Wormlike micellar solutions formed by an anionic surfactant and a cationic surfactant with two head groups.

Innovation in the molecular structure of surfactants is important for the preparation of soft materials with novel properties. In this study, we synthesized a cationic surfactant, N1,N1,N1,N1,N3,N3,N3-pentamethyl-N3-(3-stearamidopropyl)propane-1,3-diammonium bromide, hereafter referred to as C18-DQA. Unlike conventional cationic surfactants, C18-DQA contains two quaternary ammonium head groups and a long-saturated alkyl chain equal to a chain length of 21 carbon atoms. C18-DQA exhibits a low Krafft point of ∼0 °C and a water solubility >1000 mM at 25 °C. The critical micelle concentration (cmc) of C18-DQA was determined to be 0.59 mM using the Nile red method. C18-DQA was mixed with sodium laurate (SL) at different molar ratios to produce transparent solutions with excellent viscoelasticity over a wide concentration range. The 1 : 1.5 molar ratio C18-DQA/SL mixed solutions exhibited gel-like behavior for a total surfactant concentration of 2.88 wt% (75 mM). The solution with a total surfactant concentration of 300 mM (120 mM C18-DQA and 180 mM SL) achieved a maximum zero-shear viscosity (η0) of 4224 Pa s. Cryogenic transmission electron microscopy analysis revealed the formation of extremely long wormlike micelles, with a cross-sectional diameter of 5 nm and contour length >3 µm, in the mixed solutions. C18-DQA and SL molecules were drawn close by electrostatic attractions, leading to a suitable molecular geometry for the extensive growth of wormlike micelles. This work will act as an important reference for the future preparation of highly viscoelastic solutions by mixing cationic and anionic surfactants. The proposed system is also expected to have potential applications in cosmetic formulations, home care products, and oilfield fracturing fluids.

Toroidal micelles formed in viscoelastic aqueous solutions of a double-tailed surfactant with two quaternary ammonium head groups.

Innovation in surfactant structures is an effective way to prepare new soft materials with novel applications. In this study, we synthesized a double-tailed surfactant containing two quaternary ammonium head groups (Di-C12-N2). The Di-C12-N2 solution behavior was investigated by surface tension, fluorescence, rheology, and cryo-TEM methods. Although Di-C12-N2 contained a large double-tailed hydrophobic group, the solubility of Di-C12-N2 was ∼90 mmol L-1 at 25 °C with a Krafft temperature of ∼1 °C. The increase in Di-C12-N2 concentration in the solutions led to the formation of various aggregates, including spherical micelles, worm-like micelles, multi-layered vesicles, and a rare type of small toroidal micelles. The two quaternary ammonium head groups in Di-C12-N2 led to strong electrostatic interactions between molecules, which was critical for the formation of toroidal micelles. Moreover, with an added NaCl concentration of 40 mmol L-1, the viscosity of the 5 mmol L-1Di-C12-N2 solution increased by ∼1000 times compared to the pure 5 mmol L-1Di-C12-N2 solution, revealing the high sensitivity of the unique head groups to ionic strength. This study enriches the research on the self-assembly principles of surfactants and brings new potential applications for new soft materials.

Recyclable Nonionic-Anionic Bola Surfactant as a Stabilizer of Size-Controllable and pH-Responsive Pickering Emulsions.

A novel nonionic-anionic Bola surfactant (abbreviated as CH3O(EO)7-R11-COOH) was designed and synthesized by condensation of methyl polyoxyethylene (7) ether with 12-bromododecanoic acid. In neutral aqueous solution, the surfactant behaves as a nonionic one and can stabilize oil-in-water (O/W) conventional emulsions alone and costabilize O/W Pickering emulsions with positively charged alumina nanoparticles with n-decane as the oil. In alkaline solution, the carboxylic acid group is deprotonated, becoming anionic and the surfactant is converted to Bola form, which is an inferior emulsifier and does not adsorb on particle surfaces, resulting in demulsification of both kinds of emulsions. With strong hydrophilicity, both the Bola surfactant and the bare particles return to the aqueous phase after demulsification, which is therefore recyclable and reusable in accordance with sustainable chemistry and engineering. In acidic media between pH 3 and 6, the ethyleneoxy groups tend to desorb from particle surfaces, slightly reducing the hydrophobicity of the particles. However, Pickering emulsions are still stable but their droplet size increases on lowering the pH. The Pickering emulsions are therefore pH-responsive and size-controllable. This newly designed Bola surfactant is effective in preparing smart emulsions, which are extensively applied in heterogeneous catalysis, oil product transportation, emulsion polymerization, and new material preparation.

Ecofriendly Viscoelastic Solutions Formed from a Recyclable Rosin-Based Amine Oxide Surfactant.

Innovations in molecular structures formed using bioresources are efficient means to prepare surfactant aggregates with unique properties. Here, a rosin-based amine oxide surfactant (R-11-3-AO) containing large hydrophobic groups was synthesized from rosin derivatives, namely, dehydroabietic acid and long-chain amino acids. Cryo-transmission electron microscopy showed that R-11-3-AO molecules formed extremely long wormlike micelles with a cross-sectional diameter of 4-5 nm at a concentration of approximately 7 mmol·L-1. A gel-like system was obtained at approximately 30 mmol·L-1 due to the dense entanglement of the wormlike micelles. The solutions also exhibited unique shear thickening behavior at a shear rate of approximately 10 s-1 even at high concentrations. The large hydrophobic group contained in R-11-3-AO is the origin of the strong van der Waals interactions between the surfactant molecules, resulting in the rapid growth of wormlike micelles. This rosin-based surfactant is the first recoverable amine oxide surfactant from solutions through the salting-out effect with high recovery rates. This work demonstrates the unique capabilities of rosin-based surfactants for forming wormlike micelles and provides opportunities for the development of surfactant recovery technologies.

Pickering Emulsions Synergistically Stabilized by Aliphatic Primary Amines and Silica Nanoparticles.

Innovation in emulsion compositions is necessary to enrich emulsion formulations and applications. Herein, Pickering emulsions were prepared using silica nanoparticles and aliphatic primary amines with an oil-water ratio of 1:1 (v/v). Contact angle experiments revealed that the in situ hydrophobization of nanoparticles was caused by the surface adsorption of amine molecules. Notably, the interactions between amine compounds and the surface of silica nanoparticles were electrostatic attractions and mutual hydrogen bonding. The existence of hydrogen bonds was further confirmed by demulsification experiments using a chaotropic agent DMF and increasing temperatures. The hydrophobicity of silica nanoparticles can be effectively improved using most commercially available aliphatic primary amines such as n-hexylamine, n-octylamine, n-decylamine, dodecylamine, and tetradecylamine. The minimum concentrations of the aforementioned amines necessary for stabilizing the emulsions with 0.3 wt % silica nanoparticles are 3, 0.6, 0.3, 0.06, and 0.03 mM, respectively, decreasing significantly with increasing alkyl chain length. With the increase of the amine concentrations, the hydrophobicity of silica particles monotonically increased and finally resulted in the inversion of emulsions. The amine concentrations for emulsion phase inversion were 150, 40, 30, 20, and 20 mM, respectively, in the presence of 0.3 wt % silica nanoparticles. In this work, silica nanoparticles were hydrophobized using aliphatic primary amines. The composite stabilizers developed are useful for developing novel stimuli-responsive Pickering emulsions, while the synergistic effects introduced herein are also helpful in expanding the hydrophobization methods available for nanoparticles.

Water-in-Oil Emulsion Gels Stabilized by a Low-Molecular Weight Organogelator Derived from Dehydroabietic Acid.

High concentrations of surfactants or gelators are usually necessary to prepare emulsions gels with unusual physicochemical properties. This situation may be improved by innovating the aggregate morphology in systems. Herein, a rosin-based molecule is designed and synthesized using dehydroabietic acid as the starting material (denoted as R-Lys-R). The molecule acts as an effective organogelator and can gelate several hydrocarbon compounds with a minimum gelation concentration of 0.2% (w/v). Analysis using atomic force microscopy (AFM) and circular dichroism (CD) reveals that in n-decane, R-Lys-R forms left-handed helical fibers with a cross-sectional diameter of approximately 15 nm. The directional hydrogen bonding of the amide group is helpful to the formation of aggregates. At concentrations of R-Lys-R above 2%, water-in-oil emulsions are transformed into emulsion gels owing to the aptitude of R-Lys-R in gelating the oil phase. The concentrations of the emulsifier can be adjusted to obtain emulsion gels with different formulations. This work reveals the potential of rosin derivatives for the formation of small molecular weight organogels and provides a novel method for the utilization of natural resources in soft materials and home care products.

Rheological behavior of thread-like fiber solutions formed from a rosin-based surfactant with two head groups.

Wormlike micelles are conventional aggregates that exist in viscoelastic solutions. However, to achieve a solution with prominent viscoelasticity, rather high concentrations of surfactants are usually required due to the flexibility of aggregates in solution. If thread-like aggregates with rigidity can be formed by surfactants, the solutions are expected to show strong viscoelasticity at very low surfactant concentrations. Herein, A novel rosin-based quaternary ammonium surfactant with two head groups (abbreviated as R-11-3-DA) was synthesized. Cryogenic transmission electron microscopy (Cryo-TEM) images showed that flexible nanofibers with diameters of about 7-8 nm and lengths of over 1 µm were formed in the 1 : 1.5 R-11-3-DA : SL solutions. The rigidity of the aggregates seems to be inherited from the rigidity of the surfactant molecules. The novel aggregates endow the solutions with remarkable viscoelasticity at very low concentrations, with a critical overlap concentration of 0.01 wt% and a critical gelling concentration of 0.58 wt%. The rheological behavior of the solutions also shows excellent shear resistance and weak sensitivity to temperature below the critical gelation temperature (Tgel). This work reveals the advantages of viscoelastic solutions containing flexible nanofibers. The design principles of new molecular structures and system compositions can be applied to the preparation of smart soft materials based on the self-assembly of molecules.

Recyclable and re-usable smart surfactant for stabilization of various multi-responsive emulsions alone or with nanoparticles.

A novel multi-responsive surfactant (abbreviated as N+-8P8-N) was synthesized, in which one octyl trimethylamine group (quaternary ammonium) and one octyl dimethylamine group are connected to a benzene ring through ether bonds. This novel surfactant can stabilize conventional oil-in-water (O/W) emulsions alone, and O/W Pickering emulsions and novel oil-in-dispersion emulsions together with oppositely and similarly charged nanoparticles, respectively. In all cases rapid demulsification can be achieved through either pH or CO2/N2 triggers, by which the surfactant is reversibly converted between a normal cationic surfactant form (N+-8P8-N) and a strongly hydrophilic and surface-inactive bola form (N+-8P8-NH+). Notably, the bola form N+-8P8-NH+ dissolves in the aqueous phase alone or together with nanoparticles after demulsification without contamination of the oil phase, and the aqueous phase can be recycled many times triggered by pH or CO2/N2 in accordance with the principle of green chemistry. This newly designed re-usable smart surfactant is significant for the development of various temporarily stable emulsions, which are extensively applied in emulsion polymerization, new material synthesis, heterogeneous catalysis and oil transportation.

Salt-Resistant Switchable Pickering Emulsions Stabilized by Mesoporous Nanosilica Hydrophobized In Situ by pH-Insensitive Surfactants.

Novel oil-in-water (O/W) Pickering emulsions (PEs) were prepared using mesoporous nanosilica in combination with a pH-insensitive cationic surfactant as a stabilizer and show an interesting sensitivity to acids and bases. Adding a suitable amount of NaOH (nNaOH/ncationic surfactant ≥ 1) led to prompt demulsification within 10 s. Upon further adding HCl solutions (nHCl/nNaOH = 1), stable PEs re-formed after homogenization. These emulsions remained stable for over 30 days after 60 cycles, switching from stable to unstable and back to stable states, and showed a high salt tolerance. A mechanism for the switching of the Pickering emulsion (PE) to unstable and back to stable states was derived and involved anionic and neutral forms of hydroxyl groups at the mesopores of the mesoporous silica nanoparticles (MSNPs). This work reveals a switchable PE system involving a pH-insensitive surfactant, in which the species of oils and cationic surfactants can be arbitrarily selected, a feature that greatly expands the applicability of PEs.

Formation of asymmetric belt-like aggregates from a bio-based surfactant derived from dehydroabietic acid.

The morphology and physicochemical properties of ordered molecular aggregates are closely related to surfactant molecules. Herein, a rosin-based amine oxide surfactant containing a large hydrophobic group (abbreviated R-10-AO) was synthesized from dehydroabietic acid, which is an important derivative of rosin. Cryogenic transmission electron microscopy (cryo-TEM) images and small-angle X-ray scattering (SAXS) showed that at a concentration of ∼5 mM, R-10-AO molecules formed flexible nanobelts with a thickness of only 2-3 nm. The width of these nanobelts was 50-150 nm and the length was more than 1 µm. The formation of the stable nanobelts arose from the strong van der Waals forces of the bulky hydrophobic portions of R-10-AO in solution, facilitating the stability of the asymmetrical aggregates. Rheological tests showed that the formed nanobelts were thermodynamically stable. The entanglement of these nanobelts led to significant viscoelasticity of the solutions. The zero-shear viscosity (η0) of the R-10-AO solution reached 10 Pa s at a concentration of 5 mM, which is much greater than that of most wormlike micellar solutions. This work provides the inspirations of preparing aggregates with novel properties using natural products.

Behavior of Smart Surfactants in Stabilizing pH-Responsive Emulsions.

Newly structured pH-responsive smart surfactants (N+ -(n)-N, n=14, 16) from alkyl trimethylammonium bromides are reported. In neutral and alkaline media N+ -(n)-N behaves as a normal cationic surfactant and stabilizes conventional emulsions alone, as well as Pickering emulsions and oil-in-dispersion emulsions together with oppositely and similarly charged nanoparticles, respectively. In acidic media N+ -(n)-N becomes a hydrophilic Bola-type surfactant, N+ -(n)-NH+ , and is an inferior emulsifier either when used alone or together with charged nanoparticles, resulting in demulsification. N+ -(n)-NH+ returns to the aqueous phase alone or together with nanoparticles after demulsification without contaminating the oil phase, and the aqueous phase can be recycled when triggered by pH change. This protocol is a green process and leads to preparation of various temporarily stable emulsions which are often used in emulsion polymerization, heterogeneous catalysis, and oil transportation.

Highly wet aqueous foams stabilized by an amphiphilic bio-based hydrogelator derived from dehydroabietic acid.

Exploration of novel molecular aggregates that stabilize foam systems is helpful to optimize foam properties. Herein, solutions of a rosin-based low-molecular-weight hydrogelator, abbreviated as R-6-AO, were used to generate foams above the critical gelation temperature (Tgel). The foams with R-6-AO concentrations above the critical gelation concentration were very stable below Tgel. The high stability of the foams under such conditions was attributed to the self-assembly of nanoscale fibers of R-6-AO in the liquid films of the foams, leading to extremely slow drainage of water. The foams showed strong water retention and were classified as very wet foams. For example, the foams generated from 10 mM (0.44 wt%) R-6-AO solution subjected to a fast cooling process contained about 45 vol% trapped water after 2000 min. In comparison, the water volume fraction of a 10 mM sodium dodecyl sulfate (SDS) foam decreased from 20 vol% to 1 vol% within 18 min. Because the growth, elongation, and cross-linking of the assembled nanofibers in the liquid films were affected by the cooling process, the stability of these foams also depended on the initial preparation temperature. The present system reveals the importance of microstructures in regulating foam behavior and serves as a new type of condition-sensitive intelligent foam.

Widely Adaptable Oil-in-Water Gel Emulsions Stabilized by an Amphiphilic Hydrogelator Derived from Dehydroabietic Acid.

A surfactant, R-6-AO, derived from dehydroabietic acid has been synthesized. It behaves as a highly efficient low-molecular-weight hydrogelator with an extremely low critical gelation concentration (CGC) of 0.18 wt % (4 mm). R-6-AO not only stabilizes oil-in-water (O/W) emulsions at concentrations above its critical micelle concentration (cmc) of 0.6 mm, but also forms gel emulsions at concentrations beyond the CGC with the oil volume fraction freely adjustable between 2 % and 95 %. Cryo-TEM images reveal that R-6-AO molecules self-assemble into left-handed helical fibers with cross-sectional diameters of about 10 nm in pure water, which can be turned to very stable hydrogels at concentrations above the CGC. The gel emulsions stabilized by R-6-AO can be prepared with different oils (n-dodecane, n-decane, n-octane, soybean oil, olive oil, tricaprylin) owing to the tricyclic diterpene hydrophobic structure in their molecules that enables them to adopt a unique arrangement in the fibers.

Viscoelastic lyotropic liquid crystals formed in a bio-based trimeric surfactant system.

Exploring the self-assembly of oligomeric surfactants is expected to bridge the gap between conventional and polymeric surfactants. Using the natural resource rosin as the starting material, a bio-based star-shaped trimeric quaternary ammonium surfactant (abbreviated tri-R-4-Phe) was synthesized. With three bulky dehydroabietic acid units in the hydrophobic group, tri-R-4-Phe has a molecular weight of 1684.9 and shows strong affinity towards both water and nonpolar organic compounds. In the presence of tri-R-4-Phe, C12EO3 was able to form lamellar lyotropic liquid crystals over a wide concentration range in water. The tri-R-4-Phe/C12EO3/water tertiary system was investigated by polarizing optical microscopy (POM), small angle X-ray scattering (SAXS) and rheological measurements. The investigated samples with different formulations all showed strong viscoelasticity, and the viscosity increased with the surfactant content. All samples showed interesting shear banding phenomena due to the shear induced mesoscale phase transition in tri-R-4-Phe/C12EO3/water systems. The present work reveals the unique behaviour of trimeric surfactant involved LLC systems and the result may be helpful in investigating delicate molecular self-assembly using natural resources.

Aggregate evolution in aqueous solutions of a Gemini surfactant derived from dehydroabietic acid.

Innovations in surfactant structure are a feasible way to probe molecular self-assembly principles. Herein, the solution behaviour of a newly synthesized Gemini surfactant derived from dehydroabietic acid, abbreviated R-(EO)-E-R, was investigated using surface tension, fluorescence, isothermal titration calorimetry (ITC), rheology, freeze-fracture transmission electron microscopy (FF-TEM) and cryogenic transmission electron microscopy (cryo-TEM) methods. R-(EO)-E-R has two large, rigid hydrophobic groups. At low concentrations, R-(EO)-E-R forms micelles with an aggregation number of approximately 10, which is smaller than those of Gemini surfactants containing flexible alkyl tails. In addition, the micellization process is less exothermic because of the rigidity of the hydrophobic portions. As the concentration increases, R-(EO)-E-R without any additives forms wormlike micelles, endowing the solution with an obvious viscoelasticity. Further increases in the concentration lead to the coexistence of single-walled vesicles, double-walled vesicles and rarely observed long, tubular vesicles. This behaviour is attributed to the two large, rigid hydrophobic groups of R-(EO)-E-R, which increase the density of the hydrophobic portion around the ionic head groups and facilitate the formation of aggregates with lower curvatures and asymmetric morphology. Surfactants containing rigid hydrophobic portions are expected to result in more delicate, self-assembled morphologies with broad applications.

Novel Oil-in-Water Emulsions Stabilised by Ionic Surfactant and Similarly Charged Nanoparticles at Very Low Concentrations.

Novel oil-in-water (O/W) emulsions are prepared which are stabilised by a cationic surfactant in combination with similarly charged alumina nanoparticles at concentrations as low as 10-5 m and 10-4  wt %, respectively. The surfactant molecules adsorb at the oil-water interface to reduce the interfacial tension and endow droplets with charge ensuring electrical repulsion between them, whereas the charged particles are dispersed in the aqueous films between droplets retaining thick lamellae, reducing water drainage and hindering flocculation and coalescence of droplets. This stabilization mechanism is universal as it occurs with different oils (alkanes, aromatic hydrocarbons and triglycerides) and in mixtures of anionic surfactant and negatively charged nanoparticles. Further, such emulsions can be switched between stable and unstable by addition of an equimolar amount of oppositely charged surfactant which forms ion pairs with the original surfactant destroying the repulsion between droplets.

Photoresponsive Foams Generated by a Rigid Surfactant Derived from Dehydroabietic Acid.

Innovation in the structure of surfactants is crucial to the construction of a surfactant-based system with intriguing properties. With dehydroabietic acid as a starting material, a nearly totally rigid azobenzene surfactant (R-azo-Na) was synthesized. The trans-R-azo-Na formed stable foams with half-lives of 636, 656, 976, and 872 min for 0.3, 1, 2, and 4 mmol·L-1 aqueous solutions, respectively. Under UV light irradiation, a fast collapse of the foams was observed, showing an in situ response. The excellent foam stability of trans-R-azo-Na leads to the extremely high photoresponsive efficiency. As revealed by dynamic surface tension and pulsed-field gradient NMR methods, an obvious energy barrier existed in the adsorption/desorption process of trans-R-azo-Na on the air/water interface. The foams formed by trans-R-azo-Na are thus stable against coarsening processes. The results reveal the unique photoresponsive behavior of a surfactant with a rigid hydrophobic skeleton and provide new insights into the structure causing aggregation of surfactants.

Mechanically-sensitive hydrogels formed from ß-cyclodextrin and an anionic surfactant containing a biphenyl group.

Hydrogels are important soft materials with intriguing properties. By taking advantage of the host-guest interactions and multiple molecular interactions, it is expected that novel hydrogel systems can be formed. This strategy has been implemented here, transparent hydrogels were formed by using a newly-synthesized anionic surfactant, sodium 2-(4-phenylphenoxy)dodecanoate (C12biphNa), and ß-cyclodextrin (ß-CD) in different proportions and their properties were investigated. Gelation of water occurs at extremely low surfactant concentrations (5 mM for a 1:3 C12biphNa: ß-CD system), and a single C12biphNa with its associated ß-CDs can trap about 11,000 water molecules on average. In addition, the systems are fragile to mechanical stimulus and thus show mechanical sensitivity. Cryo-TEM reveals that the hydrogels have a microstructure consisting of rigid nanowire-like aggregates (with cross-sectional diameters of about 7-8 nm) locally distributed in a parallel manner in solution. These microstructural features are responsible for the peculiar properties of the hydrogel systems presented. The inclusion complexes formed by C12biphNa and ß-CD were investigated using (1)H NMR and 2D nuclear overhauser effect spectroscopy and their aggregation state was proposed. This work enriches the connotation of nonamphiphilic self-assembly and provides inspiration for constructing new functional soft materials.

Rosin-based chiral wormlike Micelles: Rheological behavior and its application in preparing ultrasmall gold nanoparticles.

Innovations in surfactant structures are a feasible way to prepare unique molecular aggregates with interesting properties. Herein, taking dehydroabietic acid as the starting material, a new amine oxide surfactant, abbreviated as R-8-AO, was synthesized. Cryogenic transmission electron microscopy (cryo-TEM) images and circular dichroism (CD) spectra reveal that at suitable concentrations, R-8-AO molecules form rarely discovered right-handed chiral wormlike micelles, which have a cross-sectional diameter of 5-6 nm. The overlap concentration of R-8-AO is approximately 8 mM, above which the wormlike micelles began to entangle in solutions. Due to the strong van der Waals forces between R-8-AO molecules, the scaling law gives an exponent of 7.88, which is higher than the theory predicted value. Gold nanoparticles were synthesized in-situ by irradiating mixed solutions of HAuCl4 and wormlike micelles formed by R-8-AO with UV light. These ultrasmall spherical gold nanoparticles, which are located at the surface of wormlike micelles, have a uniform particle size of 3 ± 1 nm, as observed by TEM. In addition, the gold nanoparticles form a worm-like morphology induced by the wormlike micelles, showing soft-aggregate-directed nanoparticle assembly. This work is first to reveal the effectiveness of preparing ultrasmall gold nanoparticles with new morphological wormlike micelles as soft templates. The resulting organic-inorganic hybrid aggregates are also expected to find applications in catalysis and electronic fields.

Supramolecular Hydrogels with Chiral Nanofibril Structures Formed from ß-Cyclodextrin and a Rosin-Based Amino Acid Surfactant.

The rational combination of natural molecules is expected to provide new soft material building blocks. Herein, a rosin-based amino acid surfactant was synthesized using dehydroabietic acid and l-serine as the starting materials (denoted as R-6-Ser). Supramolecular hydrogels were formed when ß-cyclodextrin (ß-CD) was mixed with R-6-Ser at molar ratios of over 0.5:1 and above certain concentrations. The hydrogels were investigated using rheometry, small-angle X-ray scattering, CD spectroscopy, and cryo-transmission electron microscopy (cryo-TEM). The ß-CD associated with the isopropyl benzyl group of the dehydroabietic acid unit in R-6-Ser and formed R-6-Ser@ß-CD complexes. The complexes and R-6-Ser self-assembled to form elongated right-handed rigid fibers with a diameter of approximately 7-8 nm, which were responsible for the elasticity of the hydrogels. This work demonstrated the feasibility of preparing supramolecular hydrogels from a diterpenoid-based surfactant and ß-CD and provides a new means of utilizing the secretions of pine trees.