Temperature‐Induced Hydrogels Through Self‐Assembly of Cholesterol‐Substituted Star PEG‐b‐PLLA Copolymers: An Injectable Scaffold for Tissue Engineering

Partially cholesterol‐substituted 8‐arm poly(ethylene glycol)‐block‐poly(L ‐lactide) (8‐arm PEG‐b‐PLLA‐cholesterol) has been prepared as a novel star‐shaped, biodegradable copolymer derivative. The amphiphilic 8‐arm PEG‐b‐PLLA‐cholesterol aqueous solution (polymer concentration, above 3 wt%) exhibits instantaneous temperature‐induced gelation at 34 °C, but the virgin 8‐arm PEG‐b‐PLLA does not, irrespective of concentration. Moreover, an extracellular matrix (ECM)‐like micrometer‐scale network structure has been created with favorable porosity for three‐dimensional proliferation of cells inside the hydrogel. This network structure is mainly attributed to specific self‐assembly between cholesterol groups. The 10 and 20 wt% hydrogels are eroded gradually in phosphate buffered saline at 37 °C over the course of a month, and after that the gel becomes completely dissociated. Moreover, L929 cells encapsulated into the hydrogel are viable and proliferate three‐dimensionally inside the hydrogels. Thus, in‐vitro cell culture studies demonstrate that 8‐arm PEG‐b‐PLLA‐cholesterol is a promising candidate as a novel injectable cellular scaffold.     

Carbonyl‐β‐Cyclodextrin as a Novel Binder for Sulfur Composite Cathodes in Rechargeable Lithium Batteries

As one of the essential components in electrodes, the binder affects the performance of a rechargeable battery. By modifying β‐cyclodextrin (β‐CD), an appropriate binder for sulfur composite cathodes is identified. Through a partial oxidation reaction in H₂O₂ solution, β‐CD is successfully modified to carbonyl‐β‐cyclodextrin (C‐β‐CD), which exhibits a water solubility ca. 100 times that of β‐CD at room temperature. C‐β‐CD possesses the typical properties of an aqueous binder: strong bonding strength, high solubility in water, moderate viscosity, and wide electrochemical windows. Sulfur composite cathodes with C‐β‐CD as the binder demonstrate a high reversible capacity of 694.2 mA h g_(composite)^?1 and 1542.7 mA h g_(sulfur)^?1, with a sulfur utilization approaching 92.2%. The discharge capacity remains at 1456 mA h g_(sulfur)^?1 after 50 cycles, which is much higher than that of the cathode with unmodified β‐CD as binder. Combined with its low cost and environmental benignity, C‐β‐CD is a promising binder for sulfur cathodes in rechargeable lithium batteries with high electrochemical performance.     

Hydrogel Scaffolds of Amphiphilic and Acidic β‐Sheet Peptides

Amphiphilic and acidic β‐sheet‐forming peptides (AAβPs) having the sequence Pro‐Y‐(Z‐Y)₅‐Pro, Y = Glu or Asp and Z = Phe or Leu may assemble into hydrogel structures at near neutral pH values, several units higher than the intrinsic pKa of their acidic amino acid side chains. The bottom‐to‐top design strategy enables the rationally supported association between the peptides' amino acids composition and bulk pH hydrogelation. Hydrogen bonds between the acidic amino acids side chains in the β‐sheet structure are found to contribute substantially to the stabilization of AAβPs hydrogels. The negatively charged peptides are also found to form gels at lower concentration in presence of calcium ions. Bone forming cells may be cultured on two‐dimensional films of AAβPs hydrogels that form at physiological pH values as well as within three dimensional hydrogel matrices. These acidic‐rich peptides hydrogels may become advantageous in applications related to engineering of mineralized tissues providing controllable, multifunctional calcified scaffolds to affect both the biological activity and the inorganic mineralization.     

A Gene Therapy Technology‐Based Biomaterial for the Trigger‐Inducible Release of Biopharmaceuticals in Mice

Gene therapy scientists have developed expression systems for therapeutic transgenes within patients, which must be seamlessly integrated into the patient's physiology by developing sophisticated control mechanisms to titrate expression levels of the transgenes into the therapeutic window. However, despite these efforts, gene‐based medicine still faces security concerns related to the administration of the therapeutic transgene vector. Here, molecular tools developed for therapeutic transgene expression can readily be transferred to materials science to design a humanized drug depot that can be implanted into mice and enables the trigger‐inducible release of a therapeutic protein in response to a small‐molecule inducer. The drug depot is constructed by embedding the vascular endothelial growth factor (VEGF₁₂₁) as model therapeutic protein into a hydrogel consisting of linear polyacrylamide crosslinked with a homodimeric variant of the human FK‐binding protein 12 (F_M), originally developed for gene therapeutic applications, as well as with dimethylsuberimidate. Administrating increasing concentrations of the inducer molecule FK506 triggers the dissociation of F_M thereby loosening the hydrogel structure and releasing the VEGF₁₂₁ payload in a dose‐adjustable manner. Subcutaneous implantation of the drug depot into mice and subsequent administration of the inducer by injection or by oral intake triggers the release of VEGF₁₂₁ as monitored in the mouse serum. This study is the first demonstration of a stimuli‐responsive hydrogel that can be used in mammals to release a therapeutic protein on demand by the application of a small‐molecule stimulus. This trigger‐inducible release is a starting point for the further development of externally controlled drug depots for patient‐compliant administration of biopharmaceuticals.     

A New Prototype Two‐Phase (TiNi)–(β‐W) SMA System with Tailorable Thermal Hysteresis

The Ti–Ni–W two‐phase shape memory alloy (SMA) thin film system is presented as a prototype for new SMAs with tailorable thermal transformation hysteresis (ΔT). The concept is to combine the SMA TiNi with almost insoluble W to create the two‐phase system (TiNi)–(β‐W). This system behaves like a pseudobinary TiNi system. Phase transformation behavior for compositions above the solubility limit of W in TiNi exhibit a B2–R phase transformation with characteristically small ΔT. Moreover, ΔT is dependent on the amount of W and it can be tailored to zero and even negative. This phenomenon is rationalized as being due to the mechanical interaction between the phases B2‐TiNi and β‐W. The presented results are very promising for the development of high‐speed Ti–Ni‐based SMA actuators.     

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.     

Biocompatible Poly(2‐hydroxyethyl methacrylate)‐b‐poly(L‐histidine) Hybrid Materials for pH‐Sensitive Intracellular Anticancer Drug Delivery

A series of synthetic polymer bioconjugate hybrid materials consisting of poly(2‐hydroxyethyl methacrylate) (p(HEMA)) and poly(l‐ histidine) (p(His)) are synthesized by combining atom transfer radical polymerization of HEMA with ring opening polymerization of benzyl‐N‐carboxy‐L ‐histidine anhydride. The resulting biocompatible and membranolytic p(HEMA)₂₅‐b‐p(His)_n (n = 15, 25, 35, and 45) polymers are investigated for their use as pH‐sensitive drug‐carrier for tumor targeting. Doxorubicin (Dox) is encapsulated in nanosized micelles fabricated by a self‐assembly process and delivered under different pH conditions. Micelle size is characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM) observations. Dox release is investigated according to pH, demonstrating the release is sensitive to pH. Antitumor activity of the released Dox is assessed using the HCT 116 human colon carcinoma cell line. Dox released from the p(HEMA)‐b‐p(His) micelles remains biologically active and has the dose‐dependent capability to kill cancer cells at acidic pH. The p(HEMA)‐b‐p(His) hybrid materials are capable of self‐assembling into nanomicelles and effectively encapsulating the chemotherapeutic agent Dox, which allows them to serve as suitable carriers of drug molecules for tumor targeting.     

A Printable Photopolymerizable Thermosensitive p(HPMAm‐lactate)‐PEG Hydrogel for Tissue Engineering

Bioprinting is a new technology in regenerative medicine that allows the engineering of tissues by specific placement of cells in biomaterials. Importantly, the porosity and the relatively small dimensions of the fibers allow rapid diffusion of nutrients and metabolites. This technology requires the availability of hydrogels that ensure viability of encapsulated cells and have adequate mechanical properties for the preparation of structurally stable and well‐defined three‐dimensional constructs. The aim of this study is to evaluate the suitability of a biodegradable, photopolymerizable and thermosensitive A–B–A triblock copolymer hydrogel as a synthetic extracellular matrix for engineering tissues by means of three dimensional fiber deposition. The polymer is composed of poly(N‐(2‐hydroxypropyl)methacrylamide lactate) A‐blocks, partly derivatized with methacrylate groups, and hydrophilic poly(ethylene glycol) B‐blocks of a molecular weight of 10 kDa. Gels are obtained by thermal gelation and stabilized with additional chemical cross‐links by photopolymerization of the methacrylate groups coupled to the polymer. A power law dependence of the storage plateau modulus of the studied hydrogels on polymer concentration is observed for both thermally and chemically cross‐linked hydrogels. The hydrogels demonstrated mechanical characteristics similar to natural semi‐flexible polymers, including collagen. Moreover, the hydrogel shows suitable mechanical properties for bioprinting, allowing subsequent layer‐by‐layer deposition of gel fibers to form stable constructs up to at least 0.6 cm (height) with different patterns and strand spacing. The resulting constructs have reproducible vertical porosity and the ability to maintain separate localization of encapsulated fluorescent microspheres. Moreover, the constructs show an elastic modulus of 119 kPa (25 wt% polymer content) and a degradation time of approximately 190 days. Furthermore, high viability is observed for encapsulated chondrocytes after 1 and 3 days of culture. In summary, we conclude that the evaluated hydrogel is an interesting candidate for bioprinting applications.     

Preparation and Characterization of a pH‐ and Thermally Responsive Poly(N‐isopropylacrylamide‐co‐acrylic acid)/Porous SiO2 Hybrid

A multifunctional nanohybrid composed of a pH‐ and thermoresponsive hydrogel, poly(N‐isopropylacrylamide‐co‐acrylic acid) [poly(NIPAM‐co‐AAc)], is synthesized in situ within the mesopores of an oxidized porous Si template. The hybrid is characterized by electron microscopy and by thin film optical interference spectroscopy. The optical reflectivity spectrum of the hybrid displays Fabry–Pérot fringes characteristic of thin film optical interference, enabling direct, real‐time observation of the pH‐induced swelling, and volume phase transitions associated with the confined poly(NIPAM‐co‐AAc) hydrogel. The optical response correlates to the percentage of AAc contained within the hydrogel, with a maximum change observed for samples containing 20% AAc. The swelling kinetics of the hydrogel are significantly altered due to the nanoscale confinement, displaying a more rapid response to pH or heating stimuli relative to bulk polymer films. The inclusion of AAc dramatically alters the thermoresponsiveness of the hybrid at pH 7, effectively eliminating the lower critical solution temperature (LCST). The observed changes in the optical reflectivity spectrum are interpreted in terms of changes in the dielectric composition and morphology of the hybrids.     

Synthesis,Crystal Structure,and Magnetic Properties of ϵ‐InxFe2–xO3 Nanorod‐Shaped Magnets

A series of ?‐In_xFe_2–xO₃ nanorods are prepared by combining the reverse‐micelle and the sol–gel methods. Metal replacement was achieved in the region of 0 ≤ x ≤ 0.24. The crystal structures are orthorhombic structures (space group: Pna2₁), which are pyroelectric with an electric polarization along the c axis. The transmission electron microscopy images show that the particle sizes are (80 ± 40) × (23 ± 5) nm (x = 0), (65 ± 30) × (30 ± 10) nm (x = 0.12), and (80 ± 40) × (35 ± 15) nm (x = 0.24). The magnetization versus temperature curves of the samples with x = 0, x = 0.12, and x = 0.24 show spontaneous magnetization with Curie temperatures of 495 K, 456 K, and 414 K, respectively. Their coercive fields at 300 K are 20 kOe (x = 0), 14 kOe (x = 0.12), and 9 kOe (x = 0.24). These samples show a spin reorientation with reorientation temperatures (T_p) of 102 K (x = 0), 149 K (x = 0.12), and 180 K (x = 0.24). In particular, the samples with x = 0.12 and x = 0.24 show antiferromagnetic behavior below T_p. This series of ?‐In_xFe_2–xO₃ is the first example of a pyroelectric material that exhibits a phase transition between ferrimagnetism and antiferromagnetism.     

Self‐Assembling Nanotubes Consisting of Rigid Cyclic γ‐Peptides

Self‐assembling cyclic peptide nanotubes (SPNs) have been extensively studied due to their potential applications in biology and material sciences. Cyclic γ‐peptides, which have a larger conformational space, have received less attention than the cyclic α‐ and β‐peptides. The self‐assembly of cyclic homo‐γ‐tetrapeptide based on cis‐3‐aminocyclohexanecarboxylic acid (γ‐Ach) residues, which can be easily synthesized by a one‐pot process is investigated. Fourier transform infrared (FTIR) and NMR analysis along with density functional theory (DFT) calculations indicate that the cyclic homo‐γ‐tetrapeptide, with a non‐planar conformation, can self‐assemble into nanotubes through hydrogen‐bond‐mediated parallel stacking. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) experiments reveal the formation of bundles of nanotubes in CH₂Cl₂/hexane, but individual nanotubes and bundles of only two nanotubes are obtained in water. The integration of TEG (triethylene glycol) monomethyl ether chains and cyclopeptide backbones may allow the control of width of single nanotubes.     

Poly(N‐isopropylacrylamide)‐Clay Nanocomposite Hydrogels with Responsive Bending Property as Temperature‐Controlled Manipulators

Novel poly(N‐isopropylacrylamide)‐clay (PNIPAM‐clay) nanocomposite (NC) hydrogels with both excellent responsive bending and elastic properties are developed as temperature‐controlled manipulators. The PNIPAM‐clay NC structure provides the hydrogel with excellent mechanical property, and the thermoresponsive bending property of the PNIPAM‐clay NC hydrogel is achieved by designing an asymmetrical distribution of nanoclays across the hydrogel thickness. The hydrogel is simply fabricated by a two‐step photo polymerization. The thermoresponsive bending property of the PNIPAM‐clay NC hydrogel is resulted from the unequal forces generated by the thermoinduced asynchronous shrinkage of hydrogel layers with different clay contents. The thermoresponsive bending direction and degree of the PNIPAM‐clay NC hydrogel can be adjusted by controlling the thickness ratio of the hydrogel layers with different clay contents. The prepared PNIPAM‐clay NC hydrogels exhibit rapid, reversible, and repeatable thermoresponsive bending/unbending characteristics upon heating and cooling. The proposed PNIPAM‐clay NC hydrogels with excellent responsive bending property are demonstrated as temperature‐controlled manipulators for various applications including encapsulation, capture, and transportation of targeted objects. They are highly attractive material candidates for stimuli‐responsive “smart” soft robots in myriad fields such as manipulators, grippers, and cantilever sensors.     

Highly Efficient Diels–Alder Crosslinkable Electro‐Optic Dendrimers for Electric‐Field Sensors

One of the most challenging tasks encountered in developing highly efficient electro‐optic (EO) devices is to find a material system that possesses all desirable properties such as large EO coefficients, good thermal and mechanical stability, and low optical loss. In order to meet this stringent requirement, we have developed a series of crosslinkable EO dendrimers using the standardized AJL8 ‐type chromophore as the center core and the furyl‐ and anthryl‐containing dendrons as the periphery. Upon adding a trismaleimide ( TMI ) dienophile, these dendrimers could be in‐situ crosslinked via the Diels–Alder cycloaddition and efficiently poled under a high electric field. Through this dynamic process, the spatially voided and π‐electron‐rich surrounding of the chromophore core changes into a dense and more aliphatic network, with the dipolar chromophore embedded and aligned inside. The resultant materials exhibit large EO coefficients (63–99 pm V^–1 at 1.31 μm), excellent temporal stability (the original r₃₃ values remain unchanged at 100 °C for more than 500 h), and blue‐shifted near‐IR absorption. With these combined desirable properties, a poled EOD2/TMI film could be processed through multiple lithographic and etching steps to fabricate a racetrack‐shaped micro‐ring resonator. By coupling this ring resonator with a side‐polished optical fiber, a novel broadband electric‐field sensor with high sensitivity of 100 mV m^–1 at 550 MHz was successfully demonstrated.     

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.     

Optimized La0.6Sr0.4CoO3–δ Thin‐Film Electrodes with Extremely Fast Oxygen‐Reduction Kinetics

La_0.6Sr_0.4CoO_3–δ (LSC) thin‐film electrodes are prepared on yttria‐stabilized zirconia (YSZ) substrates by pulsed laser deposition at different deposition temperatures. The decrease of the film crystallinity, occurring when the deposition temperature is lowered, is accompanied by a strong increase of the electrochemical oxygen exchange rate of LSC. For more or less X‐ray diffraction (XRD)‐amorphous electrodes deposited between ca. 340 and 510 °C polarization resistances as low as 0.1 Ω cm² can be obtained at 600 °C. Such films also exhibit the best stability of the polarization resistance while electrodes deposited at higher temperatures show a strong and fast degradation of the electrochemical kinetics (thermal deactivation). Possible reasons for this behavior and consequences with respect to the preparation of high‐performance solid oxide fuel cell (SOFC) cathodes are discussed.     

Self‐Assembly of m‐Diethynylbenzene Macrocycles Containing Exoannular Chiral Side Chains

Induced circular dichroism (CD) spectra of the m‐diethynylbenzene macrocycles (S)‐ 2 and (R)‐ 2 that have exoannular chiral side chains are observed in a methanol/chloroform (8:2) solution, indicating the formation of chiral, helical aggregates in solution. Solid films prepared on the surface of quartz substrates by spin‐coating solutions of (S)‐ 2 also exhibit CD signals that are remarkably dependent on the solvent used for the spin‐coating. The relationship between the CD spectra and the morphology of the solid films observed by atomic force microscopy is discussed.     

A Highly Stable,New Electrochromic Polymer: Poly(1,4‐bis(2‐(3′,4′‐ethylenedioxy) thienyl)‐2‐methoxy‐5‐2″‐ethylhexyloxybenzene)

A highly stable new electrochromic polymer, poly(1,4‐bis(2‐(3′,4′‐ethylenedioxy)thienyl)‐2‐methoxy‐5‐2″‐ethylhexyloxybenzene) (P(BEDOT‐MEHB)) was synthesized and its electrochemical and electrochromic properties are reported. P(BEDOT‐MEHB) showed a very well defined electrochemistry with a relatively low oxidation potential of the monomer at + 0.44 V versus Ag/Ag⁺, E_1/2 at – 0.35 V versus Ag/Ag⁺ and stability to long‐term switching up to 5000 cycles. A high level of stability to over‐oxidation has also been observed as this material shows limited degradation of its electroactivity at potentials 1.4 V above its half‐wave potential. Spectroelectrochemistry showed that the absorbance of the π–π* transition in the neutral state is blue‐shifted compared to PEDOT, displaying a maximum at 538 nm (onset at 640 nm), thus giving an almost colorless, highly transparent oxidized polymer with a bandgap of 1.95 eV. Different colors observed at different oxidation levels and strong absorption in the near‐IR make this polymer a good candidate for several applications.     

Positively K+‐Responsive Membranes with Functional Gates Driven by Host–Guest Molecular Recognition

A novel positively K⁺‐responsive membrane with functional gates driven by host‐guest molecular recognition is prepared by grafting poly(N‐isopropylacrylamide‐co‐acryloylamidobenzo‐15‐crown‐5) (poly(NIPAM‐co‐AAB₁₅C₅)) copolymer chains in the pores of porous nylon‐6 membranes with a two‐step method combining plasma‐induced pore‐filling grafting polymerization and chemical modification. Due to the cooperative interaction of host‐guest complexation and phase transition of the poly(NIPAM‐co‐AAB₁₅C₅), the grafted gates in the membrane pores could spontaneously switch from “closed” state to “open” state by recognizing K⁺ ions in the environment and vice versa; while other ions (e.g., Na⁺, Ca²⁺ or Mg²⁺) can not trigger such an ion‐responsive switching function. The positively K⁺‐responsive gating action of the membrane is rapid, reversible, and reproducible. The proposed K⁺‐responsive gating membrane provide a new mode of behavior for ion‐recognizable “smart” or “intelligent” membrane actuators, which is highly attractive for controlled release, chemical/biomedical separations, tissue engineering, sensors, etc.