ABSTRACT
The rational design of chemical coatings is used to control surface interactions with small molecules, biomolecules, nanoparticles, and liquids as well as optical and other properties. Specifically, micropatterned surface coatings have been used in a wide variety of applications, including biosensing, cell growth assays, multiplexed biomolecule interaction arrays, and responsive surfaces. Here, a maskless photopatterning process is studied, using the photocatalyzed thiol-yne "click" reaction to create both binary and gradient patterns on thiolated surfaces. Nearly defect-free patterns are produced by first coating glass surfaces with mercaptopropylsilatrane, a silanizing agent that forms smoother self-assembled monolayers than the commonly used 3-mercaptopropyltrimethoxysilane. Photopatterning is then performed using UV (365 nm) or visible (405 nm) light to graft molecules onto the surface in tunable concentrations based on the local exposure. The technique is demonstrated for multiple types of molecular grafts, including fluorescent dyes, poly(ethylene glycol), and biotin, the latter allowing subsequent deposition of biomolecules via biotin-avidin binding. Patterning is demonstrated in water and dimethylformamide, and the process is repeated to combine molecules soluble in different phases. The combination of arbitrary gradient formation, broad applicability, a low defect rate, and fast prototyping thanks to the maskless nature of the process creates a particularly powerful technique for molecular surface patterning that could be used for a wide variety of micropatterned applications.
Subject(s)
Biotin , Sulfhydryl Compounds , Avidin/chemistry , Biotin/chemistry , Click Chemistry , Light , Sulfhydryl Compounds/chemistry , Surface PropertiesABSTRACT
Sporopollenin exine capsules (SECs) are empty microcapsules that are 25 µm in diameter and have extensive networks of â¼200 nm diameter holes obtained by chemically removing all external and internal cytoplastic materials from the natural pollen grains. We have demonstrated that a phase change material (PCM) such as n-eicosane (EIS), a natural paraffin wax, can be successfully encapsulated in the SECs to produce [EIS@SEC]. The high stability and robust nature of SECs retain EIS in the microcavity even during phase transitions, enabling EIS to fully maintain its phase change property while also protecting the EIS from elevated temperatures and corrosive environments. [EIS@SEC] can, therefore, be incorporated into cellulose (CEL) composites with a synthetic process that uses the simple ionic liquid butylmethylimmidazolium chloride to produce [CEL+EIS@SEC] composites. Similar to EIS alone, EIS in the [CEL+EIS@SEC] composites melts when heated and crystallizes when cooled. The energies associated with the crystallization and melting processes enable the [CEL+EIS@SEC] composites to fully exhibit the properties expected of PCMs, i.e., heating the surroundings when they cool and absorbing energy from the surroundings when they warm. The efficiency of latent heat storage and release of [CEL+EIS@SEC] composites was estimated to be around 57% relative to pure EIS. The fact that the DSC curves of the [CEL+EIS@SEC] composites remain the same after going through the heating-melting cycle 220 times clearly indicates that SEC effectively retains EIS in its cavity and protects it from leaking and that the [CEL+EIS@SEC] composites are highly stable and reliable as a phase change material. The [CEL+EIS@SEC] composites are superior to any other available materials based on encapsulated PCM because they are not only robust, reliable, and stable and have strong mechanical properties. They are also are sustainable and biocompatible because as they are synthesized from all naturally abundant materials using a green and recyclable synthesis. These features enable the [CEL+EIS@SEC] composites to be uniquely suited as high performance materials for such uses as dressings to treat burnt wounds, smart textiles for clothing, smart building materials, and energy storage.
