Intracellular Communication between Synthetic Macromolecules.

Non-viral delivery is an important strategy for selective and efficient gene therapy, immunization, and RNA interference, which overcomes problems of genotoxicity and inherent immunogenicity associated with viral vectors. Liposomes and polymers are compelling candidates as carriers for intracellular, non-viral delivery, but maximal efficiencies of around 1% have been reported for the most advanced non-viral carriers. Here, we develop a library of dendronized bottlebrush polymers with controlled defects, displaying a level of precision surpassed only by biological molecules like DNA, RNA, and proteins. We test concurrent and competitive delivery of DNA and show for the first time that, while intracellular communication is thought to be an exclusively biomolecular phenomenon, such communication between synthetic macromolecular complexes can also take place. Our findings challenge the assumption that delivery agents behave as bystanders that enable transfection by passive intracellular release of genetic cargo and improve upon coarse strategies in intracellular carrier design lacking control over polymer sequence, architecture, and composition, leading to a hit-or-miss outcome. Understanding the communication that takes place between macromolecules will help improve the design of non-viral delivery agents and facilitate translation of genome engineering, vaccines, and nucleic acid-based therapies.

Outstanding Bio-Tribological Performance Induced by the Synergistic Effect of 2D Diamond Nanosheet Coating and Silk Fibroin.

Due to their excellent biocompatibility, outstanding mechanical properties, high strength-to-weight ratio, and good corrosion resistance, titanium (Ti) alloys are extensively used as implant materials in artificial joints. However, Ti alloys suffer from poor wear resistance, resulting in a considerably short lifetime. In this study, we demonstrate that the chemical self-assembly of novel two-dimensional (2D) diamond nanosheet coatings on Ti alloys combined with natural silk fibroin used as a novel lubricating fluid synergistically results in excellent friction and wear performance. Linear-reciprocating sliding tests verify that the coefficient of friction and the wear rate of the diamond nanosheet coating under silk fibroin lubrication are reduced by 54 and 98%, respectively, compared to those of the uncoated Ti alloy under water lubrication. The lubricating mechanism of the newly designed system was revealed by a detailed analysis of the involved microstructural and chemical changes. The outstanding tribological behavior was attributed to the establishment of artificial joint lubrication induced by the cross binding between the diamond nanosheets and silk fibroin. Additionally, excellent biocompatibility of the lubricating system was verified by cell viability, which altogether paves the way for the application of diamond coatings in artificial Ti joint implants.

Conformation of poly(ethylene glycol) in aqueous cholinium amino acid hybrid solvents.

HYPOTHESIS: Hybrid solvents based on cholinium amino acid ionic liquids ([Ch][AA] ILs) mixed with water are environmentally benign solvents with low toxicity. [Ch][AA] ILs are used in biomass pretreatment processes to dissolve targeted (macro)molecules such as lignin from lingnocellulose. Understanding how [Ch][AA] ILs dissolve polymers is therefore of great interest for the rational design of ILs towards industrial application. Variation of the IL anion and the water concentration are hypothesised to change the solvent properties of [Ch][AA] hybrid solvents. Therefore, we probe the solvent quality of [Ch][AA] aqueous solutions with different anions (glycinate, prolinate and argininate) and water concentration for the simple model solute poly(ethylene glycol) (PEG). EXPERIMENTS: Partial phase diagrams were produced to probe the salting-out effect of [Ch][AA] ILs towards PEG (Mw = 38 kDa). Small-angle neutron scattering experiments of deuterated PEG in hydrogenous [Ch][AA] aqueous solutions were performed to determine the polymer radius of gyration at infinite dilution (Rg,0) via Zimm-plots. Polymer concentration dependent apparent Rg values were obtained fitting an excluded volume polymer model onto the scattering data. Blends of hydrogenous and deuterated PEG under zero average contrast conditions were analysed to probe Rg at high polymer concentrations. FINDINGS: Hydrogen bond capacity of the anion is key to the salting-out effect of [Ch][AA] ILs on PEG. Rg,0 depends on anion species and water concentration. At IL:water = 1:30 (mole:mole) and 37 °C, cholinium argininate and cholinium glycinate are close to theta solvents while cholinium prolinate and dilute cholinium argininate (IL:water = 1:100) are between theta and good solvents.

Influence of temperature and molecular structure on ionic liquid solvation layers.

Atomic force microscopy (AFM) force profiling is used to investigate the structure of adsorbed and solvation layers formed on a mica surface by various room temperature ionic liquids (ILs) ethylammonium nitrate (EAN), ethanolammonium nitrate (EtAN), ethylammonium formate (EAF), propylammonium formate (PAF), ethylmethylammonium formate (EMAF), and dimethylethylammonium formate (DMEAF). At least seven layers are observed for EAN at 14 degrees C (melting point 13 degrees C), decreasing as the temperature is increased to 30 degrees C due to thermal energy disrupting solvophobic forces that lead to segregation of cation alkyl tails from the charged ammonium and nitrate moieties. The number and properties of the solvation layers can also be controlled by introducing an alcohol moiety to the cation's alkyl tail (EtAN), or by replacing the nitrate anion with formate (EAF and PAF), even leading to the detection of distinct cation and anion sublayers. Substitution of primary by secondary or tertiary ammonium cations reduces the number of solvation layers formed, and also weakens the cation layer adsorbed onto mica. The observed solvation and adsorbed layer structures are discussed in terms of the intermolecular cohesive forces within the ILs.