Nanostructured Graphene/TiO2 Hybrids as High‐Performance Anodes for Microbial Fuel Cells

A new nanostructured graphene/TiO₂ (G/TiO₂) hybrid was synthesized by a facile microwave‐assisted solvothermal process in which amorphous TiO₂ was assembled on graphene in situ. The resulting G/TiO₂ hybrids were characterized by XRD, SEM, TEM, Raman spectroscopy, and N₂ adsorption/desorption analysis. The electrochemical properties of the hybrids as anode materials for Shewanella‐inoculated microbial fuel cells (MFCs) were studied for the first time, and they proved to be effective in improving MFC performance. The significantly improved bacterial attachment and extracellular electron‐transfer efficiency could be attributed to the high specific surface area, active groups, large pore volume, and excellent conductivity of the nanostructured G/TiO₂ hybrid, and this suggests that it could be a promising candidate for high‐performance MFCs.     

Preparation of Biocomposite Microfibers Ready for Processing into Biologically Active Textile Fabrics for Bioremediation

Biocomposites, i.e., materials consisting of metabolically active microorganisms embedded in a synthetic extracellular matrix, may find applications as highly specific catalysts in bioproduction and bioremediation. 3D constructs based on fibrous biocomposites, so‐called “artificial biofilms,” are of particular interest in this context. The inability to produce biocomposite fibers of sufficient mechanical strength for processing into bioactive fabrics has so far hindered progress in the area. Herein a method is proposed for the direct wet spinning of microfibers suitable for weaving and knitting. Metabolically active bacteria (either Shewanella oneidensis or Nitrobacter winogradskyi (N. winogradskyi)) are embedded in these fibers, using poly(vinyl alcohol) as matrix. The produced microfibers have a partially crystalline structure and are stable in water without further treatment, such as coating. In a first application, their potential for nitrite removal (N. winogradskyi) is demonstrated, a typical challenge in potable water treatment.     

3‐D Interdigitated electrodes for uniform stimulation of electro‐responsive hydrogels for biomedical applications

Stimuli‐responsive hydrogels are continuing to increase in demand in biomedical applications. Occluding a blood vessel is one possible application which is ideal for a hydrogel because of their ability to expand in a fluid environment. However, typically stimuli‐responsive hydrogels focus on bending instead of radial uniform expansion, which is required for an occlusion application. This article focuses on using an interdigitated electrode device to stimulate an electro‐responsive hydrogel in order to demonstrate a uniform swelling/deswelling of the hydrogel. A Pluronic‐bismethacrylate (PF127‐BMA) hydrogel modified with hydrolyzed methacrylic acid, in order to make it electrically responsive, is used in this article. An interdigitated electrode device was manufactured containing Platinum electrodes. The results in this paper show that the electrically biased hydrogels deswelled 230% more than the non‐biased samples on average. The hydrogels deswelled uniformly and showed no visual deformations due to the electrical bias. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1523–1528     

Putting Electrospun Nanofibers to Work for Biomedical Research

Electrospinning has been exploited for almost one century to process polymers and related materials into nanofibers with controllable compositions, diameters, porosities, and porous structures for a variety of applications. Owing to its high porosity and large surface area, a non‐woven mat of electrospun nanofibers can serve as an ideal scaffold to mimic the extracellular matrix for cell attachment and nutrient transportation. The nanofiber itself can also be functionalized through encapsulation or attachment of bioactive species such as extracellular matrix proteins, enzymes, and growth factors. In addition, the nanofibers can be further assembled into a variety of arrays or architectures by manipulating their alignment, stacking, or folding. All these attributes make electrospinning a powerful tool for generating nanostructured materials for a range of biomedical applications that include controlled release, drug delivery, and tissue engineering.

     

Effect of Head Size in Head‐Tail‐Type Polycations on their in vitro Performances as Nonviral Gene Vectors

Three kinds of head‐tail‐type block copolymers composed of polyamidoamine (PAMAM) dendron heads and poly(L ‐lysine) (PLL) tail blocks (PAMAM dendron‐PLL), having PAMAM dendrons with different generations (G2.5‐PLL, G3.5‐PLL and G4.5‐PLL) were synthesized. Some of the dendron heads were located at polyplex surface, and G2.5‐PLL and G3.5‐PLL could form small polyplexes (less than 150 nm in size). G2.5‐PLL and G3.5‐PLL polyplexes were taken up into the cells more effectively. PAMAM dendron‐PLL that had a larger dendron head could show a more‐effective buffering effect. The in vitro performance of the PAMAM dendron‐PLL polyplexes was controlled by the balance of cellular uptake and endosomal escape by a buffering effect.

     

Responsive DNA‐Based Hydrogels and Their Applications

The term hydrogel describes a type of soft and wet material formed by cross‐linked hydrophilic polymers. The distinct feature of hydrogels is their ability to absorb a large amount of water and swell. The properties of a hydrogel are usually determined by the chemical properties of their constituent polymer(s). However, a group of hydrogels, called “smart hydrogels,” changes properties in response to environmental changes or external stimuli. Recently, DNA or DNA‐inspired responsive hydrogels have attracted considerable attention in construction of smart hydrogels because of the intrinsic advantages of DNA. As a biological polymer, DNA is hydrophilic, biocompatible, and highly programmable by Watson‐Crick base pairing. DNA can form a hydrogel by itself under certain conditions, and it can also be incorporated into synthetic polymers to form DNA‐hybrid hydrogels. Functional DNAs, such as aptamers and DNAzymes, provide additional molecular recognition capabilities and versatility. In this Review, DNA‐based hydrogels are discussed in terms of their stimulus response, as well as their applications.

     

Perfluorophenyl azide functionalization of electrospun poly(para‐dioxanone)

Strategies to surface‐functionalize scaffolds by covalent binding of biologically active compounds are of fundamental interest to control the interactions between scaffolds and biomolecules or cells. Poly(para‐dioxanone) (PPDO) is a clinically established polymer that has shown potential as temporary implant, eg, for the reconstruction of the inferior vena cava, as a nonwoven fiber mesh. However, PPDO lacks suitable chemical groups for covalent functionalization. Furthermore, PPDO is highly sensitive to hydrolysis, reflected by short in vivo half‐life times and degradation during storage. Establishing a method for covalent functionalization without degradation of this hydrolyzable polymer is therefore important to enable the surface tailoring for tissue engineering applications. It was hypothesized that treatment of PPDO with an N‐hydroxysuccinimide ester group bearing perfluorophenyl azide (PFPA) under UV irradiation would allow efficient surface functionalization of the scaffold. X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier‐transformed infrared spectroscopy investigation revealed the successful binding, while a gel permeation chromatography study showed that degradation did not occur under these conditions. Coupling of a rhodamine dye to the N‐hydroxysuccinimide esters on the surface of a PFPA‐functionalized scaffold via its amine linker showed a homogenous staining of the PPDO in laser confocal microscopy. The PFPA method is therefore applicable even to the surface functionalization of hydrolytically labile polymers, and it was demonstrated that PFPA chemistry may serve as a versatile tool for the (bio‐)functionalization of PPDO scaffolds.     

Visualizing Cholesterol Uptake by Self‐Assembling Rhodamine B‐Labeled Polymer Inside Living Cells via FLIM‐FRET Microscopy

Atherosclerosis is a widespread and hazardous disease characterized by the formation of arterial plaques mostly composed of fat, cholesterol, and calcium ions. The direct solubilization of cholesterol represents a promising, atheroprotective strategy to subside lipid blood levels and reverse atherosclerosis. This study deals with the in‐depth analysis of polymer‐mediated cholesterol dissolution inside living human cells. To this end, a recently described multifunctional block‐polymer is labeled with Rhodamine B (RhoB) to investigate its interaction with cells via fluorescence microscopy. This gives insight into the cellular internalization process of the polymer, which appears to be clathrin‐ and caveolae/raft‐dependent endocytosis. In cell single particle tracking reveals an active transport of RhoB polymer including structures. Förster resonance energy transfer (FRET) measurements of cells treated with a fluorophore‐tagged cholesterol derivative and the RhoB polymer indicates the uptake of cholesterol by the polymeric particles. Hence, these results present a first step toward possible applications of cholesterol‐absorbing polymers for treating atherosclerosis.     

Ultrafine hydrogel fibers with dual temperature‐ and pH‐responsive swelling behaviors

Ultrafine hydrogel fibers that were responsive to both temperature and pH signals were prepared through the electrospinning of poly(N‐isopropylacrylamide) (PNIPAAm) and poly(acrylic acid) mixtures in dimethylformamide. Both the diameters (700 nm to 1.2 μm) and packing of the fibers could be controlled through changes in the polymer compositions and PNIPAAm molecular weights. These fibers were rendered water‐insoluble by the addition of either Na₂HPO₄ or poly(vinyl alcohol) (PVA) to the solution, followed by the heat curing of the fibers. The fibers crosslinked with Na₂HPO₄ swelled to 30–120 times in water; this was significantly higher than the swelling of those crosslinked with PVA. The PVA‐crosslinked hydrogel fibers, however, exhibited faster swelling kinetics; that is, they reached equilibrium swelling in less than 5 min at 25 °C. They were also more stable after 1 week of water exposure; that is, they lost less mass and retained their fibrous form better. All the hydrogel fibers showed a drastic increase in the swelling between pH 4 and 5. The PVA‐crosslinked hydrogel fibers exhibited distinct temperature‐responsive phase‐transition behavior of PNIPAAm, whereas the Na₂HPO₄‐crosslinked hydrogel fibers showed altered two‐stage phase transitions that reflected side‐chain modification of PNIPAAm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6331–6339, 2004     

Modified Hyaluronan Hydrogels Support the Maintenance of Mouse Embryonic Stem Cells and Human Induced Pluripotent Stem Cells

These studies provide evidence for the ability of a commercially available, defined, hyaluronan‐gelatin hydrogel, HyStem‐C?, to maintain both mouse embryonic stem cells (mESCs) and human induced pluripotent stem cells (hiPSCs) in culture while retaining their growth and pluripotent characteristics. Growth curve and doubling time analysis show that mESCs and hiPSCs grow at similar rates on HyStem‐C? hydrogels and mouse embryonic fibroblasts and Matrigel?, respectively. Immunocytochemistry, flow cytometry, gene expression and karyotyping reveal that both human and murine pluripotent cells retain a high level of pluripotency on the hydrogels after multiple passages. The addition of fibronectin to HyStem‐C? enabled the attachment of hiPSCs in a xeno‐free, fully defined medium.

     

Full‐Color Emissive Poly(Ethylene Oxide) Electrospun Nanofibers Containing a Single Hyperbranched Conjugated Polymer for Large‐Scale,Flexible Light‐Emitting Sheets

White‐light‐emitting protocols based on organic materials have received much attention in the academic and industrial fields because of their potential applications in full‐color displays and back‐lighting units for liquid crystal displays. Here, the attempt is made to fabricate white‐light‐emitting, electrospun poly(ethylene oxide) (PEO) sheets containing controlled concentrations of a single light‐emitting material composed of a type of hyperbranched conjugated polymer (HCP). The HCPs used here have the unique property of exhibiting a variety of fluorescence colors in the electrospun matrix that is caused by the different distances between HCP chains depending on their concentrations, leading to different degrees of intermolecular energy transfer. Therefore, the emission colors of the PEO sheets can be easily manipulated by simply varying the HCP concentrations in the PEO matrix. The resulting method for fabricating nanofibers comprising light‐emitting materials in the polymer matrix has great potential for easy fabrication of cost‐effective, flexible light‐emitting system.

     

Dual-syringe reactive electrospinning of cross-linked hyaluronic acid hydrogel nanofibers for tissue engineering applications

A facile fabrication of a cross-linked hyaluronic acid (HA) hydrogel nanofibers by a reactive electrospinning method is described. A thiolated HA derivative, 3,3'-dithiobis(propanoic dihydrazide)-modified HA (HA-DTPH), and poly(ethylene glycol) diacrylate (PEGDA) are selected as the cross-linking system. The cross-linking reaction occurs simultaneously during the electrospinning process using a dual-syringe mixing technique. Poly(ethylene oxide) (PEO) is added into the spinning solution as a viscosity modifier to facilitate the fiber formation and is selectively removed with water after the electrospinning process. The nanofibrous structure of the electrospun HA scaffold is well preserved after hydration with an average fiber diameter of 110 nm. A cell morphology study on fibronectin (FN)-adsorbed HA nanofibrous scaffolds shows that the NIH 3T3 fibroblasts migrate into the scaffold through the nanofibrous network, and demonstrate an elaborate three-dimensional dendritic morphology within the scaffold, which reflects the dimensions of the electrospun HA nanofibers. These results suggest the application of electrospun HA nanofibrous scaffolds as a potential material for wound healing and tissue regeneration. [image: see text] Laser scanning confocal microscopy demonstrates that the NIH3T3 fibroblast develops an extended 3D dendritic morphology within the fibronectin-adsorbed electrospun HA nanofibrous scaffold.     

Thermally Tunable Surface Wettability of Electrospun Fiber Mats: Polystyrene/Poly(N‐isopropylacrylamide) Blended versus Crosslinked Poly[(N‐isopropylacrylamide)‐co‐(methacrylic acid)]

This work reports on thermally tunable surface wettability of electrospun fiber mats of: polystyrene (PS)/poly(N‐isopropylacrylamide) (PNIPA) blended (bl‐PS/PNIPA) and crosslinked poly[(N‐isopropylacrylamide)‐co‐[methacrylic acid)] (PNIPAMAA) (xl‐NIPAMAA). Both the bl‐PS/PNIPA and xl‐PNIPAMAA fiber mats demonstrate reversibly switchable surface wettability, with the bl‐PS/PNIPA fiber mats approaching superhydrophobic ≥150° and superhydrophilic contact angle (CA) values at extreme temperatures. Weight loss studies carried out at 10 °C indicate that the crosslinked PNIPAMAA fiber mats had better structural integrity than the bl‐PS/PNIPA fiber mats. PNIPA surface chemistry and the Cassie–Baxter model were used to explain the mechanism behind the observed extreme wettability.

     

Photocrosslinkable Liquid Crystal Main‐Chain Polymers: Thin Films and Electrospinning

For mechanical actuators, a response to external stimuli is required. Main‐chain liquid crystal elastomers (MCLCEs) show high response to changes in temperature especially in the vicinity of a phase transition. Most of these crosslinked materials were synthesized in a one‐step reaction which leads to a macroscopically aligned elastomer. Up to now only macroscopic samples have been prepared. We are presenting a new approach which allows us to prepare thin films as well as aligned fibers. First a liquid crystalline main‐chain polymer with a photoactive moiety was synthesized, which was oriented by a mechanical field and photocrosslinked. The thin films show exceptional mechanical properties such as large temperature‐dependent changes in length and a nonlinear stress–strain relation. To obtain fibers, we used the electrospinning process from solution with in situ UV curing. We obtained crosslinked fibers with a uniform alignment of the nematic director.

     

Effects of pigments on the volume‐phase‐transition properties of N‐isopropylacrylamide gels as light‐modulation materials

The effects of pigments contained in N‐isopropylacrylamide (NIPAM) gels on their volume‐change properties were investigated. All the NIPAM gel particles, containing various kinds and concentrations of pigments, showed a volume phase transition at 34 °C. No pigment affected the volume‐phase‐transition temperature of the NIPAM gels. As the concentration of the pigment in the NIPAM gels was increased, the amount of the volume change of the NIPAM gels was reduced. The water absorptivity of the NIPAM gels in the swollen state decreased as the pigment concentration increased, whereas the water absorptivity in the shrunken state was almost constant. Reducing the initial monomer concentration of the polymerization of the NIPAM gel increased the water absorptivity in the swollen state. With an increase in the water absorptivity, the volume changes of the NIPAM gels containing pigments were increased. Prototype light modulators in which the NIPAM gel particles containing pigment were dispersed between glass plates were fabricated. The light modulator using the gel particles with improved diameter change (d/d₀ = 2.3, where d and d₀ are the equilibrium diameter and the diameter of the fully shrunken state at 50 °C, respectively) exhibited a larger transmittance change from 8 to 79% than that using the gel particles before the improvement (d/d₀ = 1.7; from 38 to 79%) according to temperature changes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4644–4655, 2006     

Facile Fabrication of Graphene‐Containing Foam as a High‐Performance Anode for Microbial Fuel Cells

Facile fabrication of novel three‐dimensional anode materials to increase the bacterial loading capacity and improve substrate transport in microbial fuel cells (MFCs) is of great interest and importance. Herein, a novel graphene‐containing foam (GCF) was fabricated easily by freeze‐drying and pyrolysis of a graphene oxide–agarose gel. Owing to the involvement of graphene and stainless‐steel mesh in the GCF, the GCF shows high electrical conductivity, enabling the GCF to be a conductive electrode for MFC applications. With the aid of agarose, the GCF electrode possesses a supermacroporous structure with pore sizes ranging from 100–200 μm and a high surface area, which greatly increase the bacterial loading capacity. Cell viability measurements indicate that the GCF possesses excellent biocompatibility. The MFC, equipped with a 0.4 mm‐thick GCF anode, shows a maximum area power density of 786 mW m^?2, which is 4.1 times that of a MFC equipped with a commercial carbon cloth anode. The simple fabrication route in combination with the outstanding electrochemical performance of the GCF indicates a promising anode for MFC applications.     

Specific Adhesion of 3T3‐L1 Fibroblast onto Uridine‐Containing Polystyrene

A hydrophobic 96‐well multiplate was incubated with aqueous poly(uridine 5′‐p‐styrenesulfonate) (PUSS). Analysis of the PUSS‐coated surface indicated that the surface incubated at higher polymer concentration (50 mg·mL^–1) was hydrophilic while the surface incubated at lower polymer concentration (1 mg·mL^–1) was hydrophobic. Adhesion of 3T3‐L1, which has GalTase on the cell membrane, on the hydrophobic PUSS‐coated surface was greater than on the non‐coated surface. 3T3‐L1 adhesion on the hydrophilic PUSS‐coated surface was even greater. On the other hand, the adhesion of HeLa cells, which did not show GalTase on the cell membrane, on the hydrophilic surface was quite weak. It may well be said that the 3T3‐L1 adhesion on the hydrophilic PUSS‐coated surface was GalTase‐mediated.     

Field‐Driven Surface Segregation of Biofunctional Species on Electrospun PMMA/PEO Microfibers

The need to biofunctionalize polymer surfaces for targeted bio‐related applications continues to grow, and efforts designed to meet this need rely heavily on surface grafting or polymerization. In this study, we provide a viable alternative by demonstrating that the peptide segment of a polymer‐peptide conjugate can be selectively driven to the surface of polymer nano/microfibers during electrospinning due to contrast in polarizability. Judicious choice of the polymer sequence in the conjugate permits use of the conjugate with compatible fiber‐forming polymers. Here, we use a water soluble poly(ethylene oxide)‐containing conjugate in combination with a hydrophobic thermoplastic, poly(methyl methacrylate). Surface enrichment is measured by X‐ray photoelectron spectroscopy, and fiber morphology is investigated by electron microscopy. Microfibers generated from the blends examined here are largely resistant to long term water immersion and are thus suited as support scaffolds or filtration membranes.