Recent Progress in the Endosomal Escape Mechanism and Chemical Structures of Polycations for Nucleic Acid Delivery.

Nucleic acid-based therapies are seeing a spiralling surge. Stimuli-responsive polymers, especially pH-responsive ones, are gaining widespread attention because of their ability to efficiently deliver nucleic acids. These polymers can be synthesized and modified according to target requirements, such as delivery sites and the nature of nucleic acids. In this regard, the endosomal escape mechanism of polymer-nucleic acid complexes (polyplexes) remains a topic of considerable interest owing to various plausible escape mechanisms. This review describes current progress in the endosomal escape mechanism of polyplexes and state-of-the-art chemical designs for pH-responsive polymers. The importance is also discussed of the acid dissociation constant (i.e., pKa) in designing the new generation of pH-responsive polymers, along with assays to monitor and quantify the endosomal escape behavior. Further, the use of machine learning is addressed in pKa prediction and polymer design to find novel chemical structures for pH responsiveness. This review will facilitate the design of new pH-responsive polymers for advanced and efficient nucleic acid delivery.

Ionic Liquid Stabilized Gelatin-Lignin Films: A Potential UV-Shielding Material with Excellent Mechanical and Antimicrobial Properties.

Significant research is currently underway to develop environmentally friendly UV-shielding materials. Herein, we have constructed choline citrate (a biobased ionic liquid, IL) stabilized homogeneous gelatin-lignin UV-shielding films with excellent antimicrobial and mechanical properties. The synthesis procedure of the films is less energy demanding, one pot, and sustainable in nature. Prepared films were characterized by mechanical and thermal analysis using UTM and TGA, respectively. ATR-IR and PXRD was employed to explore the possible formation of H-bonding between biopolymers and the IL and the change in crystallinity in films after addition of IL to the gelatin-lignin matrix. Surface morphology of prepared films has been studied using optical microscope, AFM, and field emission SEM (FE-SEM). Optical properties of prepared films were measured using UV/Vis spectroscopy. Antimicrobial activity of the prepared films was tested against Bacillus subtilis. Prepared biofilms showed a sun-protection factor (SPF) of up to ≈45.0, large elongation ≈200 %, and tensile strength ≈70 MPa, which are as good as those values exhibited by organic polymeric films, indicating a promising renewable-resources-based material for UV light blocking.

Green and Efficient Processing of Cinnamomum cassia Bark by Using Ionic Liquids: Extraction of Essential Oil and Construction of UV-Resistant Composite Films from Residual Biomass.

There is significant interest in the development of a sustainable and integrated process for the extraction of essential oils and separation of biopolymers by using novel and efficient solvent systems. Herein, cassia essential oil enriched in coumarin is extracted from Cinnamomum cassia bark by using a protic ionic liquid (IL), ethylammonium nitrate (EAN), through dissolution and the creation of a biphasic system with the help of diethyl ether. The process has been perfected, in terms of higher biomass dissolution ability and essential oil yield through the addition of aprotic ILs (based on the 1-butyl-3-methylimidazolium (C4 mim) cation and chloride or acetate anions) to EAN. After extraction of oil, cellulose-rich material and free lignin were regenerated from biomass-IL solutions by using a 1:1 mixture of acetone-water. The purity of the extracted essential oil and biopolymers were ascertained by means of FTIR spectroscopy, NMR spectroscopy, and GC-MS techniques. Because lignin contains UV-blocking chromophores, the oil-free residual lignocellulosic material has been directly utilized to construct UV-light-resistant composite materials in conjunction with the biopolymer chitosan. Composite material thus obtained was processed to form biodegradable films, which were characterized for mechanical and optical properties. The films showed excellent UV-light resistance and mechanical properties, thereby making it a material suitable for packaging and light-sensitive applications.

Structural and functional stability of cellulase in aqueous-biamphiphilic ionic liquid surfactant solution.

In order to explore the potential of a biamphiphilic ionic liquid surfactant as an enzyme stabilizer in detergents, we have investigated the structural and functional stability of cellulase upon interaction with 3-methyl-1-octylimidazolium dodecylsulfate, [C8mim][C12OSO3], in aqueous medium at pH 4.8. Adsorption and binding isotherms determined from tensiometry and isothermal titration calorimetry indicated that [C8mim][C12OSO3] interacts with cellulase distinctly at the three critical concentrations, viz., aggregation, C1, saturation, C2, and vesicular, C3. Fluorescence (at λex = 280 nm), far UV-circular dichroism spectra, and dynamic light scattering results have shown that [C8mim][C12OSO3] alters the tertiary and secondary structure of cellulase with a slight initial unfolding in the monomeric regime (up to C1), refolding in the aggregation regime (up to C2), and unfolding in the shared aggregation regimes (below C3) and stabilizes the altered conformation in the post-vesicular regime with an overall variation of hydrodynamic diameter from 4.12 to 7.19 nm. A dinitrosalicylic acid sugar assay test showed excellent functional stability of cellulase with an activity of ≥1 unit/mg in all the concentration regimes. A very good surface activity (J. Phys. Chem. B 2012, 116, 14363) complied by the present results vindicates the candidature of [C8mim][C12OSO3] as a potential alternative of mixed micelles or nonionic surfactants for cellulase stabilization in detergent industries.