High Dielectric Poly(vinylidene fluoride)-Based Polymer Enables Uniform Lithium-Ion Transport in Solid-State Ionogel Electrolytes.

Ionic liquids (ILs)-incorporated solid-state polymer electrolytes (iono-SPEs) have high ionic conductivities but show non-uniform Li+ transport in different phases. This work greatly promotes Li+ transport in polymer phases by employing a poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE), PTC] as the framework of ILs to prepare iono-SPEs. Unlike PVDF, PTC with suitable polarity shows weaker adsorption energy on IL cations, reducing their possibility of occupying Li+ -hopping sites. The significantly higher dielectric constant of PTC than PVDF facilitates the dissociation of Li-anions clusters. These two factors motivate Li+ transport along PTC chains, narrowing the difference in Li+ transport among varied phases. The LiFePO4 /PTC iono-SPE/Li cells cycle steadily with capacity retention of 91.5 % after 1000 cycles at 1 C and 25 °C. This work paves a new way to induce uniform Li+ flux in iono-SPEs through polarity and dielectric design of polymer matrix.

HA-coated collagen nanofibers for urethral regeneration via in situ polarization of M2 macrophages.

In situ tissue engineering utilizes the regenerative potential of the human body to control cell function for tissue regeneration and has shown considerable prospect in urology. However, many problems are still to be understood, especially the interactions between scaffolds and host macrophages at the wound site and how these interactions direct tissue integration and regeneration. This study was designed to evaluate the efficacy of hyaluronic acid (HA) functionalized collagen nanofibers in modulating the pro-healing phenotype expression of macrophages for urethral regeneration. Tubular HA-collagen nanofibers with HA-coating were prepared by coaxial electrospinning. The formation of a thin HA-coating atop each collagen nanofiber endowed its nanofibrous mats with higher anisotropic wettability and mechanical softness. The macrophages growing on the surface of HA-collagen nanofibers showed an elongated shape, while collagen nanofibers' surface exhibited a pancake shape. Immunofluorescence and ELISA analysis showed that elongation could promote the expression of M2 phenotype marker and reduce the secretion of inflammatory cytokines. In vivo experiments showed that tubular HA-collagen nanofibers significantly facilitate male puppy urethral regeneration after injury. In the regenerated urethra bridged by tubular HA-collagen nanofibers, anti-inflammatory M2 macrophages are recruited to the surface of the scaffold, which can promote angiogenesis and endogenous urothelial progenitor cell proliferation.

Hydrogen bonding in aprotic solvents, a new strategy for gelation of bioinspired catecholic copolymers with N-isopropylamide.

Copolymers of N-isopropylacrylamide (NIPAM) and dopamine methacrylate can establish a reversible, self-healing 3D network in aprotic solvents based on hydrogen bonding. The reactivity and hydrogen bonding formation of catechol groups in copolymer chains are studied by UV-vis and (1) H NMR spectroscopy, while reversibility from sol to gel and inverse as well as self-healing properties are tested rheologically. The produced reversible organogel can self-encapsulate physically interacting or chemically bonded solutes such as drugs due to thermosensitivity of the used copolymer. This system offers dual-targeted and controlled drug delivery and release-by slowing down release kinetics by supramolecular bonding of the drug and by reducing diffusion rates due to modulus increase.

Network formation in graphene oxide composites with surface grafted PNIPAM chains in aqueous solution characterized by rheological experiments.

Poly N-isopropyl acrylamide (PNI) radically polymerized in aqueous solution in the presence of graphene oxide (GO) can significantly change the properties of the resulting solution from a regular polymer solution to a soft solid with a GO content of only 0.176 wt% (3 wt% with respect to PNI). However, these properties require the presence of both grafting and supramolecular interactions between polymer chains and hydrophilic groups on GO (-OH, -COOH), proven by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffraction and spectroscopy (XRD) and Raman spectra. While very low GO-contents (below 0.05 wt%) only lead to a labile structure, which can be disassembled by shear, higher contents yield composites with solid-like characteristics. This is clearly evident from the rheological behaviour, which changes significantly at a GO content around 0.15 wt%. Intensive shearing destroys the weak network, which cannot reform quickly at lower GO-concentrations, while at intermediate concentrations, restructuring is fast. GO-contents of 0.176 wt% lead to a material behaviour, which almost perfectly recovers from small deformations (creep and creep recovery compliance almost match) but larger deformations lead to permanent damage to the sample.

Biomimetic electrospun tubular PLLA/gelatin nanofiber scaffold promoting regeneration of sciatic nerve transection in SD rat.

The micro- or nanoscale surface morphology of the tissue engineering nerve guidance scaffold (NGS) will affect different cell behaviors, such as their growth rate, migration, and matrix secretion. Although different technologies for manufacturing scaffolds with biomimetic topography have been established, most of them tend to be high cost and long preparation time. Here we have prepared a biomimetic NGS with physical properties to simulate native nerve tissue more accurately. We used poly(l-lactic acid) (PLLA) nanofibers doped with gelatin to prepare a biomimetic NGS whose structure mimics the native epineurium layer. By adjusting the doping ratio of gelatin and PLLA in the tubular scaffold, the bionic scaffold's surface morphology and mechanical properties are closer to native tissues. In vitro cell scaffold interaction experiments demonstrated that the PLLA/gelatin nanofibers could significantly promote the elongation, proliferation, and the secretion of glial cell-derived neurotrophic factor (GDNF) of RSC96 Schwann cells (SCs), as well as the diffusion of GDNF. In vivo scaffold replacement of SD rat, sciatic nerves showed that the nerve guide scaffold composed of PLLA/gelatin nanofibers was helpful to the myelination of SCs and the remolding of epineurium in the injured area, which could effectively rehabilitate the motor and sensory functions of the injured nerve and prevent the atrophy of the target muscle tissue. This study showed that the synergistic impact of nano topographical and biochemical clues on designing biomimetic scaffolds could efficiently promote regenerating nerve tissue.

Hyaluronic acid-functionalized poly-lactic acid (PLA) microfibers regulate vascular endothelial cell proliferation and phenotypic shape expression.

This work was designed to evaluate the efficacy of hyaluronic acid (HA) functionalized tubular poly-lactic acid (PLA) microfibers in directing the luminal pre-endothelialization of vascular endothelial cells (ECs). Tubular HA/PLA microfibers with hierarchical architecture were prepared by electrospinning and chemical cross-linking process. A layer of HA microfibrous film coating was fixed on the inner wall surface of the tubular HA/PLA microfibers, resulting in higher anisotropy wettability and relatively lower surface energy and roughness. We confirmed that HA coating on PLA microfibers surface have reduced hemolytic activity and coagulation degree. Mouse vascular ECs exhibited surface-dependent differences in cell elongation and proliferation (HA/PLA > PLA). Compared with PLA microfibers, the gene expression levels of platelet EC adhesion molecule-1 (PECAM-1/CD31) and vascular endothelial growth factor (VEGF) in ECs of HA/PLA microfibers surface were up-regulated. Immunostaining analysis revealed that the surface of HA/PLA nanofibers supported the expression of mature vascular EC phenotype CD31 protein. In vitro co-culture analysis showed that the luminal pre-endothelialization induced vascular smooth muscle cells (SMCs) to maintain their phenotypic shape and establish natural behavior patterns in the hierarchical tubular scaffold. These studies indicate that the biophysical cues of scaffolds are potent regulators of vascular EC endothelialization.

Adsorptional-photocatalytic removal of fast sulphon black dye by using chitin-cl-poly(itaconic acid-co-acrylamide)/zirconium tungstate nanocomposite hydrogel.

In the present work, the removal of fast sulphon black (FSB) dye from water was executed by using chitin-cl-poly(itaconic acid-co-acrylamide)/zirconium tungstate nanocomposite hydrogel (Ch-cl-poly(IA-co-AAm)-ZrW NCH). The Ch-cl-poly(IA-co-AAm)-ZrW NCH was fabricated proficiently by microwave-induced sol-gel/copolymrization method. The zirconium tungstate (ZrW) photocatalyst was prepared by co-precipitation method using sodium tungstate and zirconium oxychloride in ratio (2:1). The polymeric hydrogel part has been used to support the ZrW, and it acted as an adsorbent for adsorptive removal of FSB dye. The band gap for nanocomposite hydrogel was found about 4.18 eV by using Tauc equation. The Ch-cl-poly(IA-co-AAm)-ZrW NCH was characterized by various techniques as FTIR (Fourier-transform infrared spectroscopy), X-ray diffraction (XRD), transmittance electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM). The adsorptional-photocatalytic remediation experiment of FSB dye was optimized for reaction parameters as FSB dye and Ch-cl-poly(IA-co-AAm)-ZrW NCH concentration, and pH. The maximum percentage removal for FSB dye was observed at 92.66% in 120 min under adsorptional-photocatalysis condition.

In-situ crosslinked hydrogel based on amidated pectin/oxidized chitosan as potential wound dressing for skin repairing.

Hydrogel can provide a favorable moisture environment for skin wound healing. In this study, a novel in-situ crosslinked injectable hydrogel was prepared using the water-soluble amidated pectin (AP) and oxidized chitosan (OC) through Schiff-base reaction without any chemical crosslinker. The influence of AP content on the properties of the hydrogel was systemically investigated. It showed that gelation time, pore structure, swelling capability and degradability of the hydrogel can be tuned by varying the content of amine and aldehyde groups from AP and OC. All the porous hydrogels with various AP contents (65%, 70%, and 80%) presented desirable gelation time, swelling property, high hemocompatibility and biocompatibility. Particularly, AP-OC-65 hydrogel presented superior swelling capability and better hemo- and bio-compatibility, owing to more residual amine sites in the hydrogel. Therefore, the injectable AP-OC-65 hydrogel has a greater potential for application to wound dressing or skin substitute.

Atrazine removal using chitin-cl-poly(acrylamide-co-itaconic acid) nanohydrogel: Isotherms and pH responsive nature.

Removal of commonly used pesticide, atrazine was examined by employing chitin based nanohydrogel. Chitin-cl-poly (acrylamide-co-itaconic acid) nanohydrogel was synthesized by microwave method. Dissolution of chitin was done by freezing thawing method in NaOH/urea solution. The morphology and functional characteristics were confirmed by FTIR, XRD, SEM, TGA, TEM, and EDX techniques. Maximum swelling capacity, isotherm study, kinetics, adsorption and desorption of atrazine pesticide were evaluated in this study. Maximum adsorption capacity of designed nanohydrogel was found to be 204.08 mg/g. Langmuir and pseudo- second order models were determined to be applicable for explaining the undertaken adsorption process. Neutral pH was found to be favorable for maximum adsorption. In addition, results have specified the pH responsive nature of nanohydrogel for controlled release of atrazine.

Designing a multifaceted bio-interface nanofiber tissue-engineered tubular scaffold graft to promote neo-vascularization for urethral regeneration.

Reconstitution of urethral defects through a tissue-engineered autologous urethra is an exciting area of clinical urology research. Despite rapid advances in this field, a tissue-engineered urethra is still inaccessible to clinical applications because of the poor vascularization of the current scaffold materials, especially for the reconstruction of complex urethral defects. In this study, we report the preparation of multifaceted bio-interfacing tissue-engineered autologous scaffolds based on alternating block polyurethane (abbreviated as PU-alt), a kind of tubular scaffold with a hierarchical nanofiber architecture, flexible mechanical properties and a hydrophilic PEGylation interface capable of promoting adhesion, oriented elongation, and proliferation of New Zealand rabbit autologous urethral epithelial cells (ECs) and smooth muscle cells (SMCs) simultaneously, and also upregulating the expression of keratin (AE1/AE3) in ECs and contractile protein (α-SMA) in SMCs as well as the subsequent synthesis of elastin. Three months in vivo scaffold substitution of rabbit urethras displayed that the engineered autologous PU-alt scaffold grafts, with a coating rich in seed cell-matrix, could induce local neo-vascularization, facilitating oriented SMC remodeling and lumen epithelialization as well as patency. Our findings indicate a central role of the synergistic interplay of seed cell-matrix bio-interface and nano-topographic cues in the vascularized urethral reconstruction.

Urethral reconstruction using an amphiphilic tissue-engineered autologous polyurethane nanofiber scaffold with rapid vascularization function.

Reconstruction and functional rehabilitation of the long urethra in males is one of the difficult tasks in urological treatment. Although many kinds of tissue-engineered urethra scaffold grafts have been successfully used in animals and even clinical research of urethra reconstruction, they all have the disadvantages of slow vascularization in scaffolds, which may lead to complications such as stricture and blockage of the urethra. Here, an amphiphilic polyurethane tubular nanofiber scaffold with a hierarchical structure was designed as a urethral scaffold. The scaffold can regulate the phenotypic expression of epithelial cells (ECs) and smooth muscle cells (SMCs) in vitro and in vivo. Upon transplantation into the Beagle puppy's defective urethral site, the engineered PU-ran tubular scaffold graft, rich in seeded cell-matrix bio-interfaces, could induce local neo-vascularization in a controlled way, which facilitated lumen epithelialization and functional rehabilitation. This is favorable for urethral tissue-oriented reconstruction. These findings suggest the pivotal role of nano-topographical and biochemical features in the vascularized biomimetic scaffold design for efficacious urethral reconstruction.

Agarose-based biomaterials for advanced drug delivery.

Agarose is a prominent marine polysaccharide representing reversible thermogelling behavior, outstanding mechanical properties, high bioactivity, and switchable chemical reactivity for functionalization. As a result, agarose has received particular attention in the fabrication of advanced delivery systems as sophisticated carriers for therapeutic agents. The ever-growing use of agarose-based biomaterials for drug delivery systems resulted in rapid growth in the number of related publications, however still, a long way should be paved to achieve FDA approval for most of the proposed products. This review aims at a classification of agarose-based biomaterials and their derivatives applicable for controlled/targeted drug delivery purposes. Moreover, it attempts to deal with opportunities and challenges associated with the future developments ahead of agarose-based biomaterials in the realm of advanced drug delivery. Undoubtedly, this class of biomaterials needs further advancement, and a lot of critical questions have yet to be answered.

Investigation of micromechanical properties of hard sphere filled composite hydrogels by atomic force microscopy and finite element simulations.

Atomic force microscopy (AFM) indentation is the most suitable way to characterize micromechanical properties of soft materials such as bio tissues. However, the mechanical data obtained from force-indentation measurement are still not well understood due to complex geometry of the bio tissue, nonlinearity of indentation contact, and constitutive relation of hyperelastic soft material. Poly-N-isopropyl acrylamide (PNIPAM) filled with 5wt% polystyrene (PS) sphere particles material system can be utilized as a simplified model for mimicking a whole host of soft materials. Finite element model has been constructed to simulate indentation as in AFM experiments using colloidal probes for a parametric study, with the main purpose of understanding the effect of particles on overall behavior of mechanical data and local deformation field under indentation contact. Direct comparison between finite element simulation and indentation data from AFM experiments provides a powerful method to characterize soft materials properties quantitatively, addressing the lack of analytical solutions for hard-soft composites, both biological and synthetic ones. In this framework, quantitative relations are found between the depth, at which the particle was embedded, the particle size and the elastic modulus of the overall composite. Comprehensive characterizations were established to distinguish indentation on a particle residing on top of the hydrogel from a particle embedded inside the hydrogel matrix. Finally, different assumptions of interface friction at the boundary between the particle and the hydrogel have been tested and directly compared with experimental measurements.

Facile fabrication of polyurethane microcapsules carriers for tracing cellular internalization and intracellular pH-triggered drug release.

A tailor-made traceable pH-sensitive drug delivery system based on polyurethane (PU) microcapsules was fabricated using a facile double-emulsion method containing 3,3'-dioctadecyloxacarbocyanine perchlorate, doxorubicin (DOX) and sodium bicarbonate (NaHCO3). When PU microcapsules were immersed in acidic media, NaHCO3 could react with the H+ to quickly produce CO2 bubbles to puncture the PU shell, resulting in rapid release of DOX to promptly reach the intracellular drug therapeutic threshold to kill cancer cells in a short period. Confocal laser scanning microscopic analysis showed that these traceable pH-sensitive drug carriers can be easily internalized by BGC 823 and Hela cells, and the loaded DOX can quickly release from PU microcapsules in the endo-/lysosomes to be mainly resided in cell nuclei. This traceable pH-sensitive drug carrier can achieve on-demand controlled release profiles for visualization of cancer therapy. Thus, it is a potential candidate for anticancer drug delivery system in advanced cancer therapy.

Microfluidic-assisted self-assembly of complex dendritic polyethylene drug delivery nanocapsules.

Microfluidic platform for the synthesis of complex nanocapsules is presented via a controlled self-assembly. The monodisperse nanocapsules in the range of 50-200 nm consist of a dendritic polyethylene core and a Pluronic copolymer shell. The resultant nanocarriers encapsulate large amount of hydrophobic anticancer drug like paclitaxel while providing a low complement activation as well as sustained release profile with high tunability.

High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.