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.

Luteolin Phosphate Derivatives Generated by Cultivating Bacillus subtilis var. Natto BCRC 80517 with Luteolin.

Luteolin (LUT), a plant-derived flavone, exhibits various bioactivities; however, the poor aqueous solubility hampers its applications. Here, we revealed bioconversion of LUT by Bacillus subtilis BCRC 80517, yielding three water-soluble phosphate conjugates. These derivatives were identified as luteolin 4'-O-phosphate (L4'P), luteolin 3'-O-phosphate (L3'P), and luteolin 7-O-phosphate (L7P) by LC-ESI-MS/MS and NMR. Besides, we found that Bacillus subtilis BCRC 80517 was able to convert different levels of LUT but showed a limited conversion rate. By observing bacterial morphology with transmission electron microscopy and confocal fluorescence microscopy, we found that LUT disrupted the bacterial membrane integrity, which explained the incomplete conversion. Additionally, we revealed a spontaneous intramolecular transesterification of L4'P to L3'P, the thermodynamically more stable form, under acidic conditions and proposed the possible mechanism involving a cyclic phosphate as the intermediate. This study provides insight into development of a potent structural modification strategy to enhance the solubility of LUT through biophosphorylation.

Isotope Effects and the Mechanism of Photoredox-Promoted [2 + 2] Cycloadditions of Enones.

13C kinetic isotope effects (KIEs) for the photoredox-promoted [2 + 2] cycloaddition of enones were determined in homocoupling and heterocoupling examples. The only significant KIEs were observed at the ß carbon, indicating that Cß-Cß bond formation is irreversible. However, these KIEs were much lower than computational predictions, suggesting that product selectivity is determined in part by a step prior to Cß-Cß bond formation. The results are explained as arising from a competition between C-C bond formation and electron exchange between substrate alkenes. This idea is supported by a relatively small substituent effect on substrate selectivity. The possible rates for electron transfer and bond-forming steps are analyzed, and the competition appears plausible, particularly if the mechanism involves a complex between reduced and neutral enone molecules.

Accelerated five-component spiro-pyrrolidine construction at the air-liquid interface.

Multi-component reactions assemble complex molecules in a highly effective way, however, they often suffer from long reaction times. We demonstrate that acceleration of a five-component spiro-pyrrolidine construction can be achieved in microdroplets and thin films. The deposition method and mild heating are crucial factors for product formation. Three key intermediates were captured by mass spectrometry to elucidate the tandem reaction mechanism. We also found that hydrogen bonding can significantly flatten the energy barrier at the air-liquid interface.

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.

Vibrationally Hot and Cold Triplets. Sensitizer-Dependent Dynamics and Localized Vibrational Promotion of a Di-π-methane Rearrangement.

Large intramolecular 13C kinetic isotope effects (KIEs) for the di-π-methane rearrangement of benzobarrelene fit with statistical expectations from heavy-atom tunneling when a low-energy sensitizer is employed, but much lower KIEs are observed with higher-energy sensitizers. These results in combination with trajectory studies suggest that the excess vibrational energy available from triplet energy transfer leads to hot and nonstatistical dynamics in the rearrangement.