journal Article↗

PubMed2005

Adsorption of nonionic surfactant mixtures at the hydrophilic solid-solution interface.

The adsorption of the mixed nonionic surfactants, monododecyl triethylene glycol (C2EO3) and monododecyl octaethylene glycol (C12EO8), at the hydrophilic silica-solution interface has been studied by specular neutron reflectivity. The adsorption at the solid-solution interface is compared with that previously measured at the air-solution interface. The marked differences that are observed are explained in terms of the different packing constraints or preferred curvature arising from the disparity in the respective headgroup dimensions.

Journal Article↗

PubMed2005

Structure of mixed anionic/nonionic surfactant micelles: experimental observations relating to the role of headgroup electrostatic and steric effects and the effects of added electrolyte.

The structures of the mixed anionic/nonionic surfactant micelles of SDS/C12E6 and SDS/C12E8 have been measured by small angle neutron scattering (SANS). The variations in the micelle aggregation number and surface charge with composition, measured in D2O and in dilute electrolyte, 0.01 and 0.05 M NaCl, provide data on the relative roles of the surfactant headgroup steric and electrostatic interactions and their contributions to the free energy of micellization. For the SDS/C12E8 mixture, solutions increasingly rich in C12E8 show a modest micellar growth and an increase in the surface charge. The changes with increasing electrolyte concentration are similarly modest. In contrast, for the SDS/C12E6 mixture, solutions rich in C12E6 show a more significant increase in aggregation number. Furthermore, electrolyte has a more substantial effect on the aggregation for the nonionic (C12E6) rich mixtures. The experimental results are discussed in the context of estimates of the steric and electrostatic contributions to the free energy of micellization, calculated from the molecular thermodynamic approach. The variation in micelle surface charge is discussed in the context of the "dressed micelle" theory for micelle ionization, and other related data.

Journal Article↗

PubMed2004

Adsorption of aromatic counterions at the surfactant/water interface: a neutron reflectivity study of hydroxybenzoate and chlorobenzoate counterions at the hexadecyl trimethylammonium surfactant/water interface.

Specular neutron reflectivity has been used to investigate the adsorption of the aromatic counterions hydroxybenzoate and chlorobenzoate at the hexadecyl trimethylammonium bromide surfactant monolayer/water interface. The degree of counterion binding and the location of the counterions at the interface are shown to depend on the isomeric form of the counterion. For hydroxybenzoate, the para-substituted counterion is located within the headgroup region of the surfactant monolayer, and there is of order one counterion for every two surfactant ions. For the ortho-substituted counterion, the degree of counterion binding is higher. There is of order 0.85 counterions for each surfactant ion, and the counterion is located within the hydrophobic region of the monolayer, some 5 A from the center of the headgroup distribution. Similar results were found for the chlorobenzoate counterion, but in that case it was the para-substituted counterion that was more tightly bound and located within the hydrophobic region of the surfactant monolayer. The results for the ortho-substituted hydroxybenzoate and for the para-substituted chlorobenzoate are consistent with those previously reported for the para-tosylate. The results are discussed in the context of the ability of the specific aromatic counterion isomer to promote massive micellar growth, and the results shed light on that mechanism.

Adsorption↗

PubMed2004

Manipulation of the adsorption of ionic surfactants onto hydrophilic silica using polyelectrolytes.

This paper demonstrates the use of polyelectrolytes to modify and manipulate the adsorption of ionic surfactants onto the hydrophilic surface of silica. We have demonstrated that the cationic polyelectrolyte poly(dimethyl diallylammonium chloride), poly-dmdaac, modifies the adsorption of cationic and anionic surfactants to the hydrophilic surface of silica. A thin robust polymer layer is adsorbed from a dilute polymer/surfactant solution. The resulting surface layer is cationic and changes the relative affinity of the cationic surfactant hexadecyl trimethylammonium bromide, C16TAB, and the anionic surfactant sodium dodecyl sulfate, SDS, to adsorb. The adsorption of C16TAB is dramatically reduced. In contrast, strong adsorption of SDS was observed, in situations where SDS would normally have a low affinity for the surface of silica. We have further shown that subsequent adsorption of the anionic polyelectrolyte sodium poly(styrene sulfonate), Na-PSS, onto the poly-dmdaac coated surface results in a change back to an anionic surface and a further change in the relative affinities of the cationic and anionic surfactants for the surface. The relative amounts of C16TAB and SDS adsorption depend on the coverage of the polyelectrolyte, and these preliminary measurements show that this can be manipulated.

Journal Article↗

PubMed2004

Surface ordering in dilute dihexadecyl dimethyl ammonium bromide solutions at the air-water interface.

At elevated temperatures and in dilute solution, we have observed lamellar surface ordering at the air-water interface of dihexadecyl dimethylammonium bromide, DHDAB, in the presence of electrolyte. With increasing temperature, the onset in ordering is observed between 35 and 40 degrees C. At 40 degrees C, there is an abrupt change in the lamellar spacing, from approximately 33 to approximately 40 A. Furthermore, in the presence of the cosurfactant benzyl alcohol, the ordering occurs at a lower temperature, between 20 and 25 degrees C. The change in lamellar spacing with temperature is attributed to a surface-induced transition, similar to the Lbeta to Lalpha phase transition observed in bulk lamellar dispersions.

Journal Article↗

PubMed2004

Surface and solution behavior of the mixed dialkyl chain cationic and nonionic surfactants.

The surface and solution behavior of the mixed dialkyl chain cationic and nonionic surfactant mixture of dihexadecyldimethylammonium bromide, DHDAB, and hexaethylene monododecyl ether, C12E6, has been investigated, using primarily the scattering techniques of small-angle neutron scattering and neutron reflectivity. Within the time scale of the measurements, the adsorption of the pure component C12E6 at the air-solution interface shows no time dependence. In contrast, the adsorption of the DHDAB/C12E6 mixture and pure DHDAB has a pronounced time dependence. The characteristic time for adsorption varies with surfactant concentration, composition, and temperature. It is approximately 2-3 h for the DHDAB/C12E6 mixture, dependent upon concentration and composition, and approximately 50 min for DHDAB. At the air-solution interface, the equilibrium composition of the adsorbed layer shows a marked departure from ideal mixing, which is dependent upon both the solution concentration and the concentration of added electrolyte. In contrast, the composition of the aggregates in the bulk solution that are in equilibrium with the surface is close to ideal mixing, as expected for solution concentrations well in excess of the critical micellar concentration. The structure of the mixed adsorbed layer has been measured and compared with the structure of the equivalent pure surfactant monolayer, and no substantial changes in structure or conformation are observed. The extreme departure from ideal mixing in the adsorption behavior of the DHDAB/C12E6 mixture is discussed in the context of the structure of the adsorbed layer, changes in the underlying solution structures, and the failure of regular solution theory to predict such behavior.

Journal Article↗

PubMed2003

The structure of mixed nonionic surfactant monolayers at the air-water interface: the effects of different alkyl chain lengths.

The structure of mixed nonionic surfactant monolayers of monodecyl hexaethylene glycol (C10E6) and monotetradecyl hexaethylene glycol (C14E6) adsorbed at the air-water interface has been determined by specular neutron reflectivity. Using partial isotopic labeling (deuterium for hydrogen) of the alkyl and ethylene oxide chains of each surfactant, the distribution and relative positions of the chains at the interface have been obtained. The packing of the two different alkyl chain lengths results in structural changes compared to the pure surfactant monolayers. This results in changes in the relative positions of the alkyl chains and of the ethylene oxide chains at the interface. The role of the alkyl chain length is contrasted with that of the ethylene oxide chain length, determined from results reported previously on the nonionic surfactant mixture of monododecyl triethylene glycol (C12E3) and monododecyl octaethylene glycol (C12E8).

Journal Article↗

PubMed2002

Comparison of the coadsorption of benzyl alcohol and phenyl ethanol with the cationic surfactant, hexadecyl trimethyl ammonium bromide, at the air-water interface.

A comparison of the coadsorption of benzyl alcohol and phenyl ethanol with the cationic surfactant, hexadecyl trimethyl ammonium bromide, C16TAB, at the air-water interface is made using the specular reflection of neutrons. The phenyl ethanol is more surface active than the benzyl alcohol, and competes more effectively with the C16TAB for the interface. The structure of the C16TAB component in the mixed monolayer is compared with the structure of the pure C16TAB monolayer at an equivalent area per molecule. The addition of the aromatic alcohol subtly alters the conformation of the C16TAB and draws it closer to the aqueous subphase. The center of the alcohol distribution is located in the interface adjacent to the C6 group of the C16TAB alkyl chain closest to the headgroup. Compared to the benzyl alcohol, the more hydrophobic phenyl ethanol is slightly farther away from the headgroup, and has a greater impact on the conformation of the alkyl chain of the C16TAB.

Journal Article↗

PubMed2002

Adsorption of nonionic mixtures at the air-water interface: effects of temperature and electrolyte.

Specular neutron reflection has been used to investigate the effects of temperature and added electrolyte on the adsorption of nonionic surfactants and nonionic surfactant mixtures at the air-water interface. For the alkyl poly-oxyethylene oxide nonionic surfactants, C(n)EO(m), the adsorption at the air-water interface is independent of temperature for surfactants with shorter ethylene oxide groups, whereas there is an increasing tendency for increased adsorption with temperature for surfactants with longer ethylene oxide groups. The addition of "salting in" (sodium thiocyanate, NaSCN) and "salting out" (sodium chloride, NaCl, sodium sulphate, Na2SO4) electrolyte results in reduced and enhanced adsorption, respectively, for C12EO8, whereas both types of electrolyte result in enhanced adsorption for C12EO12. The addition of electrolyte does not substantially alter the temperature dependence of the adsorption of the pure monolayers. For the nonionic mixtures of C12EO3/C12EO8 increasing temperature results in a surface richer in the least surface-active component, C12EO8. For the same nonionic mixture, the addition of "salting in" and "salting out" electrolyte results in an reduced and increased adsorption, respectively. The addition of "salting in" electrolyte results in a surface more rich in C12EO3, whereas for the addition of both "salting in" and "salting out" electrolyte the surface composition is essentially unaltered.

Journal Article↗

PubMed2001

Selection of excipients for melt extrusion with two poorly water-soluble drugs by solubility parameter calculation and thermal analysis.

The aim of this study was to determine the miscibility of drug and excipient to predict if glass solutions are likely to form when drug and excipient are melt extruded. Two poorly water-soluble drugs, indomethacin and lacidipine, were selected along with 11 excipients (polymeric and non-polymeric). Estimation of drug/excipient miscibility was performed using a combination of the Hoy and Hoftzyer/Van Krevelen methods for Hansen solubility parameter calculation. Miscibility was experimentally investigated with differential scanning calorimetry (DSC) and hot stage microscopy (HSM). Studies were performed at drug/excipient ratios, 1:4, 1:1 and 4:1. Analysis of the glass transition temperature (T(g)) was performed by quench cooling drug/excipient melts in the DSC. Differences in the drug/excipient solubility parameters of <7.0 MPa(1/2) were predicted to indicate significant miscibility and, therefore, glass solution formation on melt extrusion. In comparison, differences of >10 MPa(1/2) were expected to indicate a lack of miscibility and not form glass solutions when melt extruded. Experimentally, miscibility was shown by changes in drug/excipient melting endotherms and confirmed by HSM investigations. Experimental results were in agreement with solubility parameter predictions. In addition, drug/excipient combinations predicted to be largely immiscible often exhibited more than one T(g) upon reheating in the DSC. Melt extrusion of miscible components resulted in amorphous solid solution formation, whereas extrusion of an "immiscible" component led to amorphous drug dispersed in crystalline excipient. In conclusion, combining calculation of Hansen solubility parameters with thermal analysis of drug/excipient miscibility can be successfully applied to predict formation of glass solutions with melt extrusion.

Calorimetry, Differential Scanning↗

PubMed1997

The Structure of Nonionic Micelles in Less Polar Solvents

Small angle neutron scattering, SANS, has been used to investigate the structure and geometry of nonionic micelles of monododecyl octaethylene glycol C12EO8, monododecyl hexaethylene glycol C12EO6, and monohexadecyl octaethylene glycol C16EO8 in less polar solvents: mixed solvents of water and glycerol, sorbitol, and ethylene glycol. For C12EO8 in glycerol/water solvent mixtures the addition of glycerol results in an increase in the micelle aggregation number and a decrease in the ethylene oxide (EO) headgroup hydration. The increase in micelle size is associated with the dehydration of the ethylene oxide headgroup and the consequent closer proximity of the lower consolute boundary. This follows from the observation that the same trends are seen at fixed glycerol content and increasing temperature where the intermicellar interactions become attractive. For C12EO6 micelles in water/ethylene glycol mixtures similar trends are observed, and the same conclusions may be drawn despite an increase in the clouding temperature. This can be explained by a greater dehydration of the solvent ethylene glycols such that the rate of change of solvent quality for the micelles with temperature is suppressed. A combination of SANS and Couette shear flow alignment has been used to investigate the structure of C16EO8 micelles in water/sorbitol and water/glycerol mixtures. The addition of sorbitol or glycerol results in less anisotropically shaped micelles. The resulting micelles are more labile, and show evidence of flexibility and shear induced transformations or extreme polydispersity. The temperature dependence of the micelle rod length of C16EO8/water/glycerol is similar to that previously observed for C16EO6 and C16EO8 micelles in water and for the mixed micelles of C16EO6/C16TAB.

Journal Article↗

PubMed1996

The Influence of Sorbitol on the Adsorption of Surfactants at the Air-Liquid Interface

Neutron reflection and surface tension have been used to study the adsorption of the nonionic surfactant monododecyl hexaethylene glycol (C12E6) and the mixed nonionic-anionic surfactants n-dodecyl triethylene glycol (C12E3) and Sodium dodecyl sulfate (SDS) at the air-liquid interface. Water and a sorbitol (d-glucitol, CH2OH(HCOH)4CH2OH)/water mixture were selected as the solvents. The addition of 300 g/liter of sorbitol to an aqueous solution of C12E6 reduces the critical micellar concentration, cmc, from approximately 7 x 10(-5) to approximately 3 x 10(-5) M, and increases the surface pressure at the cmc; the effect on the C12E3/SDS mixture is less. Despite these changes, the pattern of adsorption at the air-liquid interface is essentially unaltered by the addition of sorbitol, and the surface tension and neutron reflectivity data are in good agreement. The consequences of the sorbitol addition are however seen directly in the structure of the C12E6 monolayer. The ethylene oxide (EO) chain is more extended than in water, and more displaced from the solvent, consistent with dehydration of the ethylene oxide group.

Journal Article↗