Hierarchical Mechanical Transduction of Precision-Engineered DNA Hydrogels with Sacrificial Bonds.

Engineering the response to external signals in mechanically switchable hydrogels is important to promote smart materials applications. However, comparably little attention has focused on embedded precision mechanisms for autonomous nonlinear response in mechanical profiles in hydrogels, and we lack understanding of how the behavior from the molecular scale transduces to the macroscale. Here, we design a nonlinear stress-strain response into hydrogels by engineering sacrificial DNA hairpin loops into model network hydrogels formed from star-shaped building blocks. We characterize the force-extension response of single DNA hairpins and are able to describe how the specific topology influences the nonlinear mechanical behavior at different length scales. For this purpose, we utilize force spectroscopy as well as microscopic and macroscopic deformation tests. This study contributes to a better understanding of designing nonlinear strain-adaptive features into hydrogel materials.

Adsorbing DNA to Mica by Cations: Influence of Valency and Ion Type.

Ion-mediated attraction between DNA and mica plays a crucial role in biotechnological applications and molecular imaging. Here, we combine molecular dynamics simulations and single-molecule atomic force microscopy experiments to characterize the detachment forces of single-stranded DNA at mica surfaces mediated by the metal cations Li+, Na+, K+, Cs+, Mg2+, and Ca2+. Ion-specific adsorption at the mica/water interface compensates (Li+ and Na+) or overcompensates (K+, Cs+, Mg2+, and Ca2+) the bare negative surface charge of mica. In addition, direct and water-mediated contacts are formed between the ions, the phosphate oxygens of DNA, and mica. The different contact types give rise to low- and high-force pathways and a broad distribution of detachment forces. Weakly hydrated ions, such as Cs+ and water-mediated contacts, lead to low detachment forces and high mobility of the DNA on the surface. Direct ion-DNA or ion-surface contacts lead to significantly higher forces. The comprehensive view gained from our combined approach allows us to highlight the most promising cations for imaging in physiological conditions: K+, which overcompensates the negative mica charge and induces long-ranged attractions. Mg2+ and Ca2+, which form a few specific and long-lived contacts to bind DNA with high affinity.

Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy.

Atomic force microscopy (AFM)-based single molecule force spectroscopy is an ideal tool for investigating the interactions between a single polymer and surfaces. For a true single molecule experiment, covalent attachment of the probe molecule is essential because only then can hundreds of force-extension traces with one and the same single molecule be obtained. Many traces are in turn necessary to prove that a single molecule alone is probed. Additionally, passivation is crucial for preventing unwanted interactions between the single probe molecule and the AFM cantilever tip as well as between the AFM cantilever tip and the underlying surface. The functionalization protocol presented here is reliable and can easily be applied to a variety of polymers. Characteristic single molecule events (i.e., stretches and plateaus) are detected in the force-extension traces. From these events, physical parameters such as stretching force, desorption force and desorption length can be obtained. This is particularly important for the precise investigation of stimuli-responsive systems at the single molecule level. As exemplary systems poly(ethylene glycol) (PEG), poly(N-isopropylacrylamide) (PNiPAM) and polystyrene (PS) are stretched and desorbed from SiOx (for PEG and PNiPAM) and from hydrophobic self-assembled monolayer surfaces (for PS) in aqueous environment.

Opposing Temperature Dependence of the Stretching Response of Single PEG and PNiPAM Polymers.

The response of switchable polymer blends and coatings to temperature variation is important for the development of high-performance materials. Although this has been well studied for bulk materials, a proper understanding at the molecular level, in particular for high stretching forces, is still lacking. Here we investigate the molecular details of the temperature-dependent elastic response of two widely used water-soluble polymers, namely, polyethylene glycol (PEG) and poly(N-isopropylacrylamide) (PNiPAM) with a combined approach using atomic force microscopy (AFM) based single molecule force spectroscopy (SMFS) experiments and molecular dynamics (MD) simulations. SMFS became possible by the covalent attachment of long and defined single polymers featuring a functional end group. Most interestingly, varying the temperature produces contrasting effects for PEG and PNiPAM. Surprising as these results might occur at first sight, they can be understood with the help of MD simulations in explicit water. We find that hydration is widely underestimated for the mechanics of macromolecules and that a polymer chain has competing energetic and entropic elastic components. We propose to use the temperature dependence to quantify the energetic behavior for high stretching forces. This fundamental understanding of temperature-dependent single polymer stretching response might lead to innovations like fast switchable polymer blends and coatings with polymer chains that act antagonistically.