Thermoplastic Elastomer Hydrogels via Self‐Assembly of an Elastin‐Mimetic Triblock Polypeptide

Protein‐based analogues of conventional thermoplastic elastomers can be designed with enhanced properties as a consequence of the precise control of primary structure. Protein 1 undergoes a reversible sol–gel transition, which results in the formation of a well‐defined elastomeric network above a lower critical solution temperature. The morphology of the network is consistent with selective microscopic phase separation of the endblock domains. This genetic engineering approach provides a method for specification of the critical architectural parameters, such as block length and sequence, which define macromolecular properties that are important for downstream applications.     

Regulation of the Stem Cell–Host Immune System Interplay Using Hydrogel Coencapsulation System with an Anti‐Inflammatory Drug

The host immune system is known to influence mesenchymal stem cell (MSC)‐mediated bone tissue regeneration. However, the therapeutic capacity of hydrogel biomaterial to modulate the interplay between MSCs and T‐lymphocytes is unknown. Here it is shown that encapsulating hydrogel affects this interplay when used to encapsulate MSCs for implantation by hindering the penetration of pro‐inflammatory cells and/or cytokines, leading to improved viability of the encapsulated MSCs. This combats the effects of the host pro‐inflammatory T‐lymphocyte‐induced nuclear factor kappaB pathway, which can reduce MSC viability through the CASPASE‐3 and CASPASE‐8 associated proapoptotic cascade, resulting in the apoptosis of MSCs. To corroborate rescue of engrafted MSCs from the insult of the host immune system, the incorporation of the anti‐inflammatory drug indomethacin into the encapsulating alginate hydrogel further regulates the local microenvironment and prevents pro‐inflammatory cytokine‐induced apoptosis. These findings suggest that the encapsulating hydrogel can regulate the MSC‐host immune cell interplay and direct the fate of the implanted MSCs, leading to enhanced tissue regeneration.     

Dual Stimuli‐Responsive Supramolecular Polypeptide‐Based Hydrogel and Reverse Micellar Hydrogel Mediated by Host–Guest Chemistry

Versatile strategies are currently being discovered for the fabrication of synthetic polypeptide‐based hybrid hydrogels, which have potential applications in polymer therapeutics and regenerative medicine. Herein, a new concept—the reverse micellar hydrogel—is introduced, and a versatile strategy is provided for fabricating supramolecular polypeptide‐based normal micellar hydrogel and reverse micellar hydrogels from the same polypeptide‐based copolymer via the cooperation of host–guest chemistry and hydrogen‐bonding interactions. The supramolecular hydrogels are thoroughly characterized, and a mechanism for their self‐assembly is proposed. These hydrogels can respond to dual stimuli—temperature and pH—and their mechanical and controlled drug‐release properties can be tuned by the copolymer topology and the polypeptide composition. The reverse micellar hydrogel can load 10% of the anticancer drug doxorubicin hydrochloride (DOX) and sustain DOX release for 45 days, indicating that it could be useful as an injectable drug delivery system.     

Triplet–Triplet Annihilation‐Based Anti‐Stokes Oxygen Sensing Materials with a Very Broad Dynamic Range

A novel concept for designing optical oxygen sensing materials is reported. Oxygen‐sensitive anti‐Stokes emission is generated via triplet–triplet annihilation‐based upconversion and serves as an analytical parameter. Porous glass beads are used to incorporate the “sensing chemistry” including a sensitizer and an annihilator dissolved in a high boiling solvent. The beads are dispersed in silicone rubber or Teflon AF to produce solid state optodes. Inexpensive low power light sources (LEDs) are used for the excitation. The upconverted emission shows unmatched sensitivity both for the luminescence decay time and for the luminescence intensity. The latter features unusual quadratic Stern‐Volmer plots. Much lower sensitivity of the residual NIR luminescence of the sensitizer allows determination of pO₂ in the broad dynamic range from trace oxygen quantities to ≈40 kPa. Interrogation of the sensors in frequency domain is demonstrated. Influence of the excitation light power on the calibration, temperature effects, dynamic response to altering pO₂, and photostability of the sensing materials are also investigated.     

Application of Inhibitor‐Loaded Halloysite Nanotubes in Active Anti‐Corrosive Coatings

Halloysite particles are aluminum‐silicate hollow cylinders with a length of 0.5–1 µm, an outer diameter of ca. 50 nm and a lumen of 15 nm. These nanotubes are used for loading and sustained release of corrosion inhibitors. The inhibitor is kept inside the particles infinitely long under dry conditions. Here, halloysite nanotubes filled with anticorrosive agents are embedded into a SiO_x–ZrO_x hybrid film. An aluminum plate is dip‐coated and immersed into 0.1 M sodium chloride aqueous solution for corrosion tests. A defect in the sol–gel coating induces pitting corrosion on the metal accompanied by a strong anodic activity. The inhibitor is released within one hour from halloysite nanotubes at corrosion spots and suppresses the corrosion process. The anodic activity is successfully restrained and the protection remains for a long time period of immersion in NaCl water solution. The self‐healing effect of the sol–gel coating doped with inhibitor‐loaded halloysite nanotubes is demonstrated in situ via scanning vibrating electrode technique measurements.     

Humidity‐Triggered Self‐Healing of Microporous Polyelectrolyte Multilayer Coatings for Hydrophobic Drug Delivery

Layer‐by‐layer (LbL) self‐assemblies have inherent potential as dynamic coatings because of the sensitivity of their building blocks to external stimuli. Here, humidity serves as a feasible trigger to activate the self‐healing of a microporous polyethylenimine/poly(acrylic acid) multilayer film. Microporous structures within the polyelectrolyte multilayer (PEM) film are created by acid treatment, followed by freeze‐drying to remove water. The self‐healing of these micropores can be triggered at 100% relative humidity, under which condition the mobility of the polyelectrolytes is activated. Based on this, a facile and versatile method is suggested for directly integrating hydrophobic drugs into PEM films for surface‐mediated drug delivery. The high porosity of microporous film enables the highest loading (≈303.5 μg cm^?2 for a 15‐bilayered film) of triclosan to be a one‐shot process via wicking action and subsequent solvent removal, thus dramatically streamlining the processes and reducing complexities compared to the existing LbL strategies. The self‐healing of a drug‐loaded microporous PEM film significantly reduces the diffusion coefficient of triclosan, which is favorable for the long‐term sustained release of the drug. The dynamic properties of this polymeric coating provide great potential for its use as a delivery platform for hydrophobic drugs in a wide variety of biomedical applications.     

Optoelectronic Properties of Quasi‐Linear,Self‐Assembled Platinum Complexes: Pt–Pt Distance Dependence

Charge‐carrier mobilities of various self‐assembled platinum complexes were measured by time‐resolved microwave conductivity techniques in the temperature range –80 to +100 °C. Eight compounds were investigated in the present study, including the original Magnus' green salt ([Pt(NH₃)₄][PtCl₄]) and derivatives with the general structure [Pt(NH₂R)₄][PtCl₄], where R denotes an alkyl side chain. In one instance, the chlorines were substituted with bromines. For these complexes, which all consist of a linear backbone of platinum atoms with Pt–Pt distances, d, varying from 3.1 to ≥ 3.6 Å, a strong, inverse correlation was found between d and the one‐dimensional charge‐carrier mobility, Σμ_1D. The highest value of Σμ_1D at room temperature was observed for R = (S)‐3,7‐dimethyloctyl (dmoc) with Σμ_1D ≥ 0.06 cm² V^–1 s^–1. Almost all materials exhibited a charge‐carrier mobility that was relatively independent of the temperature over the range studied. One exceptional compound (R = (R)‐2‐ethylhexyl) showed a pronounced negative temperature dependence of the charge‐carrier mobility; upon decreasing the temperature from +100 °C to –80 °C the charge‐carrier mobility increased by a factor of about ten.     

A Macroporous Hydrogel Dressing with Enhanced Antibacterial and Anti‐Inflammatory Capabilities for Accelerated Wound Healing

Here, a novel macroporous hydrogel dressing is presented that can accelerate wound healing and guard against bacteria‐associated wound infection. Carboxymethyl agarose (CMA) is successfully prepared from agarose. The CMA molecular chains are cross‐linked by hydrogen bonding to form a supramolecular hydrogel, and the hydroxy groups in the CMA molecules complex with Ag⁺ to promote hydrogel formation. This hydrogel composite exhibits pH‐responsiveness and temperature‐responsiveness and releases Ag⁺, an antibacterial agent, over a prolonged period of time. Moreover, this hydrogel exhibits outstanding cytocompatibility and hemocompatibility. In vitro and in vivo investigations demonstrate that the hydrogel has enhanced antibacterial and anti‐inflammatory capabilities and can significantly accelerate skin tissue regeneration and wound closure. Astonishingly, the hydrogel can cause the inflammation process to occur earlier and for a shorter amount of time than in a normal process. Given its excellent antibacterial, anti‐inflammatory, and physicochemical properties, the broad application of this hydrogel in bacteria‐associated wound management is anticipated.     

Protein‐Release Behavior of Self‐Assembled PEG–β‐Cyclodextrin/PEG–Cholesterol Hydrogels

This paper reports on the degradation and protein release behavior of a self‐assembled hydrogel system composed of β‐cyclodextrin‐ (βCD) and cholesterol‐derivatized 8‐arm star‐shaped poly(ethylene glycol) (PEG₈). By mixing βCD‐ and cholesterol‐derivatized PEG₈ (molecular weights 10, 20 and 40 kDa) in aqueous solution, hydrogels with different rheological properties are formed. It is shown that hydrogel degradation is mainly the result of surface erosion, which depends on the network swelling stresses and initial crosslink density of the gels. This degradation mechanism, which is hardly observed for other water‐absorbing polymer networks, leads to a quantitative and nearly zero‐order release of entrapped proteins. This system therefore offers great potential for protein delivery.     

Fabrication of All‐Water‐Based Self‐Repairing Superhydrophobic Coatings Based on UV‐Responsive Microcapsules

Superhydrophobic coatings that are also self‐healing have drawn much attention in recent years for improved durability in practical applications. Typically, the release of the self‐healing agents is triggered by temperature and moisture change. In this study, UV‐responsive microcapsules are successfully synthesized by Pickering emulsion polymerization using titania (TiO₂) and silica (SiO₂) nanoparticles as the Pickering agents to fabricate all‐water‐based self‐repairing, superhydrophobic coatings. These coatings are environmentally friendly and can be readily coated on various substrates. Compared to conventional superhydrophobic coatings, these coatings can regenerate superhydrophobicity and self‐cleaning ability under UV light, mimicking the outdoor environment, after they are mechanically damaged or contaminated with organics. They can maintain the superhydrophobicity after multiple cycles of accelerated weathering tests.     

Enhanced Omnidirectional Photovoltaic Performance of Solar Cells Using Multiple‐Discrete‐Layer Tailored‐ and Low‐Refractive Index Anti‐Reflection Coatings

An optimized four‐layer tailored‐ and low‐refractive index anti‐reflection (AR) coating on an inverted metamorphic (IMM) triple‐junction solar cell device is demonstrated. Due to an excellent refractive index matching with the ambient air by using tailored‐ and low‐refractive index nanoporous SiO₂ layers and owing to a multiple‐discrete‐layer design of the AR coating optimized by a genetic algorithm, such a four‐layer AR coating shows excellent broadband and omnidirectional AR characteristics and significantly enhances the omnidirectional photovoltaic performance of IMM solar cell devices. Comparing the photovoltaic performance of an IMM solar cell device with the four‐layer AR coating and an IMM solar cell with the conventional SiO₂/TiO₂ double layer AR coating, the four‐layer AR coating achieves an angle‐of‐incidence (AOI) averaged short‐circuit current density, J_SC, enhancement of 34.4%, whereas the conventional double layer AR coating only achieves an AOI‐averaged J_SC enhancement of 25.3%. The measured reflectance reduction and omnidirectional photovoltaic performance enhancement of the four‐layer AR coating are to our knowledge, the largest ever reported in the literature of solar cell devices.     

Temperature‐Switchable Assembly of Supramolecular Virus–Polymer Complexes

Here a method is presented for the temperature‐switchable assembly of viral particles into large hierarchical complexes. Dual‐functional diblock copolymers consisting of poly(diethyleneglycol methyl ether methacry­late) (poly(DEGMA)) and poly((2‐dimethylamino)ethyl methacrylate) (poly(DMAEMA)) blocks self‐assemble electrostatically with cowpea chlorotic mottle virus (CCMV) particles into micrometer‐sized objects as a function of temperature. The poly(DMAEMA) block carries a positive charge, which can interact electrostatically with the negatively charged outer surface of the CCMV capsid. When the solution temperature is increased above 40 °C, to cross the cloud point temperature (T_cp) of the DEGMA block, the polymer chains collapse on the surface of the virus particle, which makes them partially hydrophobic, and consequently causes the formation of large hierarchical assemblies. Disassembly of the virus–polymer complexes can be induced by reducing the solution temperature below the T_cp, which allows the poly(DEGMA) blocks to rehydrate and free virus particles to be released. The assembly process is fully reversible and can sustain several heating–cooling cycles. Importantly, this method relies on reversible supramolecular interactions and therefore avoids the irreversible covalent modification of the particle surface. This study illustrates the potential of temperature‐responsive polymers for controlled binding and releasing of virus particles.     

High‐Performance Flexible Multilayer MoS2 Transistors on Solution‐Based Polyimide Substrates

Transition metal dichalcogenides (TMDs) layers of molecular thickness, in particular molybdenum disulfide (MoS₂), become increasingly important as active elements for mechanically flexible/stretchable electronics owing to their relatively high carrier mobility, wide bandgap, and mechanical flexibility. Although the superior electronic properties of TMD transistors are usually integrated into rigid silicon wafers or glass substrates, the achievement of similar device performance on flexible substrates remains quite a challenge. The present work successfully addresses this challenge by a novel process architecture consisting of a solution‐based polyimide (PI) flexible substrate in which laser‐welded silver nanowires are embedded, a hybrid organic/inorganic gate insulator, and multilayers of MoS₂. Transistors fabricated according to this process scheme have decent properties: a field‐effect‐mobility as high as 141 cm² V^?1 s^?1 and an I_on/I_off ratio as high as 5 × 10⁵. Furthermore, no apparent degradation in the device properties is observed under systematic cyclic bending tests with bending radii of 10 and 5 mm. Overall electrical and mechanical results provide potentially important applications in the fabrication of versatile areas of flexible integrated circuitry.     

A New Anti‐Counterfeiting Feature Relying on Invisible Luminescent Full Color Images Printed with Lanthanide‐Based Inks

Europium and terbium trisdipicolinate complexes are inkjet printed onto paper with commercially available desktop inkjet printers. Together with a commercial blue luminescent ink, the red‐emitting luminescent ink containing europium and the green‐emitting luminescent ink containing terbium are used to reproduce accurate full color images that are invisible under white light and appear under a 254 nm UV light. Such invisible luminescent images are attractive anti‐counterfeiting security features. The luminescent prints have a color range (gamut) nearly as wide as the gamut of a standard sRGB display. The gamut of the luminescent prints is determined by relying on a simple model predicting the relative spectral radiant emittances of any printed luminescent color halftone. The model is also used to establish the correspondence between the surface coverages of the printed luminescent inks and the emitted color of these luminescent halftones. The accuracy of the spectral prediction model is very good and can be rationalized by the absence of quenching when the luminescent lanthanide complexes are printed in superposition with the other luminescent materials.     

The Preparation and Characterization of Small Mesopores in Siloxane‐Based Materials That Use Cyclodextrins as Templates

Porous thin films containing very small closed pores (～ 20 Å) with a low dielectric constant (～ 2.0) and excellent mechanical properties have been prepared using the mixture of cyclic silsesquioxane (CSSQ) and a new porogen, heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (tCD). The pore sizes vary from 16.3 Å to 22.2 Å when the content of tCD in the coating mixture increases to 45 wt.‐% according to positronium annihilation lifetime spectroscopy (PALS) analysis. It has also been found that the pore percolation threshold (the onset of pore interconnectivity) occurs as the ～ 50 % tCD porogen load. The dielectric constants (k = 2.4 ～ 1.9) and refractive indices of these porous thin films decreased systematically as the amount of porogen loading increased in the coating mixture. The electrical properties and mechanical properties of such porous thin films were fairly good as interlayer dielectrics.     

Nanocontainer‐Based Anticorrosive Coatings: Effect of the Container Size on the Self‐Healing Performance

Organic coatings based on inhibitor loaded inorganic containers for smart corrosion inhibition are presented. The overall coating performance is strongly influenced by the containers as well as their inhibitor capacity, compatibility with the coating matrix, and size. The important effect of container size is described for the first time in this work by investigating two types of mesoporous silica containers of different diameters: 80 and 700 nm. The coating physical properties (thickness and adhesion) are comparable for both container types. In contrast, the coating barrier properties are strongly influenced by the container size as assessed with electrochemical impedance spectroscopy (EIS). The incorporation of bigger containers reduces the coating resistance by a factor of two. Surprisingly, despite the similar amounts (20 wt%) of loaded inhibitor (2‐mercaptobenzothiazole), different active inhibition ability is detected with the scanning vibrating electrode technique (SVET). Therefore, it is found that coatings with smaller containers exhibit better self‐healing performance.     

Conception and Performance Analysis of Efficient CDMA‐Based Full‐Duplex Anti‐collision Scheme

Ultra‐high‐frequency radio‐frequency identification (UHF RFID) is widely applied in different industries. The Frame Slotted ALOHA in EPC C1G2 suffers severe collisions that limit the efficiency of tag recognition. An efficient full‐duplex anti‐collision scheme is proposed to reduce the rate of collision by coordinating the transmitting process of CDMA UWB uplink and UHF downlink. The relevant mathematical models are built to analyze the performance of the proposed scheme. Through simulation, some important findings are gained. The maximum number of identified tags in one slot is g/e (g is the number of PN codes and e is Euler's constant) when the number of tags is equal to mg (m is the number of slots). Unlike the Frame Slotted ALOHA, even if the frame size is small and the number of tags is large, there aren't too many collisions if the number of PN codes is large enough. Our approach with 7‐bit Gold codes, 15‐bit Gold codes, or 31‐bit Gold codes operates 1.4 times, 1.7 times, or 3 times faster than the CDMA Slotted ALOHA, respectively, and 14.5 times, 16.2 times, or 18.5 times faster than the EPC C1 G2 system, respectively. More than 2,000 tags can be processed within 300 ms in our approach.     

Carbon‐Nanotube–PDMS Composite Coatings on Optical Fibers for All‐Optical Ultrasound Imaging

Polymer–carbon nanotube composite coatings have properties that are desirable for a wide range of applications. However, fabrication of these coatings onto submillimeter structures with the efficient use of nanotubes has been challenging. Polydimethylsiloxane (PDMS)–carbon nanotube composite coatings are of particular interest for optical ultrasound transmission, which shows promise for biomedical imaging and therapeutic applications. In this study, methods for fabricating composite coatings comprising PDMS and multiwalled carbon nanotubes (MWCNTs) with submicrometer thickness are developed and used to coat the distal ends of optical fibers. These methods include creating a MWCNT organogel using two solvents, dip coating of this organogel, and subsequent overcoating with PDMS. These coated fibers are used as all‐optical ultrasound transmitters that achieve high ultrasound pressures (up to 21.5 MPa peak‐to‐peak) and broad frequency bandwidths (up to 39.8 MHz). Their clinical potential is demonstrated with all‐optical pulse‐echo ultrasound imaging of an aorta. The fabrication methods in this paper allow for the creation of thin, uniform carbon nanotube composites on miniature or temperature‐sensitive surfaces, to enable a wide range of advanced sensing capabilities.     

Carbon Nanotube Coatings on Bioglass‐Based Tissue Engineering Scaffolds

The coating of highly porous Bioglass^® based 3D scaffolds with multi‐walled carbon nanotubes (CNT) was investigated. Foam like Bioglass^® scaffolds were fabricated by the replica technique and electrophoretic deposition was used to deposit homogeneous layers of CNT throughout the scaffold pore structure. The optimal experimental conditions were determined to be: applied voltage 15 V and deposition time 20 minutes, utilizing a concentrated aqueous suspension of CNT with addition of a surfactant and iodine. The scaffold pore structure remained invariant after the CNT coating, as assessed by SEM. The incorporation of CNTs induced a nanostructured internal surface of the pores which is thought to be beneficial for osteoblast cell attachment and proliferation. Bioactivity of the scaffolds was assessed by immersion studies in simulated body fluid (SBF) for periods of up to 2 weeks and the subsequent determination of hydroxyapatite (HA) formation. The presence of CNTs can enhance the bioactive behaviour of the scaffolds since CNTs can serve as template for the ordered formation of a nanostructured HA layers, which does not occur on uncoated Bioglass^® surfaces.