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Phenylalanine ammonia-lyase (PAL) has gained attention in recent years for the treatment of phenylketonuria (PKU), a genetic disorder that affects ~1 in 15,000 individuals globally. However, the enzyme is easily degraded by proteases, unstable at room temperature, and is currently administered in PKU patients as daily subcutaneous injections. We report here the stabilization of the PAL from Anabaena variabilis, which is currently used to formulate pegvaliase, through incorporation in a silk fibroin matrix. The combination with silk stabilizes PAL at 37 °C. In addition, in vitro studies showed that inclusion in a silk matrix preserves the biological activity of the enzyme in simulated intestinal fluid, which will enable oral administration of PAL to treat PKU.

Biomaterial implants for the sustained delivery of therapeutics can be utilized to deliver drugs at near-constant rates over extended time frames to provide an alternative to daily oral medications. The biomaterials used to construct these systems, however, are often not bioresorbable and thus require a secondary surgery for removal from the body, and fabrication of these systems may require the use of harsh chemical solvents. To address these shortcomings, a fabrication process was developed to generate biodegradable drug reservoir systems from regenerated silk fibroin protein solution (23% w/v). The tubular systems, with an inner diameter of 2.0 mm and wall thickness < 250µm, were developed using an all-aqueous solution-gel-solid phase transition curing process. Two different clinically-relevant therapeutics were released at near-constant rates for 30 days (> 100µg/day). The protein secondary structure of the devices consisted of 40% crystalline beta sheet. Mechanically, radial compression (1mm/min) of unloaded systems demonstrated Young’s moduli similar to cancellous (spongy) bone (100 to 250 MPa) and the systems showed good recovery under cyclic compression (to 17.5% strain). The devices could be generated in complex shapes (e.g., hollow cylinders) via an additive molding process, offering the potential for drug delivery but also for broader applications in tissue engineering and diagnostics.

Cephalopods camouflage abilities arise from highly specialized chromatic elements in their skin, chromatophores, iridophores, and leucophores, that enable them to display complex and rapidly changing color patterns. Despite the extensive study of these chromatic elements in squid and cuttlefish, full characterization of their individual optical response is still elusive in the Octopus species. We present here detailed multispectral analysis and mapping of the Octopus bimaculoides skin that allows to precisely identify the spatial distribution of the animal’s pigmented and structural elements. The mutual interaction of chromatophores and iridophores is also characterized both in terms of spectral response and spatial localization. The spectral information obtained through this analysis helps to understand the complexity and behavior of these natural tissues while continuing to serve as an inspiration for the fabrication of advanced, chromatically adaptable materials.

Optical devices have been traditionally fabricated using materials whose chemical and physical properties are finely tuned to perform a specific, single, and often static function, whereby devices’ variability is achieved by design changes. Due to the integration of optical systems in multifunctional platforms, there is an increasing need for intrinsic dynamic behavior, such as devices built with materials whose optical response can be programmed to change by leveraging the material’s variability. Here, regenerated silk fibroin is presented as an enabler of devices with active optical response due to the protein’s intrinsic properties. Silk’s abilities to controllably change conformation, reversibly swell and shrink, and degrade in a programmable way affect the form and the response of the optical structure in which it is molded. Representative silk-based devices whose behavior depends on the silk variability are presented and discussed with a particular focus on structures that display reconfigurable, reversibly tunable and physically transient optical responses. Finally, new research directions are envisioned for silk-based optical materials and devices.

Bioinspired actuators with stimuli-responsive and deformable properties are being pursued in fields such as artificial tissues, medical devices and diagnostics, and intelligent biosensors. These applications require that actuator systems have biocompatibility, controlled deformability, biodegradability, mechanical durability, and stable reversibility. Herein, we report a bionic actuator system consisting of stimuli-responsive genetically engineered silk–elastin-like protein (SELP) hydrogels and wood-derived cellulose nanofibers (CNFs), which respond to temperature and ionic strength underwater by ecofriendly methods. Programmed site-selective actuation can be predicted and folded into three-dimensional (3D) origami-like shapes. The reversible deformation performance of the SELP/CNF actuators was quantified, and complex spatial transformations of multilayer actuators were demonstrated, including a biomimetic flower design with selective petal movements. Such actuators consisting entirely of biocompatible and biodegradable materials will offer an option toward constructing stimuli-responsive systems for in vivo biomedicine soft robotics and bionic research.

Recently, we have reported the preparation of a silk fibroin-supported Palladium catalyst (Pd/SF) and its use in the Suzuki-Miyaura cross-coupling of aryl iodides. Since its synthetic applicability and structural features are still far from being fully explored, a deeper investigation is reported here. Pd/SF is tested as a catalyst for the Suzuki-Miyaura and Ullmann coupling reactions of aryl chlorides, in HO/EtOH solvent mixture under atmospheric conditions. Starting from the analysis of the products of the Pd/SF promoted Ullmann reactions of poly-haloarenes, we can hypothesize the existence of catalytic pockets where monoatomic palladium species can form stable complexes with SF. To shed light on this hypothesis, Pd/SF is characterized by Wide-Angle X-ray Scattering (WAXS) analysis, which supports the supposition of catalytic pockets. Finally, using a computational model developed by Molecular Mechanic Energy Minimization we have estimated the dimension of the catalytic pocket of Pd/SF (about 15 Å), in good agreement with the experimental results.

Deformable Mirrors (DMs) have wide applications ranging from astronomical imaging to laser communications and vision science. However, they often require bulky multi-channel cables for delivering high power to their drive actuators. A low powered DM which is driven in a contactless fashion could provide a possible alternative to this problem.Here, we present a photo-magnetically actuated deformable mirror (PMADM) concept which is actuated in a contactless fashion by a permanent magnet and low power laser heating source. This paper presents the laboratory demonstration of prototype optical surface quality, magnetic control of focus, and COMSOL simulations of its precise photo-control. The PMADM prototype is made of a magnetic composite (polydimethylsiloxane [PDMS] + ferromagnetic $\text{CrO}_\text{2}$) and an optical-quality substrate layer and is 30.48 mm $\times$ 30.48 mm $\times$ 175 $\mu$ m in dimension with an optical pupil diameter of 8 mm. It deforms to 5.76 $\mu$ m when subjected to a 0.12 T magnetic flux density and relaxes to 3.76 $\mu$ m when illuminated by a 50 mW laser. A maximum stroke of 8.78 $\mu$ m before failure is also estimated considering a 3x safety factor. This works also includes simulation of astigmatism generation with the PMADM, a first step in demonstrating control of higher order modes. A fully developed PMADM can have potential application for wavefront corrections in vacuum and space environments., Comment: 19 pages, 18 figures

Embolization is a catheter-based minimally invasive procedure that deliberately occludes diseased blood vessels for treatment purposes. We report a novel silk based embolic material (SEM) that was developed and optimized to provide tandem integration of both embolization and the delivery of therapeutics. Natural silk was processed into fibroin proteins of varying lengths and combined with charged nanoclay particles to allow visibility and injectability using clinical catheters as small as 600 microns in diameter at lengths >100 cm. SEMs loaded with fluorochrome labeled bovine albumin and Nivolumab, which is among the most used immunotherapy drugs world-wide, demonstrated a sustained release profile in vitro over 28 days. In a porcine renal survival model, SEMs with labeled albumin and Nivolumab successfully embolized porcine arteries without recanalization and led to the delivery of both albumin and Nivolumab into the interstitial space of the renal cortex. Mechanistically, we show that tissue delivery is most optimal when the internal elastic membrane of the embolized artery is disrupted. SEM is a potential next-generation multifunctional embolic agent that can achieve embolization and deliver a wide range of therapeutics to treat vascular diseases including tumors. This article is protected by copyright. All rights reserved.

Bioinspired Biomaterials A silk cocoon is nestled within a mussel shell. Taking inspiration from the adhesive property of mussels and the assembly properties of silk materials new, water‐based, eco‐friendly glues with exceptional underwater adhesion performance can be formulated. More details can be found in article number 2004786 by Gianluca M. Farinola, Fiorenzo G. Omenetto, and co‐workers. [Image: see text]

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 ., pH‐responsive biomaterial‐based formulations based on fruit can be tuned to convert inert interfaces such as dental floss and highly absorbent paper points into devices for real‐time localized chemical mapping of the oral cavity. These can be extended to mouth‐conformable interfaces to acquire information on the health status of the user and for the design of point of care diagnostic devices.

Made available in DSpace on 2021-06-25T10:22:39Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-02-07 In optical biosensing, silk fibroin (SF) appears as a promising alternative where other materials, such as paper, find limitations. Besides its excellent optical properties and unmet capacity to stabilize biomacromolecules, SF in test strips exhibits additional functions,i.e.capillary pumping activity of 1.5 mm s−1, capacity to filter blood cells thanks to its small, but tuneable, porosity and enhanced biosensing sensitivity. The bulk functionalization of SF with the enzymes glucose oxidase and peroxidase and the mediator ABTS produces colourless and transparent SF films that respond to blood glucose increasing 2.5 times the sensitivity of conventional ABTS-based assays. This enhanced sensitivity results from the formation of SF-ABTS complexes, where SF becomes part of the bioassay. Additionally, SF films triple the durability of most stable cellulose-based sensors. Although demonstrated for glucose, SF microfluidic test strips may incorporate other optical bioassays,e.g.immunoassays, with the aim of transferring them from central laboratories to the place of patient's care. Instituto de Microelectrónica de Barcelona (IMB-CNM CSIC) São Carlos Institute of Physics University of São Paulo Departament de Química Universitat Autònoma de Barcelona Bellaterra (Barcelona) Instituto Murciano de Investigación y Desarrollo Agrario y Alimentario (IMIDA) Institute of Chemistry São Paulo State University (UNESP) Silklab Department of Biomedical Engineering Tufts University Department of Electrical and Computer Engineering Tufts University Department of Physics Tufts University Laboratory for Living Devices Tufts University Institute of Chemistry São Paulo State University (UNESP)

Wearable interfaces are central to multiple healthcare and wellness strategies encompassing diet and nutrition, personalized health monitoring, and performance optimization. Specifically, the advent of flexible electronic formats coupled with microfluidic interfaces has resulted in sophisticated conformal devices for biofluid sampling and quantification. Here, a complementary approach is presented to wearable sensing by using a large-scale, conformal, distributed format that relies on the use of biomaterial-based inks to print and stabilize deterministic patterns of biochemical reporters with high resolution. Colorimetric devices can vary in size and a sensing T-shirt based on a colorimetric pattern is developed to illustrate the utility that such formats can add to the wearable interface space. Image analysis allows parameter variation to be tracked in real-time, yielding a map-like format of distributed biophysical response.

Photoactive materials hold great promise for a variety of applications. We present a finite element model of light-controlled flexible magnetic composite structure composed of 33.3% Chromium dioxide (CrO2) and 66.7% Polydimethylsiloxane (PDMS) by weight. The structure has a dimension of 8 mm x 2 mm x 100 um and has been previously experimentally studied. Due to the low Curie temperature, the structure acts as an actuator, shows significant deflection under the external magnetic field and relaxation due to laser heating. Thermal and magnetic deflection analysis has been performed using the FEM model. The simulation results show a maximum structural deflection of 6.08 mm (76% of the length of the structure) when subjected to 30 mT magnetic flux density and 160 mW laser power at 303 K (room temperature). We will present the results of the simulation model and comparison to experimental data reproducing the previously observed motion of the (CrO2+PDMS). This model will enable future fracture and fatigue analysis as well as extension to new photoactive geometries., Comment: 12 pages, 10 figures, published in Proceedings Volume 11477, Molecular and Nano Machines III; 1147704 (2020), Event: SPIE Organic Photonics + Electronics, 2020, Online Only

The interaction between light and matter has been long explored, leading to insights based on the modulation and control of electrons and/or photons within a material. An opportunity exists in optomechanics, where the conversion of radiation into material strain and actuation is currently induced at the molecular level in liquid crystal systems, or at the microelectromechanical systems (MEMS) device scale, producing limited potential strain energy (or force) in light-driven systems. We present here flexible material composites that, when illuminated, are capable of macroscale motion, through the interplay of optically absorptive elements and low Curie temperature magnetic materials. These composites can be formed into films, sponges, monoliths, and hydrogels, and can be actuated with light at desired locations. Light-actuated elastomeric composites for gripping and releasing, heliotactic motion, light-driven propulsion, and rotation are demonstrated as examples of the versatility of this approach.

Freeform fabrication has emerged as a key direction in printing biologically-relevant materials and structures. With this emerging technology, complex structures with microscale resolution can be created in arbitrary geometries and without the limitations found in traditional bottom-up or top-down additive manufacturing methods. Recent advances in freeform printing have used the physical properties of microparticle-based granular gels as a medium for the submerged extrusion of bioinks. However, most of these techniques require post-processing or crosslinking for the removal of the printed structures (Miller et al., 2015; Jin et al., 2016) [1] , [2] . In this communication, we introduce a novel method for the one-step gelation of silk fibroin within a suspension of synthetic nanoclay (Laponite) and polyethylene glycol (PEG). Silk fibroin has been used as a biopolymer for bioprinting in several contexts, but chemical or enzymatic additives or bulking agents are needed to stabilize 3D structures. Our method requires no post-processing of printed structures and allows for in situ physical crosslinking of pure aqueous silk fibroin into arbitrary geometries produced through freeform 3D printing. Statement of Significance 3D bioprinting has emerged as a technology that can produce biologically relevant structures in defined geometries with microscale resolution. Techniques for fabrication of free-standing structures by printing into granular gel media has been demonstrated previously, however, these methods require crosslinking agents and post-processing steps on printed structures. Our method utilizes one-step gelation of silk fibroin within a suspension of synthetic nanoclay (Laponite), with no need for additional crosslinking compounds or post processing of the material. This new method allows for in situ physical crosslinking of pure aqueous silk fibroin into defined geometries produced through freeform 3D printing.

Conspicuous, colorful displays are often used by animals to communicate within and between species. Previously, researchers have manipulated specific components of color signals (i.e., hue, total reflectance, and/or chroma) using paints, photographs, videos, or filters. However, these manipulations may not adequately mimic the spectrum of color signals outside the range of human perception. Thus, these methods are inappropriate for organisms with unconventional visual systems, such as stomatopods (mantis shrimp). Here, we describe a novel application of a femtosecond laser to increase total reflectance of the stomatopod meral spot, a distinct area on the raptorial appendage used in territorial contests. Ultrafast lasers provide a programmable way to precisely manipulate patch total reflectance of live stomatopods without causing collateral damage. We tested how experimentally increasing meral spot reflectance impacted receiver behavior during territorial contests. Contests in which receiver stomatopods faced an opponent with a lightened meral spot were shorter and receivers showed increased rates of agonistic behaviors. This result suggests that lighter meral spots indicate lower fighting ability; thus, receivers are more willing to engage in a contest. This research provides the first demonstration that stomatopods can detect and assess achromatic variation in contests. Furthermore, we demonstrate that ultrafast lasers provide a powerful tool to investigate achromatic signaling, particularly for organisms whose size, aquatic habitat, or visual system otherwise prevent realistic alterations to color signals (e.g., butterflies, jumping spiders, or decapod crustaceans). This study advances our knowledge about stomatopod visual communication and offers a valuable tool for future research.

Transient implantable medical bionics offer great promise in the field of smart controlled release and tissue regeneration. On-board energy storage is the ideal power system to drive them. In this work, a critical component of such a device, a biodegradable polymer electrolyte (silk fibroin–choline nitrate) has been developed. The efficiency of this electrolyte is demonstrated when deployed in a biodegradable thin-film magnesium battery. The battery, encapsulated in silk, offers a specific capacity of 0.06 mAh cm–2. The enzymatic degradation of the whole device occurs over 45 days in the buffered protease XIV solution. A programmed battery lifetime can be achieved using silk protection layers. This battery system provides a new avenue for an on-board biodegradable power source for next-generation transient medical bionics.

We report simple, water-based fabrication methods based on protein self-assembly to generate 3D silk fibroin bulk materials that can be easily hybridized with water-soluble molecules to obtain multiple solid formats with predesigned functions. Controlling self-assembly leads to robust, machinable formats that exhibit thermoplastic behavior consenting material reshaping at the nanoscale, microscale, and macroscale. We illustrate the versatility of the approach by realizing demonstrator devices where large silk monoliths can be generated, polished, and reshaped into functional mechanical components that can be nanopatterned, embed optical function, heated on demand in response to infrared light, or can visualize mechanical failure through colorimetric chemistries embedded in the assembled (bulk) protein matrix. Finally, we show an enzyme-loaded solid mechanical part, illustrating the ability to incorporate biological function within the bulk material with possible utility for sustained release in robust, programmably shapeable mechanical formats.

Protein micro/nanopatterning has long provided sophisticated strategies for a wide range of applications including biointerfaces, tissue engineering, optics/photonics, and bioelectronics. We present here the use of regenerated silk fibroin to explore wrinkle formation by exploiting the structure-function relation of silk. This yields a biopolymer-based reversible, multiresponsive, dynamic wrinkling system based on the protein's responsiveness to external stimuli that allows on-demand tuning of surface morphologies and properties. The polymorphic transitions of silk fibroin enable modulation of the wrinkle patterns and, consequently, the material's physical properties. The interplay between silk protein chains and external stimuli enables control over the protein film's wrinkling dynamics. Thanks to the versatility of regenerated silk fibroin as a technological substrate, a number of demonstrator devices of varying utility are shown ranging from information encoding to modulation of optical transparency and thermal regulation.

Hierarchical molecular assembly directed by cell-regulated aqueous solvent is a fundamental strategy for manufacturing various proteinaceous structures that are of intense interest for nanotechnology, sustainable manufacturing and regenerative medicine. However, to translate the natural strategy into advanced digital manufacturing like three-dimensional (3D) printing remains a tremendous technical and theoretical challenge. This work presents a 3D printing technique of a particular protein, silk fibroin, by rationally designing an de novo aqueous salt bath capable of directing the hierarchical assembly of the protein molecules. This technique, conducted under aqueous and ambient conditions, results in 3D proteinaceous architectures characterized by intrinsic biocompatibility/biodegradability and remarkable mechanical performance. The versatility of this method is shown in a diversity of 3D shapes and a range of functional components integrated into the 3D prints. Exceptional manufacturing capability and one promising application is exemplified by the single-step construction of perfusable microfluidic chips, also an analogy of small-diameter vascular grafts, which eliminates the use of supporting or sacrificial materials owing to optimized crosslinking dynamics and compartmentalized printing parameters. The 3D shaping capability of the protein material can benefit a multitude of biomedical devices, from drug delivery to surgical implants to tissue scaffolds.

Hierarchical molecular assembly is a fundamental strategy for manufacturing protein structures in nature. However, to translate this natural strategy into advanced digital manufacturing like three-dimensional (3D) printing remains a technical challenge. This work presents a 3D printing technique with silk fibroin to address this challenge, by rationally designing an aqueous salt bath capable of directing the hierarchical assembly of the protein molecules. This technique, conducted under aqueous and ambient conditions, results in 3D proteinaceous architectures characterized by intrinsic biocompatibility/biodegradability and robust mechanical features. The versatility of this method is shown in a diversity of 3D shapes and a range of functional components integrated into the 3D prints. The manufacturing capability is exemplified by the single-step construction of perfusable microfluidic chips which eliminates the use of supporting or sacrificial materials. The 3D shaping capability of the protein material can benefit a multitude of biomedical devices, from drug delivery to surgical implants to tissue scaffolds. This work also provides insights into the recapitulation of solvent-directed hierarchical molecular assembly for artificial manufacturing.

Patterning of photonic crystals to generate rationally designed color-responsive materials has drawn considerable interest because of promising applications in optical storage, encryption, display, and sensing. Here, an inkjet-printing based strategy is presented for noncontact, rapid, and direct approaches to generate arbitrarily patterned photonic crystals. The strategy is based on the use of water-soluble biopolymer-based opal structures that can be reformed with high resolution through precise deposition of fluids on the photonic crystal lattice. The resulting digitally designed photonic lattice formats simultaneously exploit structural color and material transience opening avenues for information encoding and combining functions of optics, biomaterials, and environmental interfaces in a single device.

Biomaterial composites based on reformulated silk protein offer new routes for tough and strong, environmentally friendly leather-like materials. We present here silk-based biomaterial formulations that are scalable, amenable to digital manufacturing, thus enabling a wide variety of formats, and offering new pathways to sustainable production. Performance is tuned by controlling silk protein conformations at the molecular scale, by introducing other biomaterials and natural additives, and by computerized fabrication providing programmable layering and non-regular geometrical patterning. The resulting materials display strong, soft, pliable, durable, and biodegradable features. Further, these leather-like blends can be augmented by embedding and stabilizing active molecules for sensing of the environment surrounding them.

Regenerated silk fibroin is a high molecular weight protein obtained by purifying the cocoons of the domesticated silkworm, Bombyx mori. This report exploits the aqueous processing and tunable β sheet secondary structure of regenerated silk to produce nanostructures (i.e., inverse opals) that can be used as colorimetric immunosensors. Such sensors would enable direct detection of antigens by changes in reflectance spectra induced by binding events within the nanostructure. Silk inverse opals were prepared by solution casting and annealing in a humidified atmosphere to render the silk insoluble. Next, antigen sensing capabilities were imparted to silk through a three step synthesis: coupling of avidin to silk surfaces, coupling of biotin to antibodies, and lastly antibody attachment to silk through avidin-biotin interactions. Varying the antibody enables detection of different antigens, as demonstrated using different protein antigens: antibodies, red fluorescent protein, and the beta subunit of cholera toxin. Antigen binding to sensors induces a red shift in the opal reflectance spectra, while sensors not exposed to antigen showed either no shift or a slight blue shift. This work constitutes a first step for the design of biopolymer-based optical systems that could directly detect antigens using commercially available reagents and environmentally friendly chemistries.

Advanced personalized medical diagnostics depend on the availability of high-quality biological samples. These are typically biofluids, such as blood, saliva, or urine; and their collection and storage is critical to obtain reliable results. Without proper temperature regulation, protein biomarkers in particular can degrade rapidly in blood samples, an effect that ultimately compromises the quality and reliability of laboratory tests. Here, we present the use of silk fibroin as a solid matrix to encapsulate blood analytes, protecting them from thermally induced damage that could be encountered during nonrefrigerated transportation or freeze-thaw cycles. Blood samples are recovered by simple dissolution of the silk matrix in water. This process is demonstrated to be compatible with a number of immunoassays and provides enhanced sample preservation in comparison with traditional air-drying paper approaches. Additional processing can remediate interactions with conformational structures of the silk protein to further enhance blood stabilization and recovery. This approach can provide expanded utility for remote collection of blood and other biospecimens empowering new modalities of temperature-independent remote diagnostics.

Chloroplasts extracted from spinach leaves were entrapped in B. mori silk fibroin films to investigate the maintenance of their photosynthetic activity in a dry environment. Chloroplast stability was studied under various storage conditions (different temperature and light cycles) using electron microscopy, spectroscopic analysis and measuring of their photosynthetic activity (i.e. oxygen production). When compared to other environments previously investigated, silk fibroin films enhanced the preservation of the chloroplasts' photosynthetic activity.

Quantifying the deformation of biological tissues under mechanical loading is crucial to understand its biomechanical response in physiological conditions and important for designing materials and treatments for biomedical applications. However, strain measurements for biological tissues subjected to large deformations and humid environments are challenging for conventional methods due to several limitations such as strain range, boundary conditions, surface bonding and biocompatibility. Here we propose the use of silk solutions and printing to synthesize prototype strain gauges for large strain measurements in biological tissues. The study shows that silk-based strain gauges can be stretched up to 1300% without failure, which is more than two orders of magnitude larger than conventional strain gauges, and the mechanics can be tuned by adjusting ion content. We demonstrate that the printing approach can accurately provide well bonded fluorescent features on the silk membranes using designs which can accurately measure strain in the membrane. The results show that these new strain gauges measure large deformations in the materials by eliminating the effects of sliding from the boundaries, making the measurements more accurate than direct outputs from tensile machines., United States. National Institutes of Health (U01 EB014976), United States. Office of Naval Research (N000141010562), United States. Air Force Office of Scientific Research (FA9550-11-1-019)

We report that pure silk fibroin can be a green and biofunctional photoresist for deep ultraviolet photolithography. All processes are entirely water-based, from resist solvent to resist removal, and rely on the phototendering effect that decreases the crystallinity of silk fibroin films by DUV exposure. Additionally, the potential decrease in activity of bio-dopants due to high-energy irradiation is irrelevant to our positive-tone lithographic method.

Biomolecular proton conducting materials have been touted as promising for seamlessly and directly interfacing natural biological systems with traditional artificial electronics. As such, proton conduction has been explored for a variety of protein- and polypeptide-based materials. Within this context, cephalopod structural proteins called reflectins have demonstrated several favorable properties, including outstanding electrical figures of merit as proton conductors and intrinsic biocompatibility with cellular systems. However, the processing of reflectins into films has typically used low-throughput material-intensive strategies and has often required organic solvents. Herein, we report the preparation of devices from active layers fabricated via inkjet printing of reflectin solubilized in water and the systematic evaluation of their electrical performance. Taken together, our findings represent a step forward in the manufacturing and development of unconventional bioelectronic platforms from the reflectin family of proteins.

Inkjet printing is an attractive bottom-up microfabrication technology owing to its simplicity, ease of use, and low cost. This method is particularly suitable for patterning of biomaterials because biofunctionality and bioactivity can be preserved during the patterning process in the absence of harsh conditions such as heat, UV radiation, and plasma. However, it is still challenging to apply this technology to biomaterial-based soft photonics, which requires precise control over morphology and uniformity to confine photons efficiently. This study introduces inkjet printing to create silk protein patterns to emit/guide a single-mode distributed feedback (DFB) laser on a single platform. A thin TiO2 coated grating enables coherent feedback of the generated photons for any shape of the printed silk pattern. The lasing wavelength can be adjusted by adding gold nanoparticles to the silk/dye ink. Photonic components of lasers and waveguides are drawn on a DFB board, and the lasing light can be extracted through adjacent waveguides. The printed components can be reformed by post modification (water-removal and reprinting). Additionally, optically absorptive melanin nanoparticles placed on the waveguide can attenuate the propagating light, thus adding utility for sensing applications. This allows a new method to fabricate cost-effective, easily functionalized, and versatile biomaterial photonic chips for advanced sensing and diagnosis.

Naturally occurring iridescent systems produce brilliant color displays through multiscale, hierarchical assembly of structures that combine reflective, diffractive, diffusive, or absorbing domains. The fabrication of biopolymer-based, hierarchical 3D photonic crystals through the use of a topographical templating strategy that allows combined optical effects derived from the interplay of predesigned 2D and 3D geometries is reported here. This biomaterials-based approach generates 2D diffractive optics composed of 3D nanophotonic lattices that allow simultaneous control over the reflection (through the 3D photonic bandgap) and the transmission (through 2D diffractive structuring) of light with the additional utility of being constituted by a biocompatible, implantable, edible commodity textile material. The use of biopolymers allows additional degrees of freedom in photonic bandgap design through directed protein conformation modulation. Demonstrator structures are presented to illustrate the lattice multifunctionality, including tunable diffractive properties, increased angle of view of photonic crystals, color-mixing, and sensing applications.

Silks are natural fibrous protein polymers that are spun by silkworms and spiders. Among silk variants, there has been increasing interest devoted to the silkworm silk of B. mori, due to its availability in large quantities along with its unique material properties. Silk fibroin can be extracted from the cocoons of the B. mori silkworm and combined synergistically with other biomaterials to form biopolymer composites. With the development of recombinant DNA technology, silks can also be rationally designed and synthesized via genetic control. Silk proteins can be processed in aqueous environments into various material formats including films, sponges, electrospun mats and hydrogels. The versatility and sustainability of silk-based materials provides an impressive toolbox for tailoring materials to meet specific applications via eco-friendly approaches. Historically, silkworm silk has been used by the textile industry for thousands of years due to its excellent physical properties, such as lightweight, high mechanical strength, flexibility, and luster. Recently, due to these properties, along with its biocompatibility, biodegradability and non-immunogenicity, silkworm silk has become a candidate for biomedical utility. Further, the FDA has approved silk medical devices for sutures and as a support structure during reconstructive surgery. With increasing needs for implantable and degradable devices, silkworm silk has attracted interest for electronics, photonics for implantable yet degradable medical devices, along with a broader range of utility in different device applications. This Tutorial review summarizes and highlights recent advances in the use of silk-based materials in bio-nanotechnology, with a focus on the fabrication and functionalization methods for in vitro and in vivo applications in the field of tissue engineering, degradable devices and controlled release systems.

Structural color in naturally occurring systems is generally constituted by nanoscale lattices of biopolymers that generate beautiful iridescences through their regular structures, often interspersed with defects or period mismatch. Taking inspiration from both formats and materials found in Nature, a series of large-scale, highly reflective biopolymer-based photonic crystal superlattices constituted by stacking layers of 3D nanoscale lattices with different periodicity is presented. These silk photonic crystal superlattices (SPCSs) are fully composed of naturally derived structural proteins (silk fibroin) and exhibit brilliant structural color while being mechanically flexible. Multi-stopbands over broad wavelength ranges or single-stopbands with narrowband spectral responses can be readily realized and precisely controlled by manipulating the hierarchy of the lattice stacks or the repetition periods of the assembled colloidal monolayers. The unique ability to vary the silk protein conformation allows to vary the lattice and controllably “design” the iridescences of the SPCSs with water vapor adding versatility to this biopolymer-based photonic structure.

Light-induced material phase transitions enable the formation of shapes and patterns from the nano- to the macroscale. From lithographic techniques that enable high-density silicon circuit integration, to laser cutting and welding, light-matter interactions are pervasive in everyday materials fabrication and transformation. These noncontact patterning techniques are ideally suited to reshape soft materials of biological relevance. We present here the use of relatively low-energy (< 2 nJ) ultrafast laser pulses to generate 2D and 3D multiscale patterns in soft silk protein hydrogels without exogenous or chemical cross-linkers. We find that high-resolution features can be generated within bulk hydrogels through nearly 1 cm of material, which is 1.5 orders of magnitude deeper than other biocompatible materials. Examples illustrating the materials, results, and the performance of the machined geometries in vitro and in vivo are presented to demonstrate the versatility of the approach.

Various techniques have been employed to entrap fragrant oils within microcapsules or microparticles in the food, pharmaceutical, and chemical industries for improved stability and delivery. In the present work we describe the use of silk protein microparticles for encapsulating fragrant oils using ambient processing conditions to form an all-natural biocompatible matrix. These microparticles are stabilized via physical crosslinking, requiring no chemical agents, and are prepared with aqueous and ambient processing conditions using polyvinyl alcohol-silk emulsions. The particles were loaded with fragrant oils via direct immersion of the silk particles within an oil bath. The oil-containing microparticles were coated using alternating silk and polyethylene oxide layers to control the release of the oil from the microspheres. Particle morphology and size, oil loading capacity, release rates as well as silk-oil interactions and coating treatments were characterized. Thermal analysis demonstrated that the silk coatings can be tuned to alter both retention and release profiles of the encapsulated fragrance. These oil containing particles demonstrate the ability to adsorb and controllably release oils, suggesting a range of potential applications including cosmetic and fragrance utility.

A wafer‐scale high resolution patterning of bio‐microstructures is achieved using precise protein photolithography. In article number 1700191, the application of these micropatterned structures as cellular substrate for the successful spatial guidance of fetal neural stems cells using well‐defined silk fibroin light chain as the resist material is demonstrated by Tiger H. Tao and co‐workers.