Cécile Dreiss - Academia.edu (original) (raw)
Papers by Cécile Dreiss
Langmuir : the ACS journal of surfaces and colloids, Jan 4, 2015
Inclusion complexes between cyclodextrins (CDs) and polymers - so-called pseudopolyrotaxanes (PPR... more Inclusion complexes between cyclodextrins (CDs) and polymers - so-called pseudopolyrotaxanes (PPR) - are at the origin of fascinating supramolecular structures, which are finding increasing uses in biomedical and technological fields. In this work, we explore the complexation of a range of cyclodextrins with Tetronic T1307, a four-arm block-copolymer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with a pH-responsive central ethylene diamine spacer, and its impact on micellisation and sol-gel transition. At low concentrations, small-angle neutron scattering (SANS) combined to dynamic light scattering (DLS) measurements show the presence of spherical micelles with a highly hydrated shell and a dehydrated core. Increasing the temperature leads to more compact micelles and larger aggregation numbers, while acidic conditions induce a shrinking of the micelles, with fewer unimers per micelle and a more hydrated corona. At high concentrations, T1307 undergoes a sol-gel...
Langmuir, 2015
Inclusion complexes between cyclodextrins and polymers-so-called pseudopolyrotaxanes (PPR)-are at... more Inclusion complexes between cyclodextrins and polymers-so-called pseudopolyrotaxanes (PPR)-are at the origin of fascinating supramolecular structures, which are finding increasing uses in biomedical and technological fields. Here we explore the impact of both native and a range of modified cyclodextrins (CD) on the self-assembly of X-shaped poly(ethylene oxide)-poly(propylene oxide) block copolymers, so-called Tetronics or poloxamines, by focusing on Tetronic 904 (T904, Mw 6700). The effects are markedly dependent on the type and arrangement of the substituents on the macrocycle. While native CDs drive the formation of a solid PPR, most substituted CDs induce micellar breakup, with dimethylated β-CD (DIMEB) having the strongest impact and randomly substituted CDs a much weaker disruptive effect. Using native α-CD as a "molecular trap", we perform competitive binding experiments-where two types of CDs thread together onto the polymer chains-to establish that DIMEB indeed has the highest propensity to form an inclusion complex with the polymer, while hydroxypropylated CDs do not thread. 1D (1)H NMR and ROESY experiments confirm the formation of a soluble PPR with DIMEB in which the CD binds preferentially to the PO units, thus providing the drive for the observed demicellization. A combination of dynamic light scattering (DLS) and small-angle neutron scattering (SANS) is used to extract detailed structural parameters on the micelles. A binding model is proposed, which exploits the chemical shifts of selected protons from the CD in conjunction with the Hill equation, to prove that the formation of the PPR is a negatively cooperative process, in which threaded DIMEBs hamper the entrance of subsequent macrocycles.
Biomacromolecules, Jan 15, 2015
Small-angle neutron scattering (SANS) was used to characterize the nano-scale structure of enzyma... more Small-angle neutron scattering (SANS) was used to characterize the nano-scale structure of enzymatically cross-linked chitosan/gelatin hydrogels obtained from two protocols: a pure chemical cross-linking process (C), which uses the natural enzyme microbial transglutaminase, and a physical-co-chemical (PC) hybrid process, where covalent cross-linking is combined with the temperature-triggered gelation of gelatin, occurring through the formation of triple-helices. SANS measurements on the final and evolving networks provide a correlation length (ξ), which reflects the average size of expanding clusters. Their growth in PC gels is restricted by the triple-helices (ξ ~ 10s of Å) while ξ in pure chemical gels increases with cross-linker concentration (~ 100s of Å). In addition, the shear elastic modulus in PC gels is higher than in pure C gels. Our results thus demonstrate that gelatin triple helices provide a template to guide the cross-linking process; overall, this work provides impor...
The Journal of Physical Chemistry B, 2012
Spectroscopic measurements (uv/vis absorbance and fluorescence) and time-resolved small-angle neu... more Spectroscopic measurements (uv/vis absorbance and fluorescence) and time-resolved small-angle neutron scattering experiments (TR-SANS) were used to follow the breakdown of Pluronic micelles by heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) over time in order to elucidate the mechanism of micellar rupture, generally attributed to polypseudotorotaxane (PR) formation between the cyclodextrin and the central hydrophobic PPO block. The spectroscopic measurements with two different probes (methyl orange and nile red) suggest that very rapid changes (on the order of seconds) take place when mixing DIMEB with F127 Pluronic and that no displacement of the probe from the cyclodextrin cavity occurs, which is in disagreement with PR formation. TR-SANS measurements demonstrate for the first time that the micelles are broken down in less than 100 ms, which categorically rules out PR formation as the mechanism of rupture. In addition, the same mechanism is demonstrated with other Pluronics, P85 and P123. In the latter case, after micellar rupture, lamellar structures are seen to form over a longer period of time, thus suggesting that after the instantaneous micellar disruption, further, longer-scale rearrangements are not excluded.
Polymer, 2007
... particle content. Fig. 3 shows the experimental T 2 relaxation decays obtained for blends of ... more ... particle content. Fig. 3 shows the experimental T 2 relaxation decays obtained for blends of polysilicate resins and 100K crosslinked PDMS at 18 °C, together with the decay curve for pure un-crosslinked 116K PDMS. The intensity ...
Macromolecular Bioscience, 2014
This work investigates the effect of combining physical and chemical gelation processes in a biop... more This work investigates the effect of combining physical and chemical gelation processes in a biopolymer blend: chitosan and tilapia fish gelatin. Chemical (C) gels are obtained by cross-linking with the microbial enzyme transglutaminase at 37 °C. Hybrid physical-co-chemical (PC) gels are cross-linked at 21 °C, below gelatin gelation temperature. These protocols provide two microenvironments for the gelation process: in C gels, both gelatin and chitosan are present as single strands; in PC gels, cross-linking proceeds within a transient physical gel of gelatin, filled by chitosan strands. The chitosan/gelatin chemical networks generated in PC gels show a consistently higher shear modulus than pure C gels; they are also less turbid than their C gels counterparts, suggesting a more homogeneous network. Finally, chitosan enhances the gels' shear modulus in all gels. Proliferation assays show that MC3T3 cells proliferate in these mixed, hybrid gels and better so on PC gels than in C mixed gels.
Langmuir, 2005
The compaction of DNA by a cationic surfactant both in the bulk and adsorbed on the surface of la... more The compaction of DNA by a cationic surfactant both in the bulk and adsorbed on the surface of latex particles was followed for the first time by SANS. In the bulk, a decrease in the overall size of the DNA coil in the presence of the cationic surfactant was observed at a negative-to-positive charge ratio far below the phase separation region, at a negative-to-positive charge ratio of 18. Additionally, large surfactant aggregates seem to form within the DNA-surfactant complex. On the other hand, DNA adsorbs onto the surface of latex particles, forming a thick layer, as evidenced by the fitting of the SANS data to a core-shell form factor. Addition of a cationic surfactant to the DNA-coated latex particles at a negative-to-positive charge ratio of 38 induces a slight decrease in the size of the particle layer, where the cationic surfactant is evenly distributed within the adsorbed layer. A further decrease of the negative-to-positive charge ratio to 18 induces a dramatic change in the SANS data that suggests significant compaction of the adsorbed layer and the formation of large surfactant aggregates, similar to those detected in the bulk.
Langmuir, 2006
The structure factors of colloidal silica dispersions at rather high volume fractions (from 0.055... more The structure factors of colloidal silica dispersions at rather high volume fractions (from 0.055 to 0.22) were measured by small-angle X-ray scattering and fitted with both the equivalent hard-sphere potential model (EHS) and the Hayter-Penfold/Yukawa potential model (HPY). Both of these models described the interactions in these dispersions successfully, and the results were in reasonable agreement. The strength and range of the interaction potentials decreased with increasing particle volume fractions, which suggests shrinkage of the electrical double layer arising from an increase in the counterion concentration in the bulk solution. However, the interactions at the average interparticle separation increased as the volume fraction increased. The interaction ranges (δ) determined by the two models were very similar. Structure factors were also used to determine the size and volume fraction of the particles. The values of the size obtained from the structure factors were slightly larger than those obtained from the form factors; this difference is ascribed to the nonspherical shape and polydispersity of the colloidal particles. The volume fractions measured by these two methods were very similar and are both in good agreement with the independently measured results.
Langmuir, 2004
Small-angle neutron scattering studies were used to investigate the effect of adding an alcohol e... more Small-angle neutron scattering studies were used to investigate the effect of adding an alcohol ethoxylate nonionic surfactant (d-C12E20) to aqueous solutions of a cationic surfactant, erucyl bis(hydroxyethyl) methylammonium chloride (EHAC), with and without salt (KCl). The systematic use of contrast-matching, by alternately highlighting or hiding one of the surfactants, confirms that mixed micelles are formed. In salt-free solutions, mixed spherical micelles are formed and a core-shell model combined with a Hayter-Penfold potential was used to describe the data. The core radius is dominated by the EHAC tails and the outer radius determined by the ethoxylate headgroups of the nonionic surfactant. Addition of KCl promotes micellar growth; however, results of varying the solvent contrast revealed that when the nonionic surfactant is incorporated into the wormlike structure micellar breaking is promoted. Thus, mixed wormlike micelles with shorter contour lengths compared to the pure EHAC worms are formed.
Langmuir, 2004
The effect of adding an alcohol ethoxylate nonionic surfactant (C(18)E(18)) to aqueous solutions ... more The effect of adding an alcohol ethoxylate nonionic surfactant (C(18)E(18)) to aqueous solutions of a cationic surfactant, erucyl bis(hydroxyethyl) methylammonium chloride (EHAC,CH(3)(CH(2))(7)(CH)(2)(CH(2))(12)N(+)-(CH(2)CH(2)OH)(2)CH(3)Cl(-)), was studied using small-angle neutron scattering (SANS), steady-state rheology, and cryo-transmission electron microscopy (Cryo-TEM). This cationic surfactant has the ability to self-assemble into giant wormlike micelles in the presence of an electrolyte, such as KCl. In salt-free solutions, the mixture of the two surfactants gave rise to spherical micelles. The scattering curves obtained were fitted with a polydisperse core-shell model combined with a Hayter Penfold potential. The inner and outer radii were found to be dependent on the surfactant ratio. In the presence of KCl, mixed wormlike micelles were formed. However, further addition of C(18)E(18) promoted the breaking of the micellar worms with the appearance of a structure peak in the scattering curves. In addition, it was found that the low shear viscosity is decreased upon addition of the alcohol ethoxylate nonionic surfactant. These findings are in good qualitative agreement with the Cryo-TEM images. The results show that the addition of the nonionic surfactant to the system is a method of controlling the worm length.
Journal of the American Chemical Society, 2009
The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur musta... more The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur mustard (HD, bis(2-chlororethyl) sulfide) and a range (chloroethyl) sulfide simulants of variable lipophilicity have been examined using a hydrogen peroxide-based microemulsion system. SANS (small-angle neutron scattering), SAXS (small-angle X-ray scattering), PGSE-NMR (pulsed-gradient spin-echo NMR), fluorescence quenching, and electrospray mass spectroscopy (ESI-MS) were implemented to examine the distribution of HD, its simulants, and their oxidation/hydrolysis products in a model oil-in-water microemulsion. These measurements not only present a means of interpreting decontamination rates but also a rationale for the design of oxidation catalysts for these toxic materials. Here we show that by localizing manganese-Schiff base catalysts at the oil droplet-water interface or within the droplet core, a range of (chloroethyl) sulfides, including HD, spanning some 7 orders of octanol-water partition coefficient (K(ow)), may be oxidized with equal efficacy using dilute (5 wt. % of aqueous phase) hydrogen peroxide as a noncorrosive, environmentally benign oxidant (e.g., t(1/2) (HD) approximately 18 s, (2-chloroethyl phenyl sulfide, C(6)H(5)SCH(2)CH(2)Cl) approximately 15 s, (thiodiglycol, S(CH(2)CH(2)OH)(2)) approximately 19 s {20 degrees C}). Our observations demonstrate that by programming catalyst lipophilicity to colocalize catalyst and substrate, the inherent compartmentalization of the microemulsion can be exploited to achieve enhanced rates of reaction or to exert control over product selectivity. A combination of SANS, ESI-MS and fluorescence quenching measurements indicate that the enhanced catalytic activity is due to the locus of the catalyst and not a result of partial hydrolysis of the substrate.
Journal of Colloid and Interface Science, 2012
The effect of encapsulating oils on the phase behaviour and the microstructure of wormlike micell... more The effect of encapsulating oils on the phase behaviour and the microstructure of wormlike micelles formed by polyoxyethylene cholesteryl ether (ChEO(10)) and triethylene glycol monododecyl ether co-surfactant (C(12)EO(3)) was investigated using rheology, Cryo-TEM and small-angle neutron scattering measurements. Six alkyl ester oils bearing small, systematic variations in their molecular structure were encapsulated: ethyl butyrate (EB(24)), ethyl caproate (ECO(26)), ethyl caprylate (EC(28)), methyl enanthate (ME(17)), methyl caprylate (MC(18)) and butyl butyrate (BB(44)), where the subscripts refer to the length of the alkyl chain and fatty acid chain, respectively, on either sides of the ester link. The addition of alkyl ester oils to ChEO(10)/C(12)EO(3) solutions promotes the longitudinal growth of the surfactant aggregates into wormlike micelles possessing an elliptical cross-section, with r(minor) 31±2 Å and r(major) varying from 45 to 70 Å. At fixed alkyl chain length, oils with longer fatty acid chains were found to be more efficient in inducing wormlike micelle formation or their elongation, following the order: EC(28)>ECO(26)>EB(24). Instead, at fixed fatty acid chain length, increasing the alkyl chain has a negative effect on the longitudinal micellar growth (MC(18)>EC(28) and EB(24)>BB(44)). At high co-surfactant concentrations and in the presence of EB(24), an unusual phase of ring-like micelles was detected. Overall, the orientation of the oil molecules within the micelles enables them to act as co-surfactants with a small head-group, decreasing the average cross-section area and promoting longitudinal growth of the micelles into worms.
Journal of Colloid and Interface Science, 2010
The effect of hydrophobic and hydrophilic co-solutes on the rheological properties of wormlike mi... more The effect of hydrophobic and hydrophilic co-solutes on the rheological properties of wormlike micelles of cetyltrimethylammonium bromide (CTAB) and sodium salicylate (NaSal) or sodium bromide (NaBr) was investigated. Monomeric (ethanol, 2-propanol, benzene and benzylic alcohol) and polymeric species (poly(ethylene oxide), poly(vinyl alcohol) and poly(propylene oxide), respectively PEO, PVA and PPO) of varying molecular weight were studied in order to assess the effect of co-solute 'length' on the interactions with the wormlike micelles. Rheological properties were characterised by the plateau modulus G(0) and the relaxation time τ(R) obtained from fits to the Maxwell model, and by the zero-shear viscosity η(0). The rheological properties were unaltered by the addition of all hydrophilic solutes (up to 20 mM). With hydrophobic co-solutes instead, both η(0) and τ(R) decreased considerably, while G(0) was unaffected. The effects were particularly remarkable with PPO for concentrations as low as 5 mM (ca. 0.3 g L(-1)), and τ(R) was seen to follow an exponential decrease with polymer M(w). The effect of the aromatic solutes (benzene and benzyl alcohol) on the rheology was highly dependent on the counterions used to induce micellar growth (Sal(-) or Br(-)), revealing a different type of interaction. Surprisingly, small-angle neutron scattering and Cryo-TEM measurements showed that the drastic changes observed in the rheology were not correlated to any visible structural change. Therefore the strong decrease in viscosity and relaxation time are to be attributed to other mechanisms than micellar break-up or rod-to-sphere transition.
Soft Matter, 2011
... long micelles. Hala Afifia, Marcelo A. da Silvaa, Cécile Nouvelb, Jean-Luc Sixb, Christian Li... more ... long micelles. Hala Afifia, Marcelo A. da Silvaa, Cécile Nouvelb, Jean-Luc Sixb, Christian Ligourecd and Cécile A. Dreiss*a. a King's College London, Institute of Pharmaceutical Science, 150 Stamford Street, SE1 9NH, UK. E ...
Langmuir : the ACS journal of surfaces and colloids, Jan 4, 2015
Inclusion complexes between cyclodextrins (CDs) and polymers - so-called pseudopolyrotaxanes (PPR... more Inclusion complexes between cyclodextrins (CDs) and polymers - so-called pseudopolyrotaxanes (PPR) - are at the origin of fascinating supramolecular structures, which are finding increasing uses in biomedical and technological fields. In this work, we explore the complexation of a range of cyclodextrins with Tetronic T1307, a four-arm block-copolymer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with a pH-responsive central ethylene diamine spacer, and its impact on micellisation and sol-gel transition. At low concentrations, small-angle neutron scattering (SANS) combined to dynamic light scattering (DLS) measurements show the presence of spherical micelles with a highly hydrated shell and a dehydrated core. Increasing the temperature leads to more compact micelles and larger aggregation numbers, while acidic conditions induce a shrinking of the micelles, with fewer unimers per micelle and a more hydrated corona. At high concentrations, T1307 undergoes a sol-gel...
Langmuir, 2015
Inclusion complexes between cyclodextrins and polymers-so-called pseudopolyrotaxanes (PPR)-are at... more Inclusion complexes between cyclodextrins and polymers-so-called pseudopolyrotaxanes (PPR)-are at the origin of fascinating supramolecular structures, which are finding increasing uses in biomedical and technological fields. Here we explore the impact of both native and a range of modified cyclodextrins (CD) on the self-assembly of X-shaped poly(ethylene oxide)-poly(propylene oxide) block copolymers, so-called Tetronics or poloxamines, by focusing on Tetronic 904 (T904, Mw 6700). The effects are markedly dependent on the type and arrangement of the substituents on the macrocycle. While native CDs drive the formation of a solid PPR, most substituted CDs induce micellar breakup, with dimethylated β-CD (DIMEB) having the strongest impact and randomly substituted CDs a much weaker disruptive effect. Using native α-CD as a "molecular trap", we perform competitive binding experiments-where two types of CDs thread together onto the polymer chains-to establish that DIMEB indeed has the highest propensity to form an inclusion complex with the polymer, while hydroxypropylated CDs do not thread. 1D (1)H NMR and ROESY experiments confirm the formation of a soluble PPR with DIMEB in which the CD binds preferentially to the PO units, thus providing the drive for the observed demicellization. A combination of dynamic light scattering (DLS) and small-angle neutron scattering (SANS) is used to extract detailed structural parameters on the micelles. A binding model is proposed, which exploits the chemical shifts of selected protons from the CD in conjunction with the Hill equation, to prove that the formation of the PPR is a negatively cooperative process, in which threaded DIMEBs hamper the entrance of subsequent macrocycles.
Biomacromolecules, Jan 15, 2015
Small-angle neutron scattering (SANS) was used to characterize the nano-scale structure of enzyma... more Small-angle neutron scattering (SANS) was used to characterize the nano-scale structure of enzymatically cross-linked chitosan/gelatin hydrogels obtained from two protocols: a pure chemical cross-linking process (C), which uses the natural enzyme microbial transglutaminase, and a physical-co-chemical (PC) hybrid process, where covalent cross-linking is combined with the temperature-triggered gelation of gelatin, occurring through the formation of triple-helices. SANS measurements on the final and evolving networks provide a correlation length (ξ), which reflects the average size of expanding clusters. Their growth in PC gels is restricted by the triple-helices (ξ ~ 10s of Å) while ξ in pure chemical gels increases with cross-linker concentration (~ 100s of Å). In addition, the shear elastic modulus in PC gels is higher than in pure C gels. Our results thus demonstrate that gelatin triple helices provide a template to guide the cross-linking process; overall, this work provides impor...
The Journal of Physical Chemistry B, 2012
Spectroscopic measurements (uv/vis absorbance and fluorescence) and time-resolved small-angle neu... more Spectroscopic measurements (uv/vis absorbance and fluorescence) and time-resolved small-angle neutron scattering experiments (TR-SANS) were used to follow the breakdown of Pluronic micelles by heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) over time in order to elucidate the mechanism of micellar rupture, generally attributed to polypseudotorotaxane (PR) formation between the cyclodextrin and the central hydrophobic PPO block. The spectroscopic measurements with two different probes (methyl orange and nile red) suggest that very rapid changes (on the order of seconds) take place when mixing DIMEB with F127 Pluronic and that no displacement of the probe from the cyclodextrin cavity occurs, which is in disagreement with PR formation. TR-SANS measurements demonstrate for the first time that the micelles are broken down in less than 100 ms, which categorically rules out PR formation as the mechanism of rupture. In addition, the same mechanism is demonstrated with other Pluronics, P85 and P123. In the latter case, after micellar rupture, lamellar structures are seen to form over a longer period of time, thus suggesting that after the instantaneous micellar disruption, further, longer-scale rearrangements are not excluded.
Polymer, 2007
... particle content. Fig. 3 shows the experimental T 2 relaxation decays obtained for blends of ... more ... particle content. Fig. 3 shows the experimental T 2 relaxation decays obtained for blends of polysilicate resins and 100K crosslinked PDMS at 18 °C, together with the decay curve for pure un-crosslinked 116K PDMS. The intensity ...
Macromolecular Bioscience, 2014
This work investigates the effect of combining physical and chemical gelation processes in a biop... more This work investigates the effect of combining physical and chemical gelation processes in a biopolymer blend: chitosan and tilapia fish gelatin. Chemical (C) gels are obtained by cross-linking with the microbial enzyme transglutaminase at 37 °C. Hybrid physical-co-chemical (PC) gels are cross-linked at 21 °C, below gelatin gelation temperature. These protocols provide two microenvironments for the gelation process: in C gels, both gelatin and chitosan are present as single strands; in PC gels, cross-linking proceeds within a transient physical gel of gelatin, filled by chitosan strands. The chitosan/gelatin chemical networks generated in PC gels show a consistently higher shear modulus than pure C gels; they are also less turbid than their C gels counterparts, suggesting a more homogeneous network. Finally, chitosan enhances the gels' shear modulus in all gels. Proliferation assays show that MC3T3 cells proliferate in these mixed, hybrid gels and better so on PC gels than in C mixed gels.
Langmuir, 2005
The compaction of DNA by a cationic surfactant both in the bulk and adsorbed on the surface of la... more The compaction of DNA by a cationic surfactant both in the bulk and adsorbed on the surface of latex particles was followed for the first time by SANS. In the bulk, a decrease in the overall size of the DNA coil in the presence of the cationic surfactant was observed at a negative-to-positive charge ratio far below the phase separation region, at a negative-to-positive charge ratio of 18. Additionally, large surfactant aggregates seem to form within the DNA-surfactant complex. On the other hand, DNA adsorbs onto the surface of latex particles, forming a thick layer, as evidenced by the fitting of the SANS data to a core-shell form factor. Addition of a cationic surfactant to the DNA-coated latex particles at a negative-to-positive charge ratio of 38 induces a slight decrease in the size of the particle layer, where the cationic surfactant is evenly distributed within the adsorbed layer. A further decrease of the negative-to-positive charge ratio to 18 induces a dramatic change in the SANS data that suggests significant compaction of the adsorbed layer and the formation of large surfactant aggregates, similar to those detected in the bulk.
Langmuir, 2006
The structure factors of colloidal silica dispersions at rather high volume fractions (from 0.055... more The structure factors of colloidal silica dispersions at rather high volume fractions (from 0.055 to 0.22) were measured by small-angle X-ray scattering and fitted with both the equivalent hard-sphere potential model (EHS) and the Hayter-Penfold/Yukawa potential model (HPY). Both of these models described the interactions in these dispersions successfully, and the results were in reasonable agreement. The strength and range of the interaction potentials decreased with increasing particle volume fractions, which suggests shrinkage of the electrical double layer arising from an increase in the counterion concentration in the bulk solution. However, the interactions at the average interparticle separation increased as the volume fraction increased. The interaction ranges (δ) determined by the two models were very similar. Structure factors were also used to determine the size and volume fraction of the particles. The values of the size obtained from the structure factors were slightly larger than those obtained from the form factors; this difference is ascribed to the nonspherical shape and polydispersity of the colloidal particles. The volume fractions measured by these two methods were very similar and are both in good agreement with the independently measured results.
Langmuir, 2004
Small-angle neutron scattering studies were used to investigate the effect of adding an alcohol e... more Small-angle neutron scattering studies were used to investigate the effect of adding an alcohol ethoxylate nonionic surfactant (d-C12E20) to aqueous solutions of a cationic surfactant, erucyl bis(hydroxyethyl) methylammonium chloride (EHAC), with and without salt (KCl). The systematic use of contrast-matching, by alternately highlighting or hiding one of the surfactants, confirms that mixed micelles are formed. In salt-free solutions, mixed spherical micelles are formed and a core-shell model combined with a Hayter-Penfold potential was used to describe the data. The core radius is dominated by the EHAC tails and the outer radius determined by the ethoxylate headgroups of the nonionic surfactant. Addition of KCl promotes micellar growth; however, results of varying the solvent contrast revealed that when the nonionic surfactant is incorporated into the wormlike structure micellar breaking is promoted. Thus, mixed wormlike micelles with shorter contour lengths compared to the pure EHAC worms are formed.
Langmuir, 2004
The effect of adding an alcohol ethoxylate nonionic surfactant (C(18)E(18)) to aqueous solutions ... more The effect of adding an alcohol ethoxylate nonionic surfactant (C(18)E(18)) to aqueous solutions of a cationic surfactant, erucyl bis(hydroxyethyl) methylammonium chloride (EHAC,CH(3)(CH(2))(7)(CH)(2)(CH(2))(12)N(+)-(CH(2)CH(2)OH)(2)CH(3)Cl(-)), was studied using small-angle neutron scattering (SANS), steady-state rheology, and cryo-transmission electron microscopy (Cryo-TEM). This cationic surfactant has the ability to self-assemble into giant wormlike micelles in the presence of an electrolyte, such as KCl. In salt-free solutions, the mixture of the two surfactants gave rise to spherical micelles. The scattering curves obtained were fitted with a polydisperse core-shell model combined with a Hayter Penfold potential. The inner and outer radii were found to be dependent on the surfactant ratio. In the presence of KCl, mixed wormlike micelles were formed. However, further addition of C(18)E(18) promoted the breaking of the micellar worms with the appearance of a structure peak in the scattering curves. In addition, it was found that the low shear viscosity is decreased upon addition of the alcohol ethoxylate nonionic surfactant. These findings are in good qualitative agreement with the Cryo-TEM images. The results show that the addition of the nonionic surfactant to the system is a method of controlling the worm length.
Journal of the American Chemical Society, 2009
The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur musta... more The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur mustard (HD, bis(2-chlororethyl) sulfide) and a range (chloroethyl) sulfide simulants of variable lipophilicity have been examined using a hydrogen peroxide-based microemulsion system. SANS (small-angle neutron scattering), SAXS (small-angle X-ray scattering), PGSE-NMR (pulsed-gradient spin-echo NMR), fluorescence quenching, and electrospray mass spectroscopy (ESI-MS) were implemented to examine the distribution of HD, its simulants, and their oxidation/hydrolysis products in a model oil-in-water microemulsion. These measurements not only present a means of interpreting decontamination rates but also a rationale for the design of oxidation catalysts for these toxic materials. Here we show that by localizing manganese-Schiff base catalysts at the oil droplet-water interface or within the droplet core, a range of (chloroethyl) sulfides, including HD, spanning some 7 orders of octanol-water partition coefficient (K(ow)), may be oxidized with equal efficacy using dilute (5 wt. % of aqueous phase) hydrogen peroxide as a noncorrosive, environmentally benign oxidant (e.g., t(1/2) (HD) approximately 18 s, (2-chloroethyl phenyl sulfide, C(6)H(5)SCH(2)CH(2)Cl) approximately 15 s, (thiodiglycol, S(CH(2)CH(2)OH)(2)) approximately 19 s {20 degrees C}). Our observations demonstrate that by programming catalyst lipophilicity to colocalize catalyst and substrate, the inherent compartmentalization of the microemulsion can be exploited to achieve enhanced rates of reaction or to exert control over product selectivity. A combination of SANS, ESI-MS and fluorescence quenching measurements indicate that the enhanced catalytic activity is due to the locus of the catalyst and not a result of partial hydrolysis of the substrate.
Journal of Colloid and Interface Science, 2012
The effect of encapsulating oils on the phase behaviour and the microstructure of wormlike micell... more The effect of encapsulating oils on the phase behaviour and the microstructure of wormlike micelles formed by polyoxyethylene cholesteryl ether (ChEO(10)) and triethylene glycol monododecyl ether co-surfactant (C(12)EO(3)) was investigated using rheology, Cryo-TEM and small-angle neutron scattering measurements. Six alkyl ester oils bearing small, systematic variations in their molecular structure were encapsulated: ethyl butyrate (EB(24)), ethyl caproate (ECO(26)), ethyl caprylate (EC(28)), methyl enanthate (ME(17)), methyl caprylate (MC(18)) and butyl butyrate (BB(44)), where the subscripts refer to the length of the alkyl chain and fatty acid chain, respectively, on either sides of the ester link. The addition of alkyl ester oils to ChEO(10)/C(12)EO(3) solutions promotes the longitudinal growth of the surfactant aggregates into wormlike micelles possessing an elliptical cross-section, with r(minor) 31±2 Å and r(major) varying from 45 to 70 Å. At fixed alkyl chain length, oils with longer fatty acid chains were found to be more efficient in inducing wormlike micelle formation or their elongation, following the order: EC(28)>ECO(26)>EB(24). Instead, at fixed fatty acid chain length, increasing the alkyl chain has a negative effect on the longitudinal micellar growth (MC(18)>EC(28) and EB(24)>BB(44)). At high co-surfactant concentrations and in the presence of EB(24), an unusual phase of ring-like micelles was detected. Overall, the orientation of the oil molecules within the micelles enables them to act as co-surfactants with a small head-group, decreasing the average cross-section area and promoting longitudinal growth of the micelles into worms.
Journal of Colloid and Interface Science, 2010
The effect of hydrophobic and hydrophilic co-solutes on the rheological properties of wormlike mi... more The effect of hydrophobic and hydrophilic co-solutes on the rheological properties of wormlike micelles of cetyltrimethylammonium bromide (CTAB) and sodium salicylate (NaSal) or sodium bromide (NaBr) was investigated. Monomeric (ethanol, 2-propanol, benzene and benzylic alcohol) and polymeric species (poly(ethylene oxide), poly(vinyl alcohol) and poly(propylene oxide), respectively PEO, PVA and PPO) of varying molecular weight were studied in order to assess the effect of co-solute 'length' on the interactions with the wormlike micelles. Rheological properties were characterised by the plateau modulus G(0) and the relaxation time τ(R) obtained from fits to the Maxwell model, and by the zero-shear viscosity η(0). The rheological properties were unaltered by the addition of all hydrophilic solutes (up to 20 mM). With hydrophobic co-solutes instead, both η(0) and τ(R) decreased considerably, while G(0) was unaffected. The effects were particularly remarkable with PPO for concentrations as low as 5 mM (ca. 0.3 g L(-1)), and τ(R) was seen to follow an exponential decrease with polymer M(w). The effect of the aromatic solutes (benzene and benzyl alcohol) on the rheology was highly dependent on the counterions used to induce micellar growth (Sal(-) or Br(-)), revealing a different type of interaction. Surprisingly, small-angle neutron scattering and Cryo-TEM measurements showed that the drastic changes observed in the rheology were not correlated to any visible structural change. Therefore the strong decrease in viscosity and relaxation time are to be attributed to other mechanisms than micellar break-up or rod-to-sphere transition.
Soft Matter, 2011
... long micelles. Hala Afifia, Marcelo A. da Silvaa, Cécile Nouvelb, Jean-Luc Sixb, Christian Li... more ... long micelles. Hala Afifia, Marcelo A. da Silvaa, Cécile Nouvelb, Jean-Luc Sixb, Christian Ligourecd and Cécile A. Dreiss*a. a King's College London, Institute of Pharmaceutical Science, 150 Stamford Street, SE1 9NH, UK. E ...