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An unprecedented double photoexcitation mechanism for photoswitching in conjugated-dienes to trigger physiological processes for photopharmacology.

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January 2025

Laboratory of Advanced Computation and Theory for Materials and Chemistry, Department of Chemistry, National Institute of Technology Warangal (NITW), Warangal, Telangana-506004, India.

The optical control of physiological processes with high precision using photoswitches is an emerging strategy for non-invasive diagnosis and therapies, providing innovative solutions to complex biomedical challenges. Light-responsive cyclic conjugated-dienes (cCDs) have long been recognized for their 4π-photocyclization; however, photoswitching behaviour in medium-sized cCDs has recently been reported, representing a pioneering discovery in the field. Reinforced by previous experimental evidence corroborating the Woodward-Hoffmann rules, this report provides insight into the origin of the exotic dual photoexcitation mechanism devised to achieve thermo-reversible photoswitching in large cCDs with cyclodeca-1,3-diene as a prototype.

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Oleogels (organogels) are systems resembling a solid substance based on the gelation of organic solvents (oil or non-polar liquid) through components of low molecular weight or oil-soluble polymers. Such compounds are organogelators that produce a thermoreversible three-dimensional gel network that captures liquid organic solvents. Oleogels based on natural oils are attracting more attention due to their numerous advantages, such as their unsaturated fatty acid contents, ease of preparation, and safety of use.

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In this study, we demonstrate a unique and promising approach to access peptide-based diverse nanostructures in a single gelator regime that is capable of exhibiting different surface topographies and variable physical properties, which, in turn, can effectively mimic the extracellular matrix (ECM) and regulate variable cellular responses. These diverse nanostructures represent different energy states in the free energy landscape, which have been created through different self-assembling pathways by providing variable energy inputs by simply altering the gelation induction temperature from 40 °C to 90 °C. The highly entangled network structure with long fibers was created by higher energy inputs, , inducing the gelation at a higher temperature in the 70-90 °C range, whereas the less entangled nanoscale network with short fibers was obtained at a lower gelation induction temperature of 40-60 °C.

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Covalent organic nanotubes offer enhanced stability, robustness, and functionality, compared to their noncovalent counterparts. This study explores constructing polydiacetylene (PDA) nanotubes using a two-step process: self-assembly via noncovalent interactions followed by UV-induced polymerization of a diacetylene template. A promising building block consisting of a hydrogen-bonding headgroup, barbituric acid, linked to a linear diacetylene chain was prepared.

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Capsular contracture, a significant complication of breast-implant surgery, causes pain and deformation following the formation of a tight capsule around an implant. Current surgical and non-surgical treatment options are invasive, expensive, and typically administered for prolonged periods, potentially leading to side effects. To address these challenges, we developed a novel fish oil-encapsulated, poloxamer-based nanoemulsion gel with omega-3 (ω3) as the primary active component (NE-ω3 gel; N3G).

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