skip to main content


Title: Translation of protein charge and hydrophilicity to materials surface properties using thermal treatment in fluorous media
Protein-based materials provide an inherently biocompatible and sustainable platform for the generation of functional materials. Translating protein properties into protein films resistant to aqueous degradation is crucial for most applications such as tissue engineering and controlled drug delivery. Current methods to stabilize protein films use three main strategies: employing the relatively limited variety of naturally self-assembling proteins, using added cross-linkers or heat curing. While the cross-linking strategy generates functionally diverse structures, unreacted additives retained in cross-linked protein films can adversely affect their final behavior. Traditional heat curing results in hydrophobic surface and loss of protein inherent properties. We demonstrate here a scalable, additive-free, fluorous media assisted thermal treatment for the fabrication of stable, hydrophilic protein films. This approach is general in terms of protein building block, retaining much of their native structure and surface properties upon heating. We demonstrate the versatility of this strategy through fabrication of antifouling coatings on complex three-dimensional surfaces. The utility of these films as biomaterials is highlighted through the generation of highly biocompatible non-fouling surfaces and regulation of cellular adhesion through choice of protein precursor.  more » « less
Award ID(s):
1740597
NSF-PAR ID:
10076022
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Materials Horizons
Volume:
5
Issue:
2
ISSN:
2051-6347
Page Range / eLocation ID:
268 to 274
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Thin polymeric films are being explored for biomedical uses such as drug delivery, biofiltration, biosensors, and tissue regeneration. Of specific interest is the formation of mechanically flexible sheets, which can be formed with controllable thickness for sealing wounds, or as biomimetic cellular constructs. Flexible substrates with precise micro‐ and nanopatterns can function as supports for cell growth with conformal contact at the biointerface. To date, approaches to form free‐standing, thin sheets are limited in the ability to present patterned architectures and micro/nanotextured surfaces. Other materials have a lack of degradability, precluding their application as cellular scaffolds. An approach is suggested using biocompatible and biodegradable films fabricated from silk fibroin. This work presents the fabrication and characterization of flexible, micropatterned, and biodegradable 2D fibroin sheets for cell adhesion and proliferation. A facile and scalable technique using photolithography is shown to fabricate optically transparent, strong, and flexible fibroin substrates with tunable and precise micropatterns over large areas. By controlling the surface architectures, the control of cell adhesion and spreading can be observed. Additionally, the base material is fully degradable via proteolysis. Through mechanical control and directing the adherent cells, it is possible to explore interactions of cells and the microscale geometric topography.

     
    more » « less
  2. Advances in solution-phase graphene patterning has provided a facile route for rapid, low-cost and scalable manufacturing of electrochemical devices, even on flexible substrates. While graphene possesses advantageous electrochemical properties of high surface area and fast heterogenous charge transport, these properties are attributed to the edge planes and defect sites, not the basal plane. Herein, we demonstrate enhancement of the electroactive nature of patterned solution-phase graphene by increasing the porosity and edge planes through the construction of a multidimensional architecture via salt impregnated inkjet maskless lithography (SIIML) and CO 2 laser annealing. Various sized macroscale pores (<25 to ∼250 μm) are patterned directly in the graphene surface by incorporating porogens ( i.e. , salt crystals) in the graphene ink which act as hard templates for pore formation and are later dissolved in water. Subsequently, microsized pores (∼100 nm to 2 μm in width) with edge plane defects are etched in the graphene lattice structure by laser annealing with a CO 2 laser, simultaneously improving electrical conductivity by nearly three orders of magnitude (sheet resistance decreases from >10 000 to ∼50 Ω sq −1 ). We demonstrate that this multidimensional porous graphene fabrication method can improve electrochemical device performance through design and manufacture of an electrochemical organophosphate biosensor that uses the enzyme acetylcholinesterase for detection. This pesticide biosensor exhibits enhanced sensitivity to acetylthiocholine compared to graphene without macropores (28.3 μA nM −1 to 13.3 μA nM −1 ) and when inhibited by organophosphate pesticides (paraoxon) has a wide linear range (10 nM to 500 nM), low limit of detection (0.6 nM), and high sensitivity (12.4 nA nM −1 ). Moreover, this fabrication method is capable of patterning complex geometries [ i.e. interdigitated electrodes (IDEs)] even on flexible surfaces as demonstrated by an IDE supercapacitor made of SIIML graphene on a heat sensitive polymer substrate. The supercapacitor demonstrates a high energy density of 0.25 mW h cm −3 at a power density of 0.3 W cm −3 . These electrochemical devices demonstrate the benefit of using SIIML and CO 2 laser annealing for patterning graphene electrodes with a multidimensional porous surface even on flexible substrates and is therefore a platform technology which could be applied to a variety of different biosensors and other electrochemical devices. 
    more » « less
  3. Fabrication of microfluidic devices by photolithography generally requires specialized training and access to a cleanroom. As an alternative, 3D printing enables cost-effective fabrication of microdevices with complex features that would be suitable for many biomedical applications. However, commonly used resins are cytotoxic and unsuitable for devices involving cells. Furthermore, 3D prints are generally refractory to elastomer polymerization such that they cannot be used as master molds for fabricating devices from polymers ( e.g. polydimethylsiloxane, or PDMS). Different post-print treatment strategies, such as heat curing, ultraviolet light exposure, and coating with silanes, have been explored to overcome these obstacles, but none have proven universally effective. Here, we show that deposition of a thin layer of parylene, a polymer commonly used for medical device applications, renders 3D prints biocompatible and allows them to be used as master molds for elastomeric device fabrication. When placed in culture dishes containing human neurons, regardless of resin type, uncoated 3D prints leached toxic material to yield complete cell death within 48 hours, whereas cells exhibited uniform viability and healthy morphology out to 21 days if the prints were coated with parylene. Diverse PDMS devices of different shapes and sizes were easily cast from parylene-coated 3D printed molds without any visible defects. As a proof-of-concept, we rapid prototyped and tested different types of PDMS devices, including triple chamber perfusion chips, droplet generators, and microwells. Overall, we suggest that the simplicity and reproducibility of this technique will make it attractive for fabricating traditional microdevices and rapid prototyping new designs. In particular, by minimizing user intervention on the fabrication and post-print treatment steps, our strategy could help make microfluidics more accessible to the biomedical research community. 
    more » « less
  4. Recent advances in 3D printing have enabled the creation of novel 3D constructs and devices with an unprecedented level of complexity, properties, and functionalities. In contrast to manufacturing techniques developed for mass production, 3D printing encompasses a broad class of fabrication technologies that can enable 1) the creation of highly customized and optimized 3D physical architectures from digital designs; 2) the synergistic integration of properties and functionalities of distinct classes of materials to create novel hybrid devices; and 3) a biocompatible fabrication approach that facilitates the creation and co-integration of biological constructs and systems. Developing the ability to 3D print various classes of materials possessing distinct properties could enable the freeform generation of active electronics in unique functional, interwoven architectures. Here we are developing a multiscale 3D printing approach that enables the integration of diverse classes of materials to create a variety of 3D printed electronics and functional devices with active properties that are not easily achieved using standard microfabrication techniques. In one of the examples, we demonstrate an approach to prolong the gastric residence of wireless electronics to weeks via multimaterial three-dimensional design and fabrication. The surgical-free approach to integrate biomedical electronics with the human body can revolutionize telemedicine by enabling a real-time diagnosis and delivery of therapeutic agents. 
    more » « less
  5. Favorable polymer-substrate interactions induce surface orientation fields in block copolymer (BCP) melts. In linear BCP processed near equilibrium, alignment of domains generally persists for a small number of periods (∼4–6 D 0 ) before randomization of domain orientation. Bottlebrush BCP are an emerging class of materials with distinct chain dynamics stemming from substantial molecular rigidity, enabling rapid assembly at ultrahigh (>100 nm) domain periodicities with strong photonic properties (structural color). This work assesses interface-induced ordering in PS- b -PLA bottle b rush diblock copolymer films during thermal annealing between planar surfaces. To clearly observe the decay in orientational order from surface to bulk, we choose to study micron-scale films spanning greater than 200 lamellar periods. In situ optical microscopy and transmission UV-Vis spectroscopy are used to monitor photonic properties during annealing and paired with ex situ UV-Vis reflection measurement, cross-sectional scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS) to probe the evolution of domain microstructure. Photonic properties were observed to saturate within minutes of annealing at 150 °C, with distinct variation in transmission response as a function of film thickness. The depth of the highly aligned surface region was found to vary stochastically in the range of 30–100 lamellar periods, with the sharpness of the orientation gradient decreasing substantially with increasing film thickness. This observation suggests a competition between growth of aligned, heterogeneously nucleated, grains at the surface and orientationally isotropic, homogeneously nucleated, grains throughout the bulk. This work demonstrates the high potential of bottlebrush block copolymers in rapid fabrication workflows and provides a point of comparison for future application of directed self-assembly to BBCP ordering. 
    more » « less