Thiol Surfactants Research Articles

Aqueous Solution Properties of Disulfide-Linked Fluorinated Gemini and Cleaved Monomeric Thiol Surfactants

We prepared a fluorinated gemini surfactant containing a disulfide bond in its spacer chain, [C₈F₁₇(CH₂)₃N(CH₃)₂CH₂CH₂SSCH₂CH₂N(CH₃)₂(CH₂)₃C₈F₁₇]2Cl, and its analogue with a hexamethylene spacer. Monomeric thiol surfactant, [C₈F₁₇(CH₂)₃N(CH₃)₂CH₂CH₂SH]Cl, was readily produced by the cleavage of the gemini surfactant using dithiothreitol in water. The critical micelle concentration was determined using surface tension, conductivity, and fluorescence probe methods. The critical micelle concentration of the monomeric surfactant was significantly larger than that of the gemini surfactant. The surface tension of aqueous solution for the cleaved monomeric thiol surfactant returned gradually to the original value through the formation of the disulfide bond via air oxidation.

Organo-Soluble Chiral Thiol-Monolayer-Protected Gold Nanorods

Here, we report the synthesis and characterization of organo-soluble chiral thiol-monolayer-protected gold nanorods. The resulting gold nanorods respectively covered with two opposite enantiomers via the strong covalent Au-S linkage were found to not only be stable in both organic media and solid state, but also show optical activity. Their circular dichroism (CD) spectra exhibited a mirror image relationship, indicating that enantiomeric thiol surfactant on gold surface can produce the corresponding enantiomeric gold nanorods. The densely packed azobenzene thiol monolayer on gold surface exhibited a photoresponsive behavior upon irradiation with 254 nm light instead of 365 nm light, which was found to have an effect on plasmonic absorption of gold nanorods.

Synthesis of hydrophobic gold nanoclusters: growth mechanism study, luminescence property and catalytic application

One-pot synthesis of well dispersed, size-controlled gold nanoparticles with the average size of 10–15 nm and luminescent gold nanoclusters with average size of 1.7–2.0 nm were successfully achieved by thermal decomposition of gold organometallic precursor CH3AuPPh3 in the presence of thiol surfactants in o-xylene. Only difference between the preparations of two types of Au nanoparticles is the amount of thiol surfactant employed. The mechanistic study of formation of gold nanoparticles was carried out by analyzing the samples at different reaction time intervals and revealed that two-staged growth process was involved. The nanoclusters showed strong red emission with the maximum intensity at about 600 nm. The maximum room temperature photoluminescence quantum yield was measured as 1.2%. The catalytic ability of the Au nanoclusters to promote Suzuki–Miyaura coupling involving the C–C bond formation was also investigated.

Surface and antimicrobial properties of semi-fluorinated quaternary ammonium thiol surfactants potentially usable for Self-Assembled Monolayers

The surfactant and antimicrobial activities of thiol and disulfide derivatives containing a quaternary ammonium group bearing variable perfluorinated carbon chains via an amide connector between the sulfur and nitrogen atoms were evaluated with the future aim to be grafted on metal surfaces for obtaining contact-active and non-adhesive auto-biocidal surfaces. Their biostatic and bactericidal activities against four microbial strains (Pseudomonas aeruginosa, Staphylococcus aureus, Aspergillus niger and Candida albicans) were measured. The presence of the thiol, disulfide and amide functions in these surfactants were discussed in relation with antimicrobial activity along with the influence of the length of fluorinated chains in order to determine which molecular parameters are ‘critical’ for biological activity.

Synthesis and Characterization of Self-Assembling Some Thiol Surfactants on Gold Nanoparticles

The purpose of this work is to study the self-assembling of some synthesized thiol surfactants namely (mercaptopropane-, mercaptohexane-, mercaptooctane-, and mercaptodecane sodium sulfonate) on the fabricated gold nanoparticles. The self-assembling of these surfactants on gold nanoparticles characterized using different techniques such as FTIR spectroscopy, UV spectroscopy, and transmission electron microscopy (TEM). Spectroscopic evidence suggests that the synthesized thiol surfactants have been attached to the gold nanoparticles. The effect of self-assembling of these surfactants on the size of the gold nanoparticles was studied using TEM images. The growth of the gold nanoparticles was investigated with respect to the increase of alkyl chain in the synthesized thiol surfactants. The results show that the stabilization of gold nanoparticles was affected by the increase in alkyl chain length of these surfactants. The effect of gold nanoparticles on the interfacial tension and the emulsion stability of these surfactants with crude oil was studied.

Quantitatively Modeling the Equilibrium Properties of Thiol-Decorated Gold Nanoparticles

We employ a molecular mean-field theory to quantitatively understand the sizes, surfactant surface coverage, and size fluctuations of gold nanocrystals decorated with thiol surfactants of different chain lengths. Our model assumes that surfactant-coated nanoparticles are equilibrium structures. We find that packing constraints experienced by the surfactant tails are less significant for more curved (smaller) particles. This effect enables us to rationalize the experimental observations/deductions that the thiol coverage per unit area increases with decreasing particle size. The reduction of surface coverage with increasing size also explains the fact that size polydispersity increases with increasing nanoparticle size. We find that increasing the length of the surfactants results in larger nanoparticles.

Aqueous Solution Properties of Disulfide Linked Gemini and Cleaved Monomeric Thiol Surfactants

Monomeric thiol surfactants, [C(n)H(2n+1)N(CH(3))(2)CH(2)CH(2)SH]Br, were produced by the cleavage of gemini surfactant containing a disulfide bond in the spacer chain, [C(n)H(2n+1)N(CH(3))(2)CH(2)CH(2)SSCH(2)CH(2)N(CH(3))(2)C(n)H(2n+1)]2Br. The disulfide bond was completely reduced by the addition of four times moles of dithiothreitol in water at room temperature. The critical micelle concentrations of monomeric surfactants were significantly increased in comparison with original gemini surfactants. The monomeric thiol surfactants were stable in the presence of dithiothreitol, whereas they returned gradually to their original gemini surfactants within several days due to air oxidation in water without dithiothreitol. The micelle formation induced by the disulfide linkage formation was suggested by the fluorescence intensity ratio of pyrene. The time course of decrease in thiol concentration associated with the recovery of gemini surfactants was confirmed by the absorption spectra utilizing the reactions with 4,4'-dithiopyridine.

Selective adsorption of alkyl thiols on gold in different geometries

The adsorption of mixtures of alkyl thiol surfactants on the Au(111) surface as well as on icosahedral gold nanocrystals (NCs) was investigated by molecular simulation. We compared the molfraction of each surfactant type on the gold structure with the molfraction of each surfactant type in the surrounding bulk solvent. For alkyl thiol surfactants with 1 to 4 carbon atoms difference, we found that, in contrast to the (111) surface, the adsorption selectivity on a NC is almost identical to that in the solvent.

A facile synthesis of aliphatic thiol surfactant with tunable length as a stabilizer of gold nanoparticles in organic solvents

Three new aliphatic thiol surfactants were synthesized by reacting alkyl bromide with hexamethyldisilathiane under a mild condition. This approach provides an easy access for the direct synthesis of various different length thiol surfactants which play a crucial role in tuning the properties of gold nanoparticles. Gold nanoparticles encapsulated with one of our synthetic thiols were prepared and well characterized by H NMR, UV–vis, FT-IR, and TEM. The hybrid nanoparticles are very stable in both organic solvents and the solid state.

Colloidal particle foams: Templates for Au nanowire networks?

Spin coating a dilute solution of thiol-passivated Au nanoparticles onto silicon produces nanostructured cellular networks. Photoemission measurements, coupled with atomic force microscopy imaging and a statistical crystallography analysis, show that although annealing in the 500–600 K range removes the thiol surfactants surrounding the nanoparticles, the cellular morphology of the nanocrystal foam is preserved following annealing. Thus, self-assembled nanocrystal arrays may be exploited as templates for (bare) Au nanostructures on Si. Although appreciable particle diffusion during annealing does not occur, significant sintering of Au nanocrystals within the cellular network branches is observed.

Time dependent wettability of mineral and metal surfaces in the presence of thiol surfactants

The decrease in wettability of mineral and metal surfaces due to the adsorption of surfactants is crucial for flotation recovery and upgrading of these materials in mineral processing. Because of limited residence time in flotation processing, the kinetics of the wettability changes of the mineral surface becomes an important issue. The time dependent wettabilities of silver and galena (PbS) surfaces in aqueous solutions of di-isobutyl dithiophosphinate, a commercial flotation reagent, were determined from in situ measurements of advancing and receding bubble contact angles. Kinetic parameters were calculated from these data. By comparing the in situ measurements with ex situ measurements of water contact angles and external reflection FTIR of the adsorbed organic films on silver, a physical interpretation of the wettability data is given in terms of the evolution of these thin organic films on the mineral surfaces.

Selective Destruction of the Synthetic Vesicles by the Reductive Cleavage of Disulfide Linkage

Abstract A series of dialkyl disulfide surfactants were prepared by the reaction of different aliphatic amines with S-acetylmercaptosuccinic anhydride followed by the oxidation with iodine. Selective destruction of the vesicles formed by the above surfactants were successfully performed by the reductive. cleavage of dialkyl disulfide to its monoalkyl thiol surfactants with various mercaptans.