Rheological dynamics and structural characteristics of supramolecular assemblies of ß-cyclodextrin and sulfonic surfactants.

Cyclodextrins are highly functional compounds with a hydrophobic cavity capable of forming supramolecular inclusion complexes with various classes of molecules including surfactants. The resultant rich nanostructures and their dynamics are an interesting research problem in the area of soft condensed matter and related applications. Herein, we report novel dynamical supramolecular assemblies based on the complexation of ß-cyclodextrin with 3 different sulfonic surfactants, which are sodium hexadecylsulfate, sodium dodecylbenzenesulfonate, and myristyl sulfobetaine. It was observed that a ß-cyclodextrin : surfactant/2 : 1 molar ratio was ideal for inducing axial growth and imparting large viscosities in the suspensions. Such complexation processes were accompanied by intriguing nanostructural phase behaviors and rheological properties that were very sensitive to the molecular architecture of sulfonic surfactants. The presence of an amino group in the head group of the surfactant allowed for large viscosities that reached 2.4 × 104 Pa s which exhibited gel-like behavior. In contrast, smaller viscosity values with a lower consistency index were observed when a bulky aromatic ring was present instead. DIC microscopy was used to visually probe the microstructure of the systems with respect to sulfonate molecular architecture. Additionally, surface tension measurements, and FTIR and NMR spectroscopies were used to gain insights into the nature of interactions that lead to the complexation and nanostructural characteristics. Finally, mechanics correlating the supramolecular morphologies to the rheological properties were proposed.

pH- and temperature-responsive supramolecular assemblies with highly adjustable viscoelasticity: a multi-stimuli binary system.

Stimuli-responsive materials are increasingly needed for the development of smart electronic, mechanical, and biological devices and systems relying on switchable, tunable, and adaptable properties. Herein, we report a novel pH- and temperature-responsive binary supramolecular assembly involving a long-chain hydroxyamino amide (HAA) and an inorganic hydrotrope, boric acid, with highly tunable viscous and viscoelastic properties. The system under investigation demonstrates a high degree of control over its viscosity, with the capacity to achieve over four orders of magnitude of control through the concomitant manipulation of pH and temperature. In addition, the transformation from non-Maxwellian to Maxwellian fluid behavior could also be induced by changing the pH and temperature. Switchable rheological properties were ascribed to the morphological transformation between spherical vesicles, aggregated/fused spherical vesicles, and bicontinuous gyroid structures revealed by cryo-TEM studies. The observed transitions are attributed to the modulation of the head group spacing between HAA molecules under different pH conditions. Specifically, acidic conditions induce electrostatic repulsion between the protonated amino head groups, leading to an increased spacing. Conversely, under basic conditions, the HAA head group spacing is reduced due to the intercalation of tetrahydroxyborate, facilitated by hydrogen bonding.

Stimuli-responsive viscosity modifiers.

Stimuli responsive viscosity modifiers entail an important class of materials which allow for smart material formation utilizing various stimuli for switching such as pH, temperature, light and salinity. They have seen applications in the biomedical space including tissue engineering and drug delivery, wherein stimuli responsive hydrogels and polymeric vessels have been extensively applied. Applications have also been seen in other domains like the energy sector and automobile industry, in technologies such as enhanced oil recovery. The chemistry and microstructural arrangements of the aqueous morphologies of dissolved materials are usually sensitive to the aforementioned stimuli which subsequently results in rheological sensitivity as well. Herein, we overview different structures capable of viscosity modification as well as go over the rheological theory associated with classical systems studied in literature. A detailed analysis allows us to explore correlations between commonly discussed models such as molecular packing parameter, tube reptation and stress relaxation with structural and rheological changes. We then present five primary mechanisms corresponding to stimuli responsive viscosity modification: (i) packing parameter modification via functional group conditioning and (ii) via dynamic bond formation, (iii) mesh formation by interlinking of network nodes, (iv) viscosity modification by chain conformation changes and (v) viscosity modification by particle jamming. We also overview several recent examples from literature that employ the concepts discussed to create novel classes of intriguing stimuli responsive structures and their corresponding rheological properties. Furthermore, we also explore systems that are responsive to multiple stimuli which can provide enhanced functionality and versatility by providing multi-level and precise actuation. Such systems have been used for programmed site-specific drug delivery.

Supramolecular dynamic binary complexes with pH and salt-responsive properties for use in unconventional reservoirs.

Hydraulic fracturing of unconventional reservoirs has seen a boom in the last century, as a means to fulfill the growing energy demand in the world. The fracturing fluid used in the process plays a substantial role in determining the results. Hence, several research and development efforts have been geared towards developing more sustainable, efficient, and improved fracturing fluids. Herein, we present a dynamic binary complex (DBC) solution, with potential to be useful in the hydraulic fracturing domain. It has a supramolecular structure formed by the self-assembly of low molecular weight viscosifiers (LMWVs) oleic acid and diethylenetriamine into an elongated entangled network under alkaline conditions. With less than 2 wt% constituents dispersed in aqueous solution, a viscous gel that exhibits high viscosities even under shear was formed. Key features include responsiveness to pH and salinity, and a zero-shear viscosity that could be tuned by a factor of ~280 by changing the pH. Furthermore, its viscous properties were more pronounced in the presence of salt. Sand settling tests revealed its potential to hold up sand particles for extended periods of time. In conclusion, this DBC solution system has potential to be utilized as a smart salt-responsive, pH-switchable hydraulic fracturing fluid.

pH-responsive viscoelastic supramolecular viscosifiers based on dynamic complexation of zwitterionic octadecylamidopropyl betaine and triamine for hydraulic fracturing applications.

Viscosity modifying agents are one of the most critical components of hydraulic fracturing fluids, ensuring the efficient transport and deposition of proppant into fissures. To improve the productivity index of hydraulic fracturing processes, better viscosifiers with a higher proppant carrying capacity and a lower potential of formation damage are needed. In this work, we report the development of a novel viscoelastic system relying on the complexation of zwitterionic octadecylamidopropyl betaine (OAPB) and diethylenetriamine (DTA) in water. At a concentration of 2 wt%, the zwitterionic complex fluid had a static viscosity of 9 to 200 poise, which could be reversibly adjusted by changing the suspension pH. The degree of pH-responsiveness ranged from 10 to 27 depending on the shear rate. At a given concentration and optimum pH value, the zwitterionic viscosifiers showed a two-orders-of-magnitude reduction in settling velocity of proppant compared to polyacrylamide solution (slickwater). By adjusting the pH between 4 and 8, the networked structure of the gel could be fully assembled and disassembled. The lack of macromolecular residues at the dissembled state can be beneficial for hydraulic fracturing application in avoiding the permeation damage issues encountered in polymer and linear-gel-based fracturing fluids. The reusability and the unnecessary permanent breakers are other important characteristics of these zwitterionic viscosifiers.