Silk fibroin as a surfactant for water-based nanofabrication.

Water-based processing plays a crucial role in high technology, especially in electronics, material sciences and life sciences, with important implications in the development of high-quality reliable devices, fabrication efficiency, safety and sustainability. At the micro- and nanoscale, water is uniquely enabling as a bridge between biological and technological systems. However, new approaches are needed to overcome fundamental challenges that arise from the high surface tension of water, which hinders wetting and, thus, fabrication at the bio-nano interface. Here we report the use of silk fibroin as a surfactant to enable water-based processing of nanoscale devices. Even in minute quantities (for example, 0.01 w/v%), silk fibroin considerably enhances surface coverage and outperforms commercial surfactants in precisely controlling interfacial energy between water-based solutions and hydrophobic surfaces. This effect is ascribed to the amphiphilic nature of the silk molecule and its adaptive adsorption onto substrates with diverse surface energy, facilitating intermolecular interactions between unlikely pairs of materials. The approach's versatility is highlighted by manufacturing water-processed nanodevices, ranging from transistors to photovoltaic cells. Its performance is found to be equivalent to analogous vacuum-processed devices, underscoring the utility and versatility of this approach for water-based nanofabrication.

Bimodal Gating Mechanism in Hybrid Thin-Film Transistors Based on Dynamically Reconfigurable Nanoscale Biopolymer Interfaces.

In recent years, increased control over naturally derived structural protein formulations and their self-assembly has enabled the application of high-resolution manufacturing techniques to silk-based materials, leading to bioactive interfaces with unprecedented miniaturized formats and functionalities. Here, a hybrid biopolymer-semiconductor device, obtained by integrating nanoscale silk layers in a well-established class of inorganic field-effect transistors (silk-FETs), is presented. The devices offer two distinct modes of operation-either traditional field-effect or electrolyte-gated-enabled by the precisely controlled thickness, morphology, and biochemistry of the integrated silk layers. The different operational modes are selectively accessed by dynamically modulating the free-water content within the nanoscale protein layer from the vapor phase. The utility of these hybrid devices is illustrated in a highly sensitive and ultrafast breath sensor, highlighting the opportunities offered by the integration of nanoscale biomaterial interfaces in conjunction with traditional semiconductor devices, enabling functional outcomes at the intersection between the worlds of microelectronics and biology.

Functionalized Mouth-Conformable Interfaces for pH Evaluation of the Oral Cavity.

Oral health monitoring is highly desired, especially for in home use, however, current methods are not sensitive enough and technically convoluted for this purpose. This paper presents incorporation of bioactive materials and colorimetric chemical sensors into routinely used oral appliances transforming them into bioresponsive, conformable interfaces. Specifically, endodontic paper points and dental floss can be functionalized to locally sense and monitor pH variations within the oral cavity via color changes. Moreover, edible colorimetric indicators are developed and used to make sensing, edible devices in the form factor of candies that can dynamically and visually respond to acidity changes in saliva. These interfaces would enable early detection of caries (e.g., using dental floss and paper points) providing low-cost point of care devices that respond in real-time by detecting pH variations in biological fluids thus bringing monitoring to home settings .

Photolithographic Masking Method to Chemically Pattern Silk Film Surfaces.

A method has been developed for selectively patterning silk surfaces using a photolithographic process to mask off sections of silk films, which allows selective and precise patterning of features down to 40 µm. This process is highly versatile, utilizes only low-cost equipment and can be used to rapidly prototype flat silk substrates with spatially controlled chemical patterns. Here we demonstrate the usefulness of this technique to deposit fluorescent dyes, labeled proteins and conducting polymers or to modify the surface charge of the silk protein in desired regions on a silk film surface.

Conductive Silk-Polypyrrole Composite Scaffolds with Bioinspired Nanotopographic Cues for Cardiac Tissue Engineering.

We report on the development of bioinspired cardiac scaffolds made from electroconductive acid-modified silk fibroin-poly(pyrrole) (AMSF+PPy) substrates patterned with nanoscale ridges and grooves reminiscent of native myocardial extracellular matrix (ECM) topography to enhance the structural and functional properties of cultured human pluripotent stem cells (hPSC)-derived cardiomyocytes. Nanopattern fidelity was maintained throughout the fabrication and functionalization processes, and no loss in conductive behavior occurred due to the presence of the nanotopographical features. AMSF+PPy substrates were biocompatible and stable, maintaining high cell viability over a 21-day culture period while displaying no signs of PPy delamination. The presence of anisotropic topographical cues led to increased cellular organization and sarcomere development, and electroconductive cues promoted a significant improvement in the expression and polarization of connexin 43 (Cx43), a critical regulator of cell-cell electrical coupling. The combination of biomimetic topography and electroconductivity also increased the expression of genes that encode key proteins involved in regulating the contractile and electrophysiological function of mature human cardiac tissue.

Versatile Method for Producing 2D and 3D Conductive Biomaterial Composites Using Sequential Chemical and Electrochemical Polymerization.

Flexible and conductive biocompatible materials are attractive candidates for a wide range of biomedical applications including implantable electrodes, tissue engineering, and controlled drug delivery. Here, we demonstrate that chemical and electrochemical polymerization techniques can be combined to create highly versatile silk-conducting polymer (silk-CP) composites with enhanced conductivity and electrochemical stability. Interpenetrating silk-CP composites were first generated via in situ deposition of polypyrrole during chemical polymerization of pyrrole. These composites were sufficiently conductive to serve as working electrodes for electropolymerization, which allowed an additional layer of CP to be deposited on the surface. This sequential method was applied to both 2D films and 3D sponge-like silk scaffolds, producing conductive materials with biomimetic architectures. Overall, this two-step technique expanded the range of available polymers and dopants suitable for the synthesis of mechanically robust, biocompatible, and highly conductive silk-based materials.