Deposition and Spread of Aqueous Pesticide Droplets on Hydrophobic/Superhydrophobic Surfaces by Fast Aggregation of Surfactants.

Deposition and spread of aqueous droplets on hydrophobic/superhydrophobic surfaces are of great significance in many practical applications, such as spraying, coating, and printing, and particularly in improving pesticide utilization efficiency because the intrinsic hydrophobicity/superhydrophobicity of most plant leaves results in serious loss of water-based pesticides during spraying. It has been found that proper surfactants can promote the droplet spread on such surfaces. However, most reports involved the effects of surfactants on the spread of the gently released droplets over hydrophobic or highly hydrophobic substrates, while the situation on superhydrophobic substrates has rarely been explored. Moreover, high-speed impact makes it extremely difficult to deposit and spread the aqueous droplets on superhydrophobic surfaces; thus, the deposition and spread have just been achieved by surfactants in recent years. Here, we give an overview concerning the influence factors on the deposition and spreading performance of gently released and high-speed impacted droplets on hydrophobic/superhydrophobic substrates and emphasize the effects of fast aggregation of surfactants at the interface and in solution. We also outline perspectives on the future development of surfactant-assisted deposition and spreading after high-speed impact.

Chirality-Selected Coacervate by Chiral Gemini Surfactant.

Chiral surfactants present opportunities to self-assemble into supramolecules with a chiral trait; however, the effects of stereochemistry on the formation of simple coacervates remain unclear. Here, we investigate the chirality-selected phase behavior in mixtures of chiral gemini surfactant 1,4-bis(dodecyl-N,N-dimethylammonium bromide)-2,3-butanediol (12-4(OH)2-12) with an oppositely charged chiral mandelic acid (MA). It demonstrates that altering the chirality of surfactants yields a heightened ability to regulate the phase behavior, leading to the formation of three different network-like structures, i.e., wormlike micelle, coacervate, and hydrogel, in the racemate, enantiomer, and mesomer, respectively. The different aggregate structures arise from the intermolecular and intramolecular hydrogen-bond interactions of the two hydroxyl groups located at stereogenic centers. Intriguingly, although they contain similar microstructures, the solid-like hydrogel and liquid-like wormlike micelle show similar low hydration ability and have no encapsulation capability, whereas only coacervate formed by the enantiomers of 12-4(OH)2-12 displays liquid-like characteristics, strong capacity to sequester diverse solutes, and high affinity for tightly bound water simultaneously. These findings further highlight the unique and advantageous properties of coacervates as a promising model for exploring the biological process and understanding how chirality plays a crucial role in early life scenarios and cell evolution at the molecular level.

Noncovalent Bile Acid Oligomers as Facial Amphiphilic Antimicrobials.

New antimicrobial agents are needed to address the ever-growing risk of bacterial resistance, particularly for methicillin- and vancomycin-resistant Staphylococcus aureus (S. aureus). Here, we report a class of bile acid oligomers as facial amphiphilic antimicrobials, which are noncovalently fabricated by cholic acid (CA) and deoxycholic acid (DCA) with polyamines (e.g., diamines, diethylenetriamine, spermidine, and spermine). The antibacterial activities of these bile acid oligomers (CA/polyamines and DCA/polyamines) against S. aureus become stronger with increasing the amine group numbers of polyamines without obviously enhanced cytotoxicity and skin irritation. DCA/spermine, entirely composed of natural products, exhibits the best antibacterial activity but the lowest cytotoxicity and the weakest skin irritation. All CA/polyamines and DCA/polyamines form well-ordered ribbon-like aggregates, collecting numerous facial amphiphilic structures to significantly enhance the interactions with bacterial membranes. In particular, the biogenic polyamines with more than two amine groups provide extra positively charged sites, hence facilitating the binding of bile acid oligomers to the negatively charged outer membrane of the bacteria via electrostatic interaction. This in turn promotes more oligomeric bile acid units that can be inserted into the membrane through hydrophobic interaction between bile acids and lipid domains. The noncovalently constructed and separable amphiphilic antimicrobials can avoid the long-term coexistence of microorganisms and antibacterial molecules in different acting modes. Therefore, the noncovalent bile acid oligomers, especially those with higher oligomerization degrees, can be a potential approach to effectively enhance antibacterial activity, improve environmental friendliness, and reduce bacterial drug resistance.

Strong Inhibition of Ice Growth by Biomimetic Crowding Coacervates.

The freezing of biological fluids is intensively studied but remains elusive as it is affected not only by the various components but also by the crowding nature of the biological fluids. Herein, we constructed spherical crowders, fibrous crowders, and coacervates by various components ranging from surfactants to polymers and proteins, to mimic three typical crowders in biological fluids, i.e., globular proteins, fibrous networks, and condensates of biomolecules. It is elucidated that the three crowders exhibit low, moderate, and strong ice growth inhibition activity, respectively, resulting from their different abilities in slowing down water dynamics. Intriguingly, the coacervate consisting of molecules without obvious ice growth inhibition activity strongly inhibits ice growth, which is firstly employed as a highly-potent cryoprotectant. This work provides new insights into the survival of freezing-tolerant organisms and opens an avenue for the design of ice-controlling materials.

Modulating the Excited State Chirality of Dynamic Chemical Reactions in Chiral Micelles.

Chirality generation and transfer is not only of critical importance in resolving the origin of biological homochirality, but also is of great significance for exploring the chirality-related functionalities in nanomaterials and supramolecular systems. Although modulating the ground state chirality in chiral nanomaterials has been widely demonstrated, it remains a big challenge to steer the excited state chirality (circularly polarized luminescence, CPL). Herein, we present a kind of chiral spherical micelles constructed by chiral cationic gemini surfactants, whose surfaces and cavities could co-assemble with hydrophilic and hydrophobic emitters concurrently. Subsequently, the hydrophilic and hydrophobic emitters could be endowed with CPL activity in the aqueous phase. Additionally, the cavities of such micelles can be regarded as the powerful chiral confined space, which could effectively modulate the excited state chirality of dynamic chemical reactions, enabling color-adjustable CPL emission.

Trimeric Cationic Surfactant Coacervation as a Versatile Approach for Removing Organic Pollutants.

A versatile method to remove a broad spectrum of dye pollutants from wastewater rapidly and efficiently is highly desirable. Here, we report that the complex coacervation of cationic trimeric imine-based surfactants (TISn) with negatively charged hydrolyzed polyacrylamide (HPAM) can be used for this purpose. The coacervation occurs in a wide concentration and composition range and requires the HPAM and TISn concentrations as low as 0.1 g/L and 0.1 mM, respectively. Dye effluents treated by trimeric surfactants and HPAM complete phase separation within 30 s under turbulent conditions, which generates an exceedingly small volume fraction (0.4%) of viscoelastic coacervate and a clear supernatant with a dye removal efficiency of up to 99.9% for anionic and neutral dyes in dosages of up to 120 mg/L. Crowded molecular arrangement and thick framework in coacervate are responsible for the rapid phase separation rate and low volume fraction. The trimeric imine surfactant/polymer coacervation provides a simple, effective, and sustainable approach for the rapid removal of dyes and other organic pollutants.

pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants.

Surfactant aggregates have long been considered as a tool to improve drug delivery and have been widely used in medical products. The pH-responsive aggregation behavior in anionic gemini surfactant 1,3-bis(N-dodecyl-N-propanesulfonate sodium)-propane (C12C3C12(SO3)2) and its mixture with a cationic monomeric surfactant cetyltrimethylammonium bromide (CTAB) have been investigated. The spherical-to-wormlike micelle transition was successfully realized in C12C3C12(SO3)2 through decreasing the pH, while the rheological properties were perfectly enhanced for the formation of wormlike micelles. Especially at 140 mM and pH 6.7, the mixture showed high viscoelasticity, and the maximum of the zero-shear viscosity reached 1530 Pa·s. Acting as a sulfobetaine zwitterionic gemini surfactant, the electrostatic attraction, the hydrogen bond and the short spacer of C12C3C12(SO3)2 molecules were all responsible for the significant micellar growth. Upon adding CTAB, the similar transition could also be realized at a low pH, and the further transformation to branched micelles occurred by adjusting the total concentration. Although the mixtures did not approach the viscosity maximum appearing in the C12C3C12(SO3)2 solution, CTAB addition is more favorable for viscosity enhancement in the wormlike-micelle region. The weakened charges of the headgroups in a catanionic mixed system minimizes the micellar spontaneous curvature and enhances the intermolecular hydrogen-bonding interaction between C12C3C12(SO3)2, facilitating the formation of a viscous solution, which would greatly induce entanglement and even the fusion of wormlike micelles, thus resulting in branched microstructures and a decline of viscosity.

Partition and Solubilization of Phospholipid Vesicles by Noncovalently Constructed Oligomeric-like Surfactants.

This work has investigated the interaction of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) vesicles with oligomeric surfactants noncovalently formed by sodium dodecyl sulfate (SDS) and a series of polyamines, 1,3-diaminopropane (PDA), triamine, spermidine, and spermine. The partition coefficients (P) of these surfactants between lipid bilayers and the aqueous phase are measured by isothermal titration microcalorimetry (ITC), showing that the P value increases and the Gibbs free energy of the partition becomes more negative with increasing oligomerization degree of the surfactants. This changing trend is similar to that of synthetic oligomeric surfactants regardless of the charge properties, suggesting that the polyamine and SDS molecules interact with the DOPC bilayer simultaneously. Meanwhile, the DOPC solubilization by these surfactants is evaluated by the effective surfactant-to-lipid molar ratios for the onset (Resat) and end (Resol) of the solubilization process, which are determined from the phase boundaries obtained by ITC, turbidity, and dynamic light scattering measurements. With the increment of oligomerization degree, the Resat and Resol values increase anomalously and are much larger than those of the synthetic surfactants with the same oligomerization degree, suggesting that noncovalently constructed oligomeric surfactants exhibit lower solubilization ability to phospholipid vesicles than the corresponding covalent oligomeric surfactants. Therefore, the noncovalently constructed oligomeric-like surfactants facilitate strong partition but weak solubilization to phospholipid vesicles, which may provide a useful strategy to mildly adjust the permeation and fluidity of phospholipid vesicles with solubilization delay.

Effects of Hyaluronan Molecular Weight on the Lubrication of Cartilage-Emulating Boundary Layers.

Osteoarthritic joints contain lower-molecular-weight (MW) hyaluronan (hyaluronic acid, HA) than healthy joints. To understand the relevance of this HA size effect for joint lubrication, the friction and surface structure of cartilage-emulating surfaces with HA of different MWs were studied using a surface force balance (SFB) and atomic force microscopy (AFM). Gelatin (gel)-covered mica surfaces were coated with high-MW HA (HHA), medium-MW HA (MHA), or low-MW HA (LHA), and lipids of hydrogenated soy l-α-phosphatidylcholine (HSPC) in the form of small unilamellar vesicles, using a layer-by-layer assembly method. SFB results indicate that the gel-HHA-HSPC boundary layer provides very efficient lubrication, attributed to hydration lubrication at the phosphocholine headgroups exposed by the HA-attached lipids, with friction coefficients (COF) as low as 10-3-10-4 at contact stresses at least up to P = 120 atm. However, for the gel-MHA-HSPC and gel-LHA-HSPC surfaces, the friction, initially low, increases sharply at much lower pressures (up to 30-60 atm at most). This higher friction with the shorter chains may be due to their weaker total adhesion energy to the gelatin, where the attraction between the negatively charged HA and the weakly positively charged gelatin is attributed largely to counterion-release entropy. Thus, the complexes of LHA and MHA with the lubricating HSPC lipids are more easily removed by shear during sliding, especially at high stresses, than the HHA-HSPC complex, which is strongly adhered to gelatin. This is ultimately the reason for lower-pressure lubrication breakdown with the shorter polysaccharides. Our results provide molecular-level insight into why the decrease in HA molecular weight in osteoarthritic joints may be associated with higher friction at the articular cartilage surface, and may have relevance for treatments of osteoarthritis involving intra-articular HA injections.

Effects of Gold Nanospheres and Nanocubes on Amyloid-ß Peptide Fibrillation.

Direct exposure or intake of engineered nanoparticles (ENPs) to the human body will trigger a series of complicated biological consequences. Especially, ENPs could either up- or downregulate peptide fibrillation, which is associated with various degenerative diseases like Alzheimer's and Parkinson's diseases. This work reports the effects of gold nanoparticles (AuNPs) with different shapes on the aggregation of an amyloid-ß peptide (Aß(1-40)) involved in Alzheimer's disease. Two kinds of AuNPs were investigated, i.e., gold nanospheres (AuNSs, ∼20 nm in diameter) and gold nanocubes (AuNCs, ∼20 nm in edge length). It was found that AuNPs play a catalytic role in peptide nucleation through interfacial adsorption of Aß(1-40). AuNSs with hybrid facets have higher affinity to Aß(1-40) because of the higher degree of surface atomic unsaturation than the {100}-faceted AuNCs. Therefore, AuNSs exert a more significant acceleration effect on the fibrillation process of Aß(1-40) than AuNCs. Besides, a shape-dependent secondary structure transformation of Aß(1-40) with different AuNPs was observed using Fourier transform infrared spectroscopy. The variation of peptide-NP and peptide-peptide interactions caused by the shape alteration of AuNPs influences the equilibrium of inter- and intramolecular hydrogen bonds, which is believed to be responsible for the shape-dependent secondary structure transformation. The study offers further understanding on the complicated NP-mediated Aß aggregation and also facilitates further development on designing and synthesizing task-specific AuNPs for amyloid disease diagnosis and therapy.

Self-Assembly and Functions of Star-Shaped Oligomeric Surfactants.

Oligomeric surfactants consist of three or more amphiphilic moieties which are connected by spacer groups covalently at the level of headgroups. It provides a possible route to bridge the gap from conventional single-chain surfactants to polymeric surfactants and leads to many profound improvements in the properties of surfactants in aqueous solution and at the air/water and water/solid interfaces. Generally, oligomeric surfactants are categorized into linear, ring-like, and star-shaped on the basis of the topological structures of their spacer groups, and their aggregation behavior strongly depends on the resultant topological structures. In recent years, we studied trimeric, tetrameric, and hexameric surfactants with a star-shaped spacer which spreads from a central site of elemental nitrogen or carbon, and their charged headgroups connect with each other through the spacers. It has been found that both the nature of spacer groups and the degree of oligomerization show important influences on the self-assembly of oligomeric surfactants and provide great possibilities in fabricating various surfactant aggregate morphologies by adjusting the molecule conformations. The unique self-assembly behavior endows them with superior physicochemical properties and potential applications. This feature article summarizes the development of star-shaped oligomeric surfactants, including self-assembly at the air/water and water/solid interfaces, self-assembly in aqueous solution, and their functions. We expect that this review could provide a comprehensive understanding of the structure-property relationship and various potential applications of star-shaped oligomeric surfactants and offer additional motivation for their future research.

Self-Assembly and Chiral Recognition of Chiral Cationic Gemini Surfactants.

Chiral cationic gemini surfactants 1,4-bis(dodecyl- N, N-dimethylammonium bromide)-2,3-butanediol (12-4(OH)2-12) including racemate, mesomer, and two enantiomers were synthesized and their self-assembly in aqueous solution has been comparatively investigated by tensiometry, conductometry, 1H NMR, small-angle neutron scattering, cryogenic transmission electron microscopy, and cryogenic scanning electron microscopy. The chirality at spacer induces different self-assembly behaviors due to the hydrogen-bonding interaction between the hydroxyl groups at the chiral centers. The stereochemistry of the spacer has little effect on the release of the counterions from the surfactant headgroups and on the molecular packing at the air-water interface. The critical micelle concentration (CMC) decreases in the order of racemate > enantiomer > mesomer. Above the CMC, the aggregates of enantiomers transit from small spherical micelles to rodlike and wormlike micelles with increasing concentration, whereas the mesomer and racemate aggregates transform from spherical micelles to rodlike micelles and platelet-like aggregates. The differences may be because the mesomer and racemate molecules mainly form intermolecular hydrogen bonds between the -OH groups, but the enantiomer molecules dominantly form intramolecular hydrogen bonds. Furthermore, it was found that the chiral micelles formed by the enantiomers exhibit enantioselection ability for bilirubin (BR) enantiomers. The recognition capability can be adjusted by the micellar structure, i.e., the rodlike micelles are better than either small spherical micelles or wormlike micelles, which might possess different chiral cavities, controlling BR shape and location. These results demonstrate that the aggregates of chiral gemini surfactants can be used to mimic the chiral recognition in biological membrane.

Selective separation of heavy metal ions from dilute aqueous solutions by foams and micelles of surfactants.

Traditional metal ion separation by surfactant foams is dependent on the interaction difference of various metal ions with surfactant monomers rather than surfactant aggregates, because the binding of metal ions with surfactant aggregates retains the metal ions in bulk solution. This kind of separation method is only effective for the metal ions with obvious differences in valence, size or coordination ability. The present study proposes a novel separation method based on the binding affinity difference of metal ions with micelles and monomers of two surfactants to selectively separate multivalent ions Cr3+, Ni2+ and Cu2+ from their dilute mixed aqueous solution. The two surfactants are single-chain surfactant sodium dodecyl sulfate (SDS) and gemini surfactant 1,3-bis(N-dodecyl-N-propanesulfonate sodium)-propane (C12C3C12(SO3)2), which show negligible synergism because they are both negatively charged and hold a significantly different self-assembling ability, thus allowing the coexistence of SDS/C12C3C12(SO3)2 micelles with SDS monomers. At first, Cr3+ ions were separated from Cu2+ and Ni2+ ions by the foam generated by the SDS monomers due to more intensive electrostatic interaction of Cr3+ ions with the SDS monomers. Afterwards Ni2+ ions were separated from Cu2+ ions by utilizing the high binding affinity of Cu2+ with the SDS/C12C3C12(SO3)2 micelles in the bulk solution and Ni2+ with the SDS monomers in the foam. This work has proved that micelles can assist the selective separation of "twin-like" metal ions Ni2+ and Cu2+ when the concentrations of monomers and micelles are properly adjusted.

Coacervate of Polyacrylamide and Cationic Gemini Surfactant for the Extraction of Methyl Orange from Aqueous Solution.

Coacervation in aqueous solution of the mixture of cationic ammonium surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) and 10% hydrolyzed polyacrylamide (PAM) has been investigated. It was found that the 12-6-12/PAM mixture forms coacervate with a large network structure over a wide concentration range of surfactant and polyelectrolyte and shows great efficiency in the extraction of Methyl Orange (MO) from water owing to the cooperation of hydrophobic, electrostatic, and π-cation interactions. Meanwhile, the dye joins the coacervate and strengthens the network structure of the coacervate. In particular, benefiting from partial excess of 12-6-12 molecules, the coacervate phase presents selective adsorption behavior toward anionic dye MO in the presence of cationic dye methylene blue (MB). Furthermore, the coacervate phase is utilized to modify quartz sand and melamine foam, and the coacervate-treated adsorbents can adsorb MO efficiently. Moreover, the MO-loaded adsorbents are easily regenerated with hydrochloric acid, making this an inexpensive and environmentally benign process. These findings offer a simple and effective alternative for the treatment of dye contaminated water and the recovery of dyes.

Interactions of Cationic/Anionic Mixed Surfactant Aggregates with Phospholipid Vesicles and Their Skin Penetration Ability.

This work studied the interactions of an oppositely charged surfactant mixture of oleyl bis(2-hydroxyethyl)methyl ammonium bromide (OHAB) and sodium dodecyl sulfate (SDS) with 1,2-di-(9Z-octadecenoyl)-sn-glycero-3-phosphocholine (DOPC) vesicles as well as the penetration of the OHAB/SDS mixture through model skin, aimed at understanding the relationship between the ability of different surfactant aggregates in solubilizing phospholipid vesicles and their potential in irritating skin. By changing the molar fraction of OHAB (XOHAB), five kinds of aggregates are constructed: OHAB and SDS separately form cationic and anionic small micelles, whereas the OHAB/SDS mixtures form cationic and anionic vesicles at XOHAB = 0.30 and 0.70, respectively, and weakly charged vesicles at XOHAB = 0.50. The mixtures have much lower critical micellar concentrations (CMCs) and much larger aggregates than either OHAB or SDS alone, and the CMC and the size of the OHAB/SDS vesicles decrease with the increase in XOHAB. The phase diagrams indicate that the OHAB/SDS mixtures show much stronger ability in solubilizing the DOPC vesicles than individual OHAB and SDS and decrease in the order of XOHAB = 0.30 > 0.50 > 0.70 ≫ 1.00 > 0. However, the ability of the surfactants in penetrating the model skin decreases reversely, and the penetration of the surfactants are significantly reduced by mixing. These results indicate that the surfactant mixture with a larger aggregate size and a smaller CMC value displays much stronger ability in solubilizing the DOPC vesicles but much weaker ability in penetrating the skin.

Effects of length and hydrophilicity/hydrophobicity of diamines on self-assembly of diamine/SDS gemini-like surfactants.

This work studied gemini-like surfactants formed from anionic surfactant sodium dodecyl sulfate (SDS) and cationic charged bola-type diamines with hydrophilic or hydrophobic spacers of different lengths using surface tension, small angle neutron scattering, isothermal titration microcalorimetry and cryogenic transmission electron microscopy. The critical micelle concentrations (CMC) and the surface tension at CMC (γCMC) for all the diamine/SDS mixtures are markedly lower than that of SDS. The shorter diamines reduce γCMC to a greater extent regardless of the hydrophilicity/hydrophobicity of the diamines. Meanwhile, either the hydrophobic diamine with a longer spacer or the hydrophilic diamine with a shorter spacer is more beneficial to decrease CMC and leads to the transition from spherical micelles into rodlike or wormlike micelles. This is principally because of the formation of gemini-like surfactants by the electrostatic binding between SDS and the diamines, where the electrostatic repulsion between the adjacent headgroups of SDS becomes much weaker due to the electrostatic binding of oppositely charged diamine with SDS, and the longer hydrophobic spacer may also bend into the hydrophobic domain of micelles to promote micellar growth. However, the hydrophilic spacers are more compatible with the headgroup region, leading to micelles with a larger curvature. This work contributes to the understanding of the relationship between the properties of constructed gemini-like surfactants and the natures of connecting molecules, and provides guidance to efficiently improve the performance of surfactants.

Modulation of partition and localization of perfume molecules in sodium dodecyl sulfate micelles.

The influence of perfume molecules on the self-assembly of the anionic surfactant sodium dodecyl sulfate (SDS) and their localization in SDS micelles have been investigated by ζ potential, small angle X-ray scattering (SAXS), one- and two-dimensional NMR and isothermal titration microcalorimetry (ITC). A broad range of perfume molecules varying in octanol/water partition coefficients P are employed. The results indicate that the surface charge, size and aggregation number of the SDS micelles strongly depend on the hydrophobicity/hydrophilicity degree of perfume molecules. Three distinct regions along the log P values are identified. Hydrophilic perfumes (log P < 2.0) partially incorporate into the SDS micelles and do not lead to micelle swelling, whereas hydrophobic perfumes (log P > 3.5) are solubilized close to the end of the hydrophobic chains in the SDS micelles and enlarge the micelles with higher ζ potential and a larger aggregation number. The incorporated fraction and micelle properties show increasing tendency for the perfumes in the intermediate log P region (2.0 < log P < 3.5). Besides, the molecular conformation of perfume molecules also affects these properties. The perfumes with a linear chain structure or an aromatic group can penetrate into the palisade layer and closely pack with the SDS molecules. Furthermore, the thermodynamic parameters obtained from ITC show that the binding of the perfumes in the intermediate log P region is more spontaneous than those in the other two log P regions, and the micellization of SDS with the perfumes is driven by entropy.

Surfactant selection principle for reducing critical micelle concentration in mixtures of oppositely charged gemini surfactants.

Cationic quaternary ammonium gemini surfactants C(n)H(2n+1)(CH3)2N(+)CH2CHCHCH2(CH3)2N(+)C(n)H(2n+1)2Br(-) (C(n)C4C(n), n = 12, 8, 6) with alkyl spacers, C(n)H(2n+1)(CH3)2N(+)CH2CHOHCHOHCH2(CH3)2N(+)C(n)H(2n+1)2Br(-) (C(n)C4(OH)2C(n), n = 12, 8, 6, 4) with two hydroxyl groups in alkyl spacers, and cationic ammonium single-chain surfactants C(n)H(2n+1)(CH3)2N(+)Br(-) (C(n)TAB, n = 12, 8, 6) have been chosen to fabricate oppositely charged surfactant mixtures with anionic sulfonate gemini surfactant C12H25N(CH2CH2CH2SO3(-))CH2CH2CH2(CH3)2N(CH2CH2CH2SO3(-))C12H252Na (C12C3C12(SO3)2). Surface tension, electrical conductivity, and isothermal titration microcalorimetry (ITC) were used to study their surface properties, aggregation behaviors, and intermolecular interactions. The mixtures of C12C3C12(SO3)2/C(n)C4(OH)2C(n) (n = 12, 8) and C12C3C12(SO3)2/C12C4C12 show anomalous larger critical micelle concentration (CMC) than C12C3C12(SO3)2, while the mixtures of C12C3C12(SO3)2/C(n)C4(OH)2C(n) (n = 6, 4), C12C3C12(SO3)2/C(n)C4(OH)2C(n) (n = 6, 4), and C12C3C12(SO3)2/C(n)TAB (n = 12, 8, 6) exhibit much lower CMC than C12C3C12(SO3)2. The results indicate that strong hydrophobic interactions between the alkyl chains assisted by strong electrostatic attractions between the headgroups and hydrogen bonds between the spacers lead to the formation of less surface active premicellar aggregates in bulk solution, resulting in the increase of CMC. If these interactions are weakened or inhibited, less surface active premicellar aggregates are no longer formed in the mixtures, and thus the CMC values are reduced. The work reveals that the combination of two surfactants with great self-assembling ability separately may have strong intermolecular binding interactions; however, their mixtures do not always generate superior synergism properties. Only moderate intermolecular interaction can generate the strongest synergism in CMC reduction.

Self-assembled structures of anionic hydrophobically modified polyacrylamide with star-shaped trimeric and hexameric quaternary ammonium surfactants.

The self-assembly of a 1% hydrophobically modified and 30% hydrolyzed polyacrylamide (C12PAM) with cationic star-shaped oligomeric surfactants has been investigated by isothermal titration microcalorimetry, turbidimetry, ζ potential, scanning electron microscopy, and (1)H NMR techniques. The oligomeric surfactants are composed of quaternary dodecyldimethylammonium ions with three or six hydrophobic chains connected by a polyamine spacer at the headgroup level, abbreviated as DTAD and PAHB, respectively. DTAD/C12PAM and PAHB/C12PAM mixed systems undergo the same aggregate transitions with increases in surfactant concentration from soluble networklike aggregates to precipitated denser and more cross-linked structures and then to soluble spherical aggregates. The networklike aggregates are generated at very low surfactant concentration. However, at the corresponding surfactant concentration without C12PAM, DTAD cannot form aggregates and PAHB forms only networklike aggregates with a very loose structure. The strong electrostatic and hydrophobic interaction of DTAD and PAHB with C12PAM and the hydrophobic interaction between the alkyl chains of DTAD and PAHB themselves evidently promote the formation of networklike aggregates. As the surfactant concentration increases, cationic surfactants become excessive. The molecular configuration is changed by the stronger hydrophobic association among the DTAD and PAHB molecules and the enhanced electrostatic repulsion between the mixed aggregates. Thus, the networklike aggregates transfer to spherical aggregates.

Interactions of cationic trimeric, gemini and monomeric surfactants with trianionic curcumin in aqueous solution.

Interactions of trianionic curcumin (Cur(3-)) with a series of cationic surfactants, monomeric surfactant dodecyl trimethylammonium bromide (DTAB), dimeric surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) and trimeric surfactant tri(dodecyldimethylammonioacetoxy)diethyltriamine trichloride (DTAD), have been investigated in aqueous solution of pH 13.0. Surface tension and spectral measurements indicate that the cationic surfactants display a similar surfactant concentration dependent interaction process with Cur(3-), involving three interaction stages. At first the three cationic surfactants electrostatically bind on Cur(3-) to form the surfactant-Cur(3-) complex. Then the bound and unbound cationic surfactants with Cur(3-) aggregate into surfactant-Cur(3-) mixed micelles through hydrophobic interactions above the critical micelle concentration of the surfactants (CMCC) in the presence of Cur(3-). Finally excess unbound surfactants self-assemble into micelles like those without Cur(3-). For all the three surfactants, the addition of Cur(3-) only decreases the critical micelle concentration of 12-6-12 but does not affect the critical micelle concentration of DTAB and DTAD. As the oligomeric degree of surfactants increases, the intermolecular interaction of the cationic surfactants with Cur(3-) increases and the surfactant amount needed for Cur(3-) encapsulation decreases. Compared with 12-6-12, either the weaker interaction of DTAB with Cur(3-) or stronger interaction of DTAD with Cur(3-) limits the stability or solubility of Cur(3-) in surfactant micelles. Therefore, gemini surfactant 12-6-12 is the best choice to effectively suppress Cur(3-) degradation at very low concentrations. Isothermal titration microcalorimetry, surface tension and (1)H NMR results reveal that 12-6-12 and Cur(3-) form a (12-6-12)2-Cur(3-) complex and start to form micelles at extremely decreased concentrations, where either 12-6-12 or Cur(3-) works as a bridge linkage and the resultant structure exhibits the characteristics of oligomeric surfactants.