Wearable pH sensors are useful tools in the healthcare and fitness industries, allowing consumers to access information related to their health in a convenient manner via the monitoring of body fluids. In this work, we tailored novel protein-textile composites to fluorescently respond to changing pH. To do so, we used amyloid curli fibers, a key component in the extracellular matrix of Escherichia coli, as genetic scaffold to fuse a pH-responsive fluorescent protein, pHuji. Engineered amyloids form macroscopic and environmentally resistant aggregates that we isolated to use as stand-alone hydrogel-based sensors, and that we trapped within textile matrices to create responsive biocomposites. We showed that these composites were mechanically robust and vapor-permeable, thus exhibiting favorable characteristics for wearable platforms. CsgA-pHuji fibers integrated in the textile allowed the final device to respond to pH changes and distinguish between alkaline and acidic solutions. We demonstrated that the resulting composites could sustain their fluorescence response over days, and that their sensing ability was reversible for at least 10 high/low pH cycles, highlighting their potential for continuous monitoring. Overall, we introduced a biosynthesized amyloid-based textile composite that could be used as biosensing patch for a variety of applications in the smart textile industry. Epidermal pH is an effective biomarker for preliminary detection of skin-related ailments such as dermatitis, acne and other bacterial and fungal infections 1. The pH of healthy skin is slightly acidic (pH 4-6.5) due to the presence of an 'acid mantle' , a protective barrier against harsh environmental stresses and invasive organisms 2. Low epidermal pH also promotes vital physiological processes in the skin, including but not limited to, antimicrobial defense, periodic skin differentiation and shedding 3. Monitoring changes in epidermal pH is therefore an essential aspect of skincare and dermatological diagnostics. Wearable sensors that can be directly mounted onto one's body to detect and respond to the physiological status of the wearer's skin are making diagnostic data more accessible 4. Irrespective of their final application, wearable devices are ideally designed to be flexible (in order to blend seamlessly with movements of the body), tunable (to detect diverse physiological signals) and biocompatible 5. However, most platforms for pH sensing currently employ electrodes or organic dyes to detect pH electrochemically or optically 6-9. Using electrodes limits the mechanical flexibility of the system, renders the device sensitive to background motion, and often requires multistep chemical functionalization processes 10. Dyes used in wearable sensors face a major issue of not being easily tunable-requiring complex chemical modifications to detect and bind new analytes. To prevent leaching out from sensors during use, devices often incorporate rigid substrates that are less likely to disintegrate in contact with solvents or diverse chem...

Poly­(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) is a highly conductive, easily processable, self-healing polymer. It has been shown to be useful in bioelectronic applications, for instance, as a biointerfacing layer for studying brain activity, in biosensitive transistors, and in wearable biosensors. A green and biofriendly method for improving the mechanical properties, biocompatibility, and stability of PEDOT:PSS involves mixing the polymer with a biopolymer. Via structural changes and interactions with PEDOT:PSS, biopolymers have the potential to improve the self-healing ability, flexibility, and electrical conductivity of the composite. In this work, we fabricated novel protein–polymer multifunctional composites by mixing PEDOT:PSS with genetically programmable amyloid curli fibers produced byEscherichia coli bacteria. Curli fibers are among the stiffest protein polymers and, once isolated from bacterial biofilms, can form plastic-like thin films that heal with the addition of water. Curli-PEDOT:PSS composites containing 60% curli fibers exhibited a conductivity 4.5-fold higher than that of pristine PEDOT:PSS. The curli fibers imbued the biocomposites with an immediate water-induced self-healing ability. Further, the addition of curli fibers lowered the Young’s and shear moduli of the composites, improving their compatibility for tissue-interfacing applications. Lastly, we showed that genetically engineered fluorescent curli fibers retained their ability to fluoresce within curli-PEDOT:PSS composites. Curli fibers thus allow to modulate a range of properties in conductive PEDOT:PSS composites, broadening the applications of this polymer in biointerfaces and bioelectronics.

Sweat is an increasingly popular biological medium for fitness monitoring and clinical diagnostics. It contains an abundance of biological information and is available continuously and noninvasively. Sweat-sensing devices often employ proteins in various capacities to create skin-friendly matrices that accurately extract valuable and time-sensitive information from sweat. Proteins were first used in sensors as biorecognition elements in the form of enzymes and antibodies, which are now being tuned to operate at ranges relevant for sweat. In addition, a range of structural proteins, sometimes assembled in conjunction with polymers, can provide flexible and compatible matrices for skin sensors. Other proteins also naturally possess a range of functionalitiesas adhesives, charge conductors, fluorescence emitters, and power generatorsthat can make them useful components in wearable devices. Here, we examine the four main components of wearable sweat sensorsthe biorecognition element, the transducer, the scaffold, and the adhesive and the roles that proteins have played so far, or promise to play in the future, in each component. On a case-by-case basis, we analyze the performance characteristics of existing protein-based devices, their applicable ranges of detection, their transduction mechanism and their mechanical properties. Thereby, we review and compare proteins that can readily be used in sweat sensors and others that will require further efforts to overcome design, stability or scalability challenges. Incorporating proteins in one or multiple components of sweat sensors could lead to the development and deployment of tunable, greener, and safer biosourced devices.

To address the increasing environmental footprint of the fast-growing textile industry, self-repairing textile composites have been developed to allow torn or damaged textiles to restore their morphological, mechanical, and functional features. A sustainable way to create these textile composites is to introduce a coating material that is biologically derived, biodegradable, and can be produced through scalable processes. Here, we fabricated self-repairing textile composites by integrating the biofilms of Escherichia coli (E. coli) bacteria into conventional knitted textiles. The major structural protein component in E. coli biofilm is a matrix of curli fibers, which has demonstrated extraordinary abilities to self-assemble into mechanically strong macroscopic structures and self-heal upon contact with water. We demonstrated the integration of biofilm through three simple, fast, and scalable methods: adsorption, doctor blading, and vacuum filtration. We confirmed that the composites were breathable and mechanically strong after the integration, with improved Young’s moduli or elongation at break depending on the fabrication method used. Through patching and welding, we showed that after rehydration, the composites made with all three methods effectively healed centimeter-scale defects. Upon observing that the biofilm strongly attached to the textiles by covering the extruding textile fibers from the self-repair failures, we proposed that the strength of the self-repairs relied on both the biofilm’s cohesion and the biofilm-textile adhesion. Considering that curli fibers are genetically-tunable, the fabrication of self-repairing curli-expressing biofilm-textile composites opens new venues for industrially manufacturing affordable, durable, and sustainable functional textiles.