The fabrication of high-density polymer microarray is described, allowing the simultaneous and efficient evaluation of more than 7000 different polymers in a single-cellular-based screen. These high-density polymer arrays are applied in the search for synthetic substrates for hESCs culture. Up-scaling of the identified hit polymers enables long-term cellular cultivation and promoted successful stem-cell maintenance.
Hydrophobic dipeptide molecules have been induced to self-assemble into thin interfacial films at the air-water interface via drop-casting. The mechanism involves fiberlike strands, which exist in the high-pH spreading solvent, becoming intertwined at the surface of a low-pH subphase. Atomic force microscopy (AFM) reveals that the strands are ∼40 nm wide and ∼20 nm high and are woven together to form layers that can be up to ∼800 nm thick. The use of Thioflavin T (ThT) fluorescence suggests that the dipeptides are ordered in a β-sheet configuration irrespective of whether they form an interfacial film, while Fourier transform infrared spectroscopy (FTIR) shows the protonation effect for those which do form an interfacial film. The entanglement between protonated strands results in the formation of an elastic sheet. The interfacial films buckled under compression in a Langmuir trough and have the ability to convey long-term stability to large air bubbles.
The structural behavior of three amphiphilic semicrystalline poly(isoprene-b-ethylene oxide) block copolymers (PI-b-PEO) with different PEO volume fraction (f(PEO) = 0.32, 0.49, and 0.66), spin-coated on freshly cleaved mica surfaces from aqueous solutions, was investigated by atomic force microscopy. We focus on the dependence of the resulting thin film nanostructures on the molecular characteristics (f(PEO) and molecular weight) and the adsorbed amount. The nanostructures obtained immediately after spin-coating were robust and remained unchanged after annealing and/or aging. The PEO affinity for the highly hydrophilic mica and the tendency of the hydrophobic and low surface energy PI to dewet and be at the free interface caused the soft PI-b-PEO micelles to collapse leading to the formation of 2D dendritic networks over mica. We show that, for all three polymers, the dendritic monolayer thickness can be predicted by a model consisting of a PEO crystallized layer (directly on top of mica) of the same thickness in all cases and a PI brush layer on top. In thicker areas, polymer material self-assembled into conelike multilamellar bilayers on top of the monolayer and oriented parallel to the substrate for both symmetric and asymmetric diblock copolymers with the lowest f(PEO). We compare the lateral morphology of the films and discuss the thickness heterogeneity, which results from the coupling and competition of crystallization kinetics, phase separation, and wetting/dewetting phenomena highlighting the role of the two blocks to inhibit or enhance certain morphologies. We show that the deviation of the f(PEO) = 0.32 thin film from its bulk phase structure (cylinders in hexagonal lattice) continues for several lamellar bilayers away from the substrate. For the asymmetric PI-b-PEO polymer with the higher PEO volume fraction (f(PEO) = 0.66) and higher APT, laterally extensive stacks of flat-on lamellar crystallites formed on the surface demonstrating the crucial role of the PEO crystallization.
We report on the drying process of sessile droplets of aqueous poly(ethylene oxide) (PEO) solutions studied by contact angle analysis. Liquid samples were prepared with the same initial concentration of four different molecular weights, M w of PEO. Droplets with initial volumes between 1 µL and 5 µL were left to evaporate while temperature, pressure and relative humidity were kept constant. Residues were formed with either a disk-like puddle or a distinctive tall conical pillar shape. The latter occurred following a four-stage deposition process: pinned drying, during which the contact line is stationary; pseudodewetting, where the receding contact line is induced by precipitation; bootstrap building, during which the liquid droplet is lifted upon freshly-precipitated solid; and late drying. Contact angle analysis allowed us to monitor all stages during drying and consider transitions between stages for different molecular weights. We illustrate the mechanisms taking place during the crucial stages of pinning and depinning, revealing the effect of adhesion and contact line friction for high molecular weights and its influence on the final 2 morphology of the dried PEO solute. To this end, we performed PEO solution droplet evaporation on PEO and PTFE films demonstrating the importance of interfacial interaction phenomena. We show that the formation of disk-like puddles for high molecular weights on glass are associated with continuous droplet contact line pinning. This results from the strong adhesion due to the interdigitation of the loops and tails of a polymer layer (adsorbed on glass during evaporation) with the polymer gel network inside the droplet that forms as water evaporates.
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