Shape‐Memory Microfluidics

Materials with embedded vascular networks afford rapid and enhanced control over bulk material properties including thermoregulation and distribution of active compounds such as healing agents or stimuli. Vascularized materials have a wide range of potential applications in self‐healing systems and tissue engineering constructs. Here, the application of vascularized materials for accelerated phase transitions in stimuli‐responsive microfluidic networks is reported. Poly(ester amide) elastomers are hygroscopic and exhibit thermo‐mechanical properties (T_g ≈ 37 °C) that enable heating or hydration to be used as stimuli to induce glassy‐rubbery transitions. Hydration‐dependent elasticity serves as the basis for stimuli‐responsive shape‐memory microfluidic networks. Recovery kinetics in shape‐memory microfluidics are measured under several operating modes. Perfusion‐assisted delivery of stimulus to the bulk volume of shape‐memory microfluidics dramatically accelerates shape recovery kinetics compared to devices that are not perfused. The recovery times are 4.2 ± 0.1 h and 8.0 ± 0.3 h in the perfused and non‐perfused cases, respectively. The recovery kinetics of the shape‐memory microfluidic devices operating in various modes of stimuli delivery can be accurately predicted through finite element simulations. This work demonstrates the utility of vascularized materials as a strategy to reduce the characteristic length scale for diffusion, thereby accelerating the actuation of stimuli‐responsive bulk materials.     

pH‐Responsive Round‐Way Motions of a Smart Device through Integrating Two Types of Chemical Actuators in One Smart System

Smart motions of objects from the submicrometer to millimeter scale through chemical control with stimulus‐responsive way are significant to achieve various applications. However, the intelligence of the current devices with chemical responding system remains to be improved; especially, achieving a round‐way motion is still a challenge. Therefore, two types of actuators are simultaneously integrated into single smart device at the opposite ends to achieve cooperated functions in an orderly manner. One actuator is the pH‐responsive power supply of hydrogen bubbles produced from the reaction between magnesium and HCl. The smart device undergoes on–off–on locomotion through control over the solution pH values by using the pH‐responsive actuator of magnesium–HCl system. The other actuator is the hydrogen peroxide‐responsive system of oxygen bubbles generated through the decomposition of hydrogen peroxide catalyzed by platinum aggregates. When introducing hydrogen peroxide solution into the system, the generated oxygen bubbles at the opposite end of the device to push the device backward for round‐way motions. For the first time, two different types of actuators are simultaneously integrated into single smart device without disturbing each other, which realize pH‐responsive round‐way motions of the smart device and improve the system intelligence for further applications.     

Lithium Tin Sulfide—a High‐Refractive‐Index 2D Material for Humidity‐Responsive Photonic Crystals

Extending the portfolio of novel stimuli‐responsive, high‐refractive‐index (RI) materials besides titania is key to improve the optical quality and sensing performance of existing photonic devices. Herein, lithium tin sulfide (LTS) nanosheets are introduced as a novel solution processable ultrahigh RI material (n = 2.50), which can be casted into homogeneous thin films using wet‐chemical deposition methods. Owing to its 2D morphology, thin films of LTS nanosheets are able to swell in response to changes of relative humidity. Integration of LTS nanosheets into Bragg stacks (BSs) based on TiO₂, SiO₂, nanoparticles or H₃Sb₃P₂O₁₄ nanosheets affords multilayer systems with high optical quality at an extremely low device thickness of below 1 µm. Owing to the ultrahigh RI of LTS nanosheets and the high transparency of the thin films, BSs based on porous titania as the low‐RI material are realized for the first time, showing potential application in light‐managing devices. Moreover, the highest RI contrast ever realized in BSs based on SiO₂ and LTS nanosheets is reported. Finally, exceptional swelling capability of an all‐nanosheet BS based on LTS and H₃Sb₃P₂O₁₄ nanosheets is demonstrated, which bodes well for a new generation of humidity sensors with extremely high sensitivity.     

Protein/Polymer‐Based Dual‐Responsive Gold Nanoparticles with pH‐Dependent Thermal Sensitivity

This article presents the synthesis and physicochemical behavior of dual‐responsive plasmonic nanoparticles with reversible optical properties based on protein‐coated gold nanoparticles grafted with thermosensitive polymer brushes by means of surface‐initiated atom transfer radical polymerization (SI‐ATRP) that exhibit pH‐dependent thermo‐responsive behavior. Spherical gold NPs of two different sizes (15 nm and 60 nm) and with different stabilizing agents (citrate and cetyltrimethylammonium bromide (CTAB), respectively) were first capped with bovine serum albumin (BSA). The resulting BSA‐capped NPs (Au@BSA NPs) exhibited not only extremely high colloidal stability under physiological conditions, but also a reversible U‐shaped pH‐responsive behavior, similar to pure BSA. The ?‐amine of the L‐lysine in the protein coating was then used to covalently bind an ATRP‐initiator, allowing for the SI‐ATRP of thermosensitive polymer brushes of oligo(ethylene glycol) methacrylates with an LCST of 42 °C in pure water and around 37 °C under physiological conditions. Such protein coated nanoparticles grafted with thermosensitive polymers exhibit a smart pH‐dependent thermosensitive behavior.     

Solvent‐Resistant PDMS Microfluidic Devices with Hybrid Inorganic/Organic Polymer Coatings

This study presents a method for the fabrication of solvent‐resistant poly(dimethylsiloxane) (PDMS) microfluidic devices by coating the microfluidic channel with a hybrid inorganic/organic polymer (HR4). This modification dramatically increases the resistance of PDMS microfluidic channels to various solvents, because it leads to a significant reduction in the rate of solvent absorption and consequent swelling. The compatibility of modified PDMS with a wide range of solvents is investigated by evaluating the swelling ratio measured through weight changes in a standard block. The HR4‐modified PDMS microfluidic device can be applied to the formation of water‐in‐oil (W/O) and oil‐in‐water (O/W) emulsions. The generation of organic solvent droplets with high monodispersity in the microfluidic device without swelling problems is demonstrated. The advantage of this proposed method is that it can be used to rapidly fabricate microfluidic devices using the bulk properties of PDMS, while also increasing their resistance to various organic solvents. This high compatibility with a variety of solvents of HR4‐modified PDMS can expand the application of microfluidic systems to many research fields.     

Recombinant Spider Silk as Mediator for One‐Step,Chemical‐Free Surface Biofunctionalization

A unique strategy for effective, versatile, and facile surface biofunctionalization employing a recombinant spider silk protein genetically functionalized with the antibody‐binding Z domain (Z‐4RepCT) is reported. It is demonstrated that Z‐silk can be applied to a variety of materials and platform designs as a truly one‐step and chemical‐free surface modification that site specifically captures antibodies while simultaneously reducing nonspecific adsorption. As a model surface, SiO₂ is used to optimize and characterize Z‐silk performance compared to the Z domain immobilized by a standard silanization method. First, Z‐silk adsorption is investigated and verified its biofunctionality in a long‐term stability experiment. To assess the binding capacity and protein–protein interaction stability of Z‐silk, the coating is used to capture human antibodies in various assay formats. An eightfold higher binding capacity and 40‐fold lower detection limit are obtained in the immunofluorescence assay, and the complex stability of captured antibodies is shown to be improved by a factor of 20. Applicability of Z‐silk to functionalize microfluidic devices is demonstrated by antibody detection in an electrokinetic microcapillary biosensor. To test Z‐silk for biomarker applications, real‐time detection and quantification of human immunoglobulin G are performed in a plasma sample and C1q capture from human serum using an anti‐C1q antibody.     

Color Tunable Poly (N‐Isopropylacrylamide)‐co‐Acrylic Acid Microgel–Au Hybrid Assemblies

A new class of materials that are capable of color tunability over 300 nm with a 15 °C temperature change is introduced. The materials are assembled from thermoresponsive poly (N‐isopropylacrylamide)‐co‐acrylic acid (pNIPAm‐co‐AAc) microgels, which are deposited on Au coated glass substrates. The films are also pH responsive; the temperature‐induced color change was suppressed at high pH and is consistent with the behavior of a solution of suspended microgels. The mechanism proposed to account for the observed optical properties suggests that they result from the two Au layers being separated from each other by the “monolithic” microgel film, much like a Fabry‐Pérot etalon or interferometer. It is the modulation of the distance between these two layers, facilitated by the microgel collapse transition at high temperature, that allows the color to be tuned. The sensitivity of the system presented here will be used for future sensing and biosensing applications, as well as for light filtering applications.     

A pH‐Responsive Gating Membrane System with Pumping Effects for Improved Controlled Release

In this study, we report on a novel composite membrane system for pH‐responsive controlled release, which is composed of a porous membrane with linear grafted, positively pH‐responsive polymeric gates acting as functional valves, and a crosslinked, negatively pH‐responsive hydrogel inside the reservoir working as a functional pumping element. The proposed system features a large responsive release rate that goes effectively beyond the limit of concentration‐driven diffusion due to the pumping effects of the negatively pH‐responsive hydrogel inside the reservoir. The pH‐responsive gating membranes were prepared by grafting poly(methacrylic acid) (PMAA) linear chains onto porous polyvinylidene fluoride (PVDF) membrane substrates using a plasma‐graft pore‐filling polymerization, and the crosslinked poly(N,N‐dimethylaminoethyl methacrylate) (PDM) hydrogels were synthesized by free radical polymerization. The volume phase‐transition characteristics of PMAA and PDM were opposite. The proposed system opens new doors for pH‐responsive “smart” or “intelligent” controlled‐release systems, which are highly attractive for drug‐delivery systems, chemical carriers, sensors, and so on.     

Glucose‐Responsive Bioinorganic Nanohybrid Membrane for Self‐Regulated Insulin Release

A bioinorganic nanohybrid glucose‐responsive membrane is developed for self‐regulated insulin delivery analogous to a healthy human pancreas. The application of MnO₂ nanoparticles as a multifunctional component in a glucose‐responsive, protein‐based membrane with embedded pH‐responsive hydrogel nanoparticles is proposed. The bio‐nanohybrid membrane is prepared by crosslinking bovine serum albumin (BSA)–MnO₂ nanoparticle conjugates with glucose oxidase and catalase in the presence of poly(N‐isopropyl acrylamide‐co‐methacrylic acid) nanoparticles. The preparation and performance of this new nanocomposite material for a glucose‐responsive insulin release system is presented. The activity and stability of immobilized glucose oxidase and the morphology and mechanical properties of the membrane are investigated. The enzymatic activity is well preserved in the membranes. The use of MnO₂ nanoparticles not only reinforces the mechanical strength and the porous structure of the BSA‐based membrane, but enhances the long‐term stability of the enzymes. The in vitro release of insulin across the membrane is modulated by changes in glucose concentration mimicking possible fluctuations of blood‐glucose level in diabetic patients. A four‐fold increase in insulin permeation is observed when the glucose concentration is increased from normal to hyperglycemic levels, which returns to the baseline level when the glucose concentration is reduced to a normal level.     

Double Stimuli‐Responsive Isoporous Membranes via Post‐Modification of pH‐Sensitive Self‐Assembled Diblock Copolymer Membranes

Double stimuli‐responsive membranes are prepared by modification of pH‐sensitive integral asymmetric polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer membranes with temperature‐responsive poly(N‐isopropylacrylamide) (pNIPAM) by a surface linking reaction. PS‐b‐P4VP membranes are first functionalized with a mild mussel‐inspired polydopamine coating and then reacted via Michael addition with an amine‐terminated pNIPAM‐NH₂ under slightly basic conditions. The membranes are thoroughly characterized by nuclear magnetic resonance (¹H‐NMR), Fourier transform infrared spectroscopy and X‐ray‐induced photoelectron spectroscopy. Additionally dynamic contact angle measurements are performed comparing the sinking rate of water droplets at different temperatures. The pH‐ and thermo‐double sensitivities of the modified membranes are proven by determining the water flux under different temperature and pH conditions.     

High Throughput Screening of Dynamic Silk‐Elastin‐Like Protein Biomaterials

The need for dynamic, elastomeric polymeric biomaterials remains high, with few options with tunable control of mechanical properties, and environmental responses. Yet the diversity of these types of protein polymers pursued for biomaterials‐related needs remains limited. Robust high‐throughput synthesis and characterization methods will address the need to expand options for protein‐polymers for a range of applications. Here, a combinatorial library approach with high throughput screening is used to select specific examples of dynamic protein silk‐elastin‐like polypeptides (SELPs) with unique stimuli responsive features, including tensile strength and adhesion. Using this approach, 64 different SELPs with different sequences and molecular weights are selected out of over 2000 recombinant E. coli colonies. New understanding of sequence‐function relationships with this family of proteins is gained through this combinatorial‐screening approach and can provide a guide to future library designs. Further, this approach yields new families of SELPs to match specific material functions.     

Self‐Supporting,Double Stimuli‐Responsive Porous Membranes From Polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) Diblock Copolymers

Asymmetric membranes are prepared via the non‐solvent‐induced phase separation (NIPS) process from a polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) (PS‐b‐PDMAEMA) block copolymer. The polymer is prepared via sequential living anionic polymerization. Membrane surface and volume structures are characterized by scanning electron microscopy. Due to their asymmetric character, resulting in a thin separation layer with pores below 100 nm on top and a macroporous volume structure, the membranes are self‐supporting. Furthermore, they exhibit a defect‐free surface over several 100 µm². Polystyrene serves as the membrane matrix, whereas the pH‐ and temperature‐sensitive minority block, PDMAEMA, renders the material double stimuli‐responsive. Therefore, in terms of water flux, the membranes are able to react on two independently applicable stimuli, pH and temperature. Compared to the conditions where the lowest water flux is obtained, low temperature and pH, activation of both triggers results in a seven‐fold permeability increase. The pore size distribution and the separation properties of the obtained membranes were tested through the pH‐dependent filtration of silica particles with sizes of 12–100 nm.     

Monodisperse Thermoresponsive Microgels with Tunable Volume‐Phase Transition Kinetics

A facile method to control the volume‐phase transition kinetics of thermo‐sensitive poly(N‐isopropylacrylamide) (PNIPAM) microgels is presented. Monodisperse PNIPAM microgels with spherical voids are prepared using a microfluidic device. The swelling and shrinking responses of these microgels with spherical voids to changes in temperature are compared with those of voidless microgels of the same size and chemical composition prepared using the same microfluidic device. It is shown that the PNIPAM microgels with voids respond faster to changes in temperature as compared with their voidless counterparts. Also, the induced void structure does not have a detrimental effect on the equilibrium volume change of the microgels. Thus, the volume phase transition kinetics of the microgels can be finely tuned by controlling the number and size of the voids. The flexibility, control, and simplicity in fabrication rendered by this approach make these microgels appealing for applications that range from drug delivery systems and chemical separations to chemical/biosensing and actuators.     

Antibiotic‐Releasing Silk Biomaterials for Infection Prevention and Treatment

Effective treatment of infections in avascular and necrotic tissues can be challenging due to limited penetration into the target tissue and systemic toxicities. Controlled‐release polymer implants have the potential to achieve the high local concentrations needed while also minimizing systemic exposure. Silk biomaterials possess unique characteristics for antibiotic delivery, including biocompatibility, tunable biodegradation, stabilizing effects, water‐based processing, and diverse material formats. The functional release of antibiotics spanning a range of chemical properties from different material formats of silk (films, microspheres, hydrogels, coatings) is reported. The release of penicillin and ampicillin from bulk‐loaded silk films, drug‐loaded silk microspheres suspended in silk hydrogels and bulk‐loaded silk hydrogels is investigated and the in vivo efficacy of the ampicillin‐releasing silk hydrogels is demonstrated in a murine infected‐wound model. Silk sponges with nanofilm coatings are loaded with gentamicin and cefazolin, and release is sustained for 5 and 3 days, respectively. The capability of silk antibiotic carriers to sequester, stabilize, and then release bioactive antibiotics represents a major advantage over implants and pumps based on liquid drug reservoirs, where instability at room or body temperature is limiting. The present studies demonstrate that silk biomaterials represent a novel, customizable antibiotic platform for focal delivery of antibiotics using a range of material formats (injectable to implantable).     

pH‐Responsive Catalytic Janus Motors with Autonomous Navigation and Cargo‐Release Functions

The fabrication of multifunctional polymeric Janus colloids that display catalytically driven propulsion, change their size in response to local variations in pH, and vary cargo release rate is demonstrated. Systematic investigation of the colloidal trajectories reveals that in acidic environments the propulsion velocity reduces dramatically due to colloid swelling. This leads to a chemotaxis‐like accumulation for ensembles of these responsive particles in low‐pH regions. In synergy with this chemically defined accumulation, the colloids also show an enhancement in the release rate of an encapsulated cargo molecule. Together, these effects result in a strategy to harness catalytic propulsion for combined autonomous transport and cargo release directed by a chemical stimulus, displaying a greater than 30 times local cargo‐accumulation enhancement. Lactic acid can be used as the stimulus for this behavior, an acid produced by some tumors, suggesting possible eventual utility as a drug‐delivery method. Applications for microfluidic transport are also discussed.     

A Natural Silk Fibroin Protein‐Based Transparent Bio‐Memristor

The recent discovery of nanoelectronics memristor devices has opened up a new wave of enthusiasm and optimism in revolutionizing electronic circuit design, marking the beginning of new era for the advancement of neuromorphic, high‐density logic and memory applications. Here a highly non‐linear dynamic response of a bio‐memristor is demonstrated using natural silk cocoon fibroin protein of silkworm, Bombyx mori. A film that is transparent across most of the visible spectrum is obtained with the electronic‐grade silk fibroin aqueous solution of ca. 2% (wt/v). Bipolar memristive switching is demonstrated; the switching mechanism is confirmed to be the filamentary switching as observed by probing local conduction behavior at nanoscale using scanning tunneling microscopy. The memristive transition is elucidated by a physical model based on the carrier trapping or detrapping in silk fibroin films and this appears to be due to oxidation and reduction procedures, as evidenced from cyclic voltammetry measurements. Hence, silk fibroin protein could be used as a biomaterial for bio‐memristor devices for applications in advanced bio‐inspired very large scale integration circuit design as well as in biologically inspired synapse links for energy‐efficient neuromorphic computing.     

Electrochemically Triggered Selective Adsorption of Biotemplated Nanoparticles on Self‐Assembled Organometallic Diblock Copolymer Thin Films

The controlled adsorption of the iron‐containing cage protein ferritin at the nanoscale using stimuli‐responsive self‐assembled diblock copolymer thin‐film templates is reported. The diblock copolymer used study consists of a cylinder‐forming polystyrene‐block‐polyferrocenylsilane (PS‐b‐PFS), with PFS as the minor block, and shows reversible redox properties. To prevent any spontaneous protein adsorption on either block, the electrolyte pH is selected to leave the ferritin negatively charged, and the protein concentration and solution ionic strength are carefully tuned. Selective adsorption of ferritin on the PFS domains of the self‐assembled thin films is then triggered in situ by applying a positive potential, simultaneously oxidizing the PFS and attracting the ferritin electrostatically.     

Silk as a Multifunctional Biomaterial Substrate for Reduced Glial Scarring around Brain‐Penetrating Electrodes

The reliability of chronic, brain‐penetrating electrodes must be improved for these ‐neural recording technologies to be viable in widespread clinical applications. One approach to improving electrode reliability is to reduce the foreign body response at the probe‐tissue interface. In this work, silk fibroin is investigated as a candidate material for fabricating mechanically dynamic neural probes with enhanced biocompatibility compared to traditional electrode materials. Silk coatings are applied to flexible cortical electrodes to produce devices that transition from stiff to flexible upon hydration. Theoretical modeling and in vitro testing show that the silk coatings impart mechanical properties sufficient for the electrodes to penetrate brain tissue. Further, it is demonstrated that silk coatings may reduce some markers of gliosis in an in vitro model and that silk can encapsulate and release the gliosis‐modifying enzyme chondroitinase ABC. This work establishes a basis for future in vivo studies of silk‐based brain‐penetrating electrodes, as well as the use of silk materials for other applications in the central nervous system where gliosis must be controlled.     

Dynamically Actuated Liquid‐Infused Poroelastic Film with Precise Control over Droplet Dynamics

Traditional dynamic adaptive materials rely on an atomic/molecular mechanism of phase transition to induce macroscopic switch of properties, but only a small number of these materials and a limited responsive repertoire are available. Here, liquid as the adaptive component is utilized to realize responsive functions. Paired with a porous matrix that can be put in motion by an actuated dielectric elastomer film, the uncontrolled global flow of liquid is broken down to well‐defined reconfigurable localized flow within the pores and conforms to the network deformation. A detailed theoretical and experimental study of such a dynamically actuated liquid‐infused poroelastic film is discussed. This system demonstrates its ability to generate tunable surface wettability that can precisely control droplet dynamics from complete pinning, to fast sliding, and even more complex motions such as droplet oscillation, jetting, and mixing. This system also allows for repeated and seamless switch among these different droplet manipulations. These are desired properties in many applications such as reflective display, lab‐on‐a‐chip, optical device, dynamic measurements, energy harvesting, and others.