Polypyrrole Derivatives: Preparation, Properties and Application.

Polypyrrole (PPy) has attracted widespread attention due to its excellent environmental stability, high conductivity, simple synthesis, good biocompatibility, and reversible redox properties. PPy derivatives not only inherit the advantages of polypyrrole, but also have some unique properties. The side and N-site substitution of PPy can not only yield polymers with good solubility, but it also endows polymers with special functionalities by controlling the introduced functional groups. The performance of copolymers can also be adjusted by the type of monomer or polymerization ratio. In this review, an overview of the different types, main preparation methods, and the application prospects of PPy derivatives reported to date are summarized and presented. The current challenges and future opportunities in this research area are also prospected.

Enhancing Mechanical Properties and Microstructures of Mass-Manufactured Sand Concrete by Incorporating Granite Powder.

The production of manufactured sand and stone processing can cause dust pollution due to the generation of a significant amount of stone powder. This dust (mainly granite powder) was collected and incorporated as a cement replacement into mass-manufactured sand concrete in order to enhance the mechanical properties and microstructures. The heat of the hydration was measured by adding the granite powder into the cementitious material system. The mechanical properties, autogenous shrinkage, and pore structures of the concrete were tested. The results showed that the mechanical strength of the concrete increased first and then decreased with the increase in granite powder content. By replacing the 5% cement with the granite powder, the 28 d compressive and flexural strength increased by 17.6% and 20.9%, respectively. The autogenous shrinkage was mitigated by the incorporation of the 10% granite powder and decreased by 19.7%. The mechanism of the granite powder in the concrete was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and mercury intrusion porosimetry (MIP). The porosity decreased significantly within the 10% granite powder. A microstructure analysis did not reveal a change in the type of hydration products but rather that the granite powder played a role in the microcrystalline nucleation during the hydration process.

Multiple Dynamic Bonds-Driven Integrated Cathode/Polymer Electrolyte for Stable All-Solid-State Lithium Metal Batteries.

All-solid-state lithium metal batteries (LMBs) are considered as the promising higher-energy and improved-safety energy-storage systems. Nevertheless, the electrolyte-electrodes interfacial issues due to the limited solid physical contact lead to discontinuous interfacial charge transport and large interfacial resistance, thereby suffering from unsatisfactory electrochemical performance. Herein, we construct an integrated cathode/polymer electrolyte for all-solid-state LMBs under the action of polymer chains exchange and recombination originating from multiple dynamic bonds in our well-designed dynamic supramolecular ionic conductive elastomers (DSICE) molecular structure. The DSICE acts as polymer electrolytes with excellent electrochemical performance and mechanical properties, achieving the ultrathin pure polymer electrolyte thickness (12 µm). Notably, the DSICE also functions as lithium iron phosphate (LiFePO4 , LFP) cathode binders with enhanced adhesive capability. Such well-constructed Li|DSICE|LFP-DSICE cells generate delicate electrolyte-electrodes interfacial contact at the molecular level, providing continuous Li+ transport pathways and promoting uniform Li+ deposition, further delivering superior long-term charge/discharge stability (>600 cycles, Coulombic efficiency, >99.8 %) and high capacity retention (80 % after 400 cycles). More practically, the Li|DSICE|LFP-DSICE pouch cells show stable electrochemical performance, excellent flexibility and safety under abusive tests.

Polypyrrole Nanomaterials: Structure, Preparation and Application.

In the past decade, nanostructured polypyrrole (PPy) has been widely studied because of its many specific properties, which have obvious advantages over bulk-structured PPy. This review outlines the main structures, preparation methods, physicochemical properties, potential applications, and future prospects of PPy nanomaterials. The preparation approaches include the soft micellar template method, hard physical template method and templateless method. Due to their excellent electrical conductivity, biocompatibility, environmental stability and reversible redox properties, PPy nanomaterials have potential applications in the fields of energy storage, biomedicine, sensors, adsorption and impurity removal, electromagnetic shielding, and corrosion resistant. Finally, the current difficulties and future opportunities in this research area are discussed.

Phase-locked constructing dynamic supramolecular ionic conductive elastomers with superior toughness, autonomous self-healing and recyclability.

Stretchable ionic conductors are considerable to be the most attractive candidate for next-generation flexible ionotronic devices. Nevertheless, high ionic conductivity, excellent mechanical properties, good self-healing capacity and recyclability are necessary but can be rarely satisfied in one material. Herein, we propose an ionic conductor design, dynamic supramolecular ionic conductive elastomers (DSICE), via phase-locked strategy, wherein locking soft phase polyether backbone conducts lithium-ion (Li+) transport and the combination of dynamic disulfide metathesis and stronger supramolecular quadruple hydrogen bonds in the hard domains contributes to the self-healing capacity and mechanical versatility. The dual-phase design performs its own functions and the conflict among ionic conductivity, self-healing capability, and mechanical compatibility can be thus defeated. The well-designed DSICE exhibits high ionic conductivity (3.77 × 10-3 S m-1 at 30 °C), high transparency (92.3%), superior stretchability (2615.17% elongation), strength (27.83 MPa) and toughness (164.36 MJ m-3), excellent self-healing capability (~99% at room temperature) and favorable recyclability. This work provides an interesting strategy for designing the advanced ionic conductors and offers promise for flexible ionotronic devices or solid-state batteries.

Pattern formation in thin polymeric films via electrohydrodynamic patterning.

The free surface of a thin polymeric film is often unstable and deforms into various micro-/nano-patterns under an externally applied electric field. This paper reviews a recent patterning technique, electrohydrodynamic patterning (EHDP), a straightforward, cost-effective and contactless bottom-up method. The theoretical and numerical studies of EHDP are shown. How the characteristic wavelength and the characteristic time depend on both the external conditions (such as voltage, film thickness, template-substrate spacing) and the initial polymer properties (such as rheological property, electrical property and surface tension) is theoretically and experimentally discussed. Various possible strategies for fabricating high-aspect-ratio or hierarchical patterns are theoretically and experimentally reviewed. Aligning and ordering of the anisotropic polymers by EHDP is emphasized. A perspective, including novelty and limitations of the methods, particularly in comparison to some conventional patterning techniques, and a possible future direction of research, is presented.

Effect of Sulfate Concentration on Chloride Diffusion of Concrete under Cyclic Load.

The existence of chloride ions, sulfate ions, and vehicle dynamic loads may lead to a shortened service life and premature failure of the road and bridge structures in northwestern China. Immersed in a dual-salt solution while simultaneously applying cyclic flexural loads, the free chloride ion concentration and erosion depth in concrete specimens were measured. The influence of the sulfate concentration on the apparent surface chloride concentration (Cs) and apparent diffusion coefficient (Dapp) was studied. An exponential model was used to fit the Cs, and the influence of sulfate concentration on the Cs was analyzed. The result showed that cyclic loading and solution concentration were two primary factors affecting chloride diffusion. Meanwhile, compared with the emersion conditions, dynamic loading would induce significantly accelerated chloride ion penetration. Under the coupling effect of sulfate and dynamic loading, as the sulfate concentration increased, the chloride ion concentration and erosion depth were both decreased. The existence of sulfate ions improved the chloride ion penetration resistance of concrete. The results provide insight in designing concrete in regions where multiple salt ingression (sulfate and chloride) is a major durability issue of the structures.

Crystallization Control of N,N'-Dioctyl Perylene Diimide by Amphiphilic Block Copolymers Containing poly(3-Hexylthiophene) and Polyethylene Glycol.

The preparation of micron- to nanometer-sized functional materials with well-defined shapes and packing is a key process to their applications. There are many ways to control the crystal growth of organic semiconductors. Adding polymer additives has been proven a robust strategy to optimize semiconductor crystal structure and the corresponding optoelectronic properties. We have found that poly(3-hexylthiophene) (P3HT) can effectively regulate the crystallization behavior of N,N'-dioctyl perylene diimide (C8PDI). In this study, we combined P3HT and polyethylene glycol (PEG) to amphiphilic block copolymers and studied the crystallization modification effect of these block copolymers. It is found that the crystallization modification effect of the block copolymers is retained and gradually enhanced with P3HT content. The length of C8PDI crystals were well controlled from 2 to 0.4 µm, and the width from 210 to 35 nm. On the other hand, due to the water solubility of PEG block, crystalline PEG-b-P3HT/C8PDI micelles in water were successfully prepared, and this water phase colloid could be stable for more than 2 weeks, which provides a new way to prepare pollution-free aqueous organic semiconductor inks for printing electronic devices.

Effects of surface condition of conductive electrospun nanofiber mats on cell behavior for nerve tissue engineering.

Electrospun nanofibrous scaffold is a promising implant for peripheral nerve regeneration. Herein, to investigate the effect of surface morphological features and electrical properties of scaffolds on nerve cell behavior, we modified electrospun cellulose (EC) fibrous mats with four kind of soluble conductive polymers derivates (poly (N-(methacryl ethyl) pyrrole) (PMAEPy), poly (N-(2-hydroxyethyl) pyrrole) (PHEPy), poly (3-(Ethoxycarbonyl) thiophene) (P3ECT) and poly (3-thiophenethanol) (P3TE)) by an in-situ polymerization method. The morphological characterization showed that conductive polymers formed aggregated nanoparticles and coatings on the EC nanofibers with the increased fiber diameter further affected the surface properties. Compared with pure EC scaffold, more PC12 cells were adhered and grown on modified mats, with more integral and clearer cell morphology. The results of protein adsorption study indicated that modified EC mats could provide more protein adsorption site due to their characteristic surface morphology, which is beneficial to cell adhesion and growth. The results in this study suggested that these conductive polymers modified scaffolds with special surface morphology have potential applications in neural tissue engineering.

Facile preparation of pH/redox dual-responsive biodegradable polyphosphazene prodrugs for effective cancer chemotherapy.

In order to maximize the therapeutic effect and and minimize the systemtic side effect of the small molecule anticancer drugs, biodegradable drug delivery systems (DDSs) that respond to tumor microenvironment (TME) have attracted significant attention. Herein, a novel redox/pH dual-responsive and biodegradable polyphosphazene (PPZ) nano-prodrugs have been prepared via one-pot crosslinking of vanillin modified DOX (VMD, acid-sensitive) and 4,4'-dihydroxydiphenyl disulfide (HPS, GSH-responsive) with hexachlorocyclotriphosphazene (HCCP). The phenol groups of the as-synthesized VMD and HPS have high nucleophilic substitution activity towards HCCP under base catalyst and afforded PPZ nano-prodrugs, denoted as HCCP-VMD-HPS, with a high drug loading ratio of up to 56.4 %. As expected, the skeleton of the PPZ consisting of imine bonds in VMD and the disulfide bonds in HPS and cyclotriphosphazenes inclined to be decomposed in low pH conditions and high level of GSH environments. The antitumor drug DOX was found to be controlled released in TME conditions (extracellular, pH∼6.8 and endosomes, lysosomes pH∼5.0 with ∼10 mM GSH), rather than neutral physiological conditions (pH 7.4 with ∼20 µM GSH). Moreover, the resulting HCCP-VMD-HPS nano-prodrug have obvious cytotoxicity to cancer cells while a negligible side effect to normal cells. We therefore believe that the prepared redox/pH dual-responsive and biodegradable PPZ DDSs have great potential in various field.

Preparation and Performance of Cement Mortar Reinforced by Modified Bamboo Fibers.

This study aims to prepare bamboo-fiber-reinforced cement composites and provide a solution to the issue of poor interfacial adhesion between bamboo fibers and cement matrix. The original bamboo fibers were modified by three moderately low-cost and easy-to-handle treatments including glycerol, aluminate ester, and silane treatments. The performance of the modified bamboo-fiber-reinforced cement composites was evaluated by a series of mechanical and durability tests, including flexural and compressive strength, water absorption, chloride ion penetration, drying shrinkage, freeze-thaw resistance, and carbonization. In addition, the microstructures of composites were characterized using a scanning electron microscope (SEM). The results showed that the composites reinforced with glycerol-modified bamboo fibers had 14% increased flexural strength and comparable compressive strength. From durability perspectives, all treatments showed similar performance in drying shrinkage, whereas aluminate ester treatment was the most effective in terms of impermeability, chloride resistance, freeze-thaw resistance, and carbonization. The results could provide insights to efficient and effective natural fiber treatment to enable better performance of natural-fiber-reinforced cement-based materials.

Formation of Stereocomplex Crystal and Its Effect on the Morphology and Property of PDLA/PLLA Blends.

Stereocomplex-polylactic acid (SC-PLA) is obtained in poly(D-lactic) acid/poly(L-lactic) acid (PDLA/PLLA) blends under adjusting processing conditions. It is found that the degree of crystallinity of overall SC-PLA is up to 43.7% in PDLA/PLLA blends of 1:1 mass ratio. Formation of stereocomplex (SC) crystals forces molecular chains in the blends to be more closely arranged and further enhances interaction between molecular chains, thus forming a physical cross-linking network in the SC crystals, resulting in the blends having a special microstructure. The mechanism of formation of the SC crystal physical cross-linking network is elucidated by dielectric spectroscopy, and the relationships between homocomplex (HC) crystals, SC crystals, and amorphous regions in the blends are also analyzed. Interestingly, mechanical properties of the blends are significantly improved due to formation of an SC crystal cross-linking network.

Electrospun cellulose-based conductive polymer nanofibrous mats: composite scaffolds and their influence on cell behavior with electrical stimulation for nerve tissue engineering.

The fabrication of scaffolds with suitable chemical, physical, and electrical properties is critical for nerve cell adhesion and proliferation. Recently, electrical stimulation on conductive polymers has been applied to construct functional nerve cell scaffolds. Herein, we prepared natural polymer (cellulose)/conductive polymer nanofibrous mats, i.e., electrospun cellulose (EC)/poly N-vinylpyrrole (PNVPY) and EC/poly(3-hexylthiophene) (P3HT) through an efficient in situ polymerization method. The surface immobilization was characterized by optical microscopy (OM), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, hydrophilicity, porosity, and cyclic voltammetry. The OM and SEM images showed that PNVPY formed polymer coatings and aggregated nanoparticles on the EC nanofibers, while P3HT only produced polymer coatings. Compared with pure EC mats, both the composite mats had increased thickness, higher porosity, and higher conductivity. Also, an increase in hydrophilicity was found for EC/P3HT. In vivo cytocompatibility of the undifferentiated PC12 cells showed that the EC/PNVPY and EC/P3HT scaffolds exhibited favorable cell activity, adhesion, and proliferation. Furthermore, the results of electrical stimulation experiments indicated that the EC/P3HT mats could effectively promote the proliferation of the PC12 cells more than the EC and EC/PNVPY mats. The findings suggest a positive outcome regarding the conductive polymer-modified EC/PNVPY and EC/P3HT nanofibrous mats in neural tissue engineering.

Electrospun natural polymer and its composite nanofibrous scaffolds for nerve tissue engineering.

Attributed to the excellent biocompatibility and desirable mechanical properties to natural tissue, natural polymer-based electrospun nanofibers have drawn extensive research interests in tissue engineering. Electrospun nanofibers have been explored as scaffolds in tissue engineering to modulate cellular behavior. Also, electrospun nanofiber matrices have morphological similarities to the natural extra-cellular matrix (ECM). Natural polymer and its composite nanofiber mats are the promising candidates in governing nerve cells growth and nerve regeneration due to their unique characteristics such as high permeability, stability, porosity, suitable mechanical performance and excellent biocompatibility. In this review, the progress in electrospun natural polymers and its composite nanofibers scaffold for neural tissue engineering are presented. The influences of fiber orientation and electrical stimulation on the nerve cell behavior and neurite growth are systematically summarized. Furthermore, the current application of natural polymer composite scaffold as in vivo implantable device for nerve regeneration is also discussed (see Figure 1).

Acid-Responsive and Biologically Degradable Polyphosphazene Nanodrugs for Efficient Drug Delivery.

To enhance the therapeutic effects and reduce the damage to normal tissues in cancer chemotherapy, it is indispensable to develop drug delivery carriers with controllable release and good biocompatibility. In this work, acid-responsive and degradable polyphosphazene (PPZ) nanoparticles were synthesized by the reaction of hexachlorotripolyphosphonitrile (HCCP) with 4-hydroxy-benzoic acid (4-hydroxy-benzylidene)-hydrazide (HBHBH) and anticancer drug doxorubicin (DOX). The controlled release of DOX could be realized based on the acid responsiveness of acylhydrazone in HBHBH. Experimental results showed that polyphosphazene nanoparticles remained stable in the body's normal fluids (pH ∼ 7.4), while they were degraded and controllable release of DOX in an acidic environment such as tumors (pH ∼ 6.8) and lysosome and endosome (∼5.0) in cancer cells In particular, the doxorubicin (DOX)-loading ratio was fair high and could be tuned from 10.6 to 52.6% by changing the dosing ratio of DOX to HBHBH. Meanwhile, the polyphosphazene nanodrugs showed excellent toxicity to tumor cells and reduced the side effect to normal cells both in vitro and in vivo due to their enhanced permeability and retention (EPR) effect and pH-sensitive degradation properties. Therefore, the constructed pH-sensitive drug delivery system has great potential for cancer chemotherapy.

Dibora[10]annulenes: Construction, Properties, and Their Ring-Opening Reactions.

The selective construction of various dibora[10]annulenes through mild boron-tin exchange reactions is reported. Dibora[10]annulenes exhibit optical and electrochemical properties of value for future sensing applications. Controlled addition of the Lewis base pyridine to dibora[10]annulenes instigates a selective ring-opening reaction. This work explores a new area of boron chemistry that represents the first step in the potential formation of dibora[10]annulene-derived polymers.

Polyacrylonitrile nanofibrous mat from electrospinning: Born with potential anti-fungal functionality.

Electrospun nanofibers have been found in many applications such as air/water filtration, performance apparel, drug delivery, and scaffold for tissue engineering and started to be integrated in commercial products, which leads to their exposure to environment. Electrospun nanofibrous material is a relatively new material to microorganism in nature and little is known about the biological implication of interactions between electrospun nanofibrous mats and cellular fungal cells. Herein the interaction between electrospun polyacrylonitrile (ESPAN) nanofibrous mat and representative non-pathogenic/pathogenic cellular yeasts (Saccharomyces cerevisiae and Candida albicans) was investigated. It is demonstrated for the first time that when these cellular yeasts, species of the kingdom fungi, were exposed to ESPAN nanofibrous mat, they exhibited lower growth rate, radical change to morphology, and reduced viability without presence of any chemical antifungal agent. These responses were distinct from the cellular interactions with other forms of PAN materials (e.g. solid film or microfibrous mat). Exploration of mechanism indicated that the interaction between yeast cell and electrospun nanofibrous mat is a complex phenomenon in which both nanofibrous morphology and fiber surface composition/property play significant roles. The inherent anti-yeast and potential anti-fungal functionality of ESPAN nanofibrous mat may make an immediate impact on environmental microorganism and could also benefit the next-generation material design to control microbial growth through solely physical contact.

High Performance Anti-Corrosion Coatings of Poly (Vinyl Butyral) Composites with Poly N-(vinyl)pyrrole and Carbon Black Nanoparticles.

Zinc is widely used in battery negative electrodes and steel coatings for automotive industries. The anti-corrosion property of zinc is the most important factor determining the performance and lifetime of the products. In this paper, both size-controlled poly N-(vinyl)pyrrole (PNVPY) nanoparticles and carbon black (CB) nanoparticles were compounded with poly (vinyl butyral) (PVB) binder developing a series of composite coatings covered on the zinc substrates using a spin-coating technique. The morphologies of the surface and cross section of the PNVPY/CB/PVB coatings indicate that the PNVPY and CB nanoparticles are uniformly distributed in the matrix. The corrosion resistance of the composite coatings was tested by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization in a 3.5% NaCl solution. It is found that the coating with 1.9 wt.% PNVPY and 2.3 wt.% CB nanoparticles shows a remarkably high resistance value (Rc) and corrosion protection efficiency (99.99%). Meanwhile, the immersion results also reveal its superior corrosion resistance. It is considered that the nanoscale dispersion of PNVPY and carbon in PVB matrix and the strong interface action between the nanoparticles and PVB result in the uniform microstructure of the composites which endues the superior corrosion properties of the coatings.

A Unique Strategy for Polyethylene Glycol/Hybrid Carbon Foam Phase Change Materials: Morphologies, Thermal Properties, and Energy Storage Behavior.

Polyethylene glycol (PEG)/hybrid carbon foam (CF) phase change materials (PCMs) were prepared by integrating PEG into CF via dynamic-vacuum impregnation. The hybrid CF was first synthesized by mixtures of graphene oxide (GO) and carbon nanotubes (CNTs) with different volume ratios. The morphologies, chemical structures, thermal conductivities, shape-stabilization levels, and photo-thermal energy conversion levels of these composite PCMs were characterized systematically. The prepared composite PCMs exhibited good shape-stabilization levels and showed their original shapes without any PEG leakage. It was found that the polyethylene glycol/carbon foam with multi-walled carbon nanotubes (PEG/MCF) composite PCMs had a better shape-stable performance below the temperature of 250 °C, and the thermal conductivity of the PEG/MCF composite PCMs reached as high as 1.535 W/(mK), which was obviously higher than that of polyethylene glycol/carbon foam with single-walled carbon nanotubes (PEG/SCF, 1.159 W/(mK)). The results of the photo-thermal simulation tests showed that the composite PCMs had the ability to absorb light energy and then convert it to thermal energy, and the maximum thermal energy storage efficiency of the PEG/MCF composite PCMs and the PEG/SCF composite PCMs was 92.1% and 90.6%, respectively. It was considered that a valuable technique to produce high-performance composite PCMs was developed.

Facile Preparation of Doxorubicin-Loaded and Folic Acid-Conjugated Carbon Nanotubes@Poly(N-vinyl pyrrole) for Targeted Synergistic Chemo-Photothermal Cancer Treatment.

We developed a bifunctional nanoplatform for targeted synergistic chemo-photothermal cancer treatment. The nanoplatform was constructed through a facile method in which poly(N-vinyl pyrrole) (PVPy) was coated on cut multiwalled carbon nanotubes (c-MWNTs); FA-PEG-SH was then linked by thiol-ene click reaction to improve the active targeting ability, water dispersibility, and biocompatibility and to extend the circulation time in blood. The PVPy shell not only enhanced the photothermal effect of c-MWNTs significantly but also provided a surface that could tailor targeting molecules and drugs. The resulting MWNT@PVPy-S-PEG-FA possessed high drug-loading ratio as well as pH-sensitive unloading capacity for a broad-spectrum anticancer agent, doxorubicin. Owing to its outstanding efficiency in photothermal conversion and ability in targeted drug delivery, the material could potentially be used as an efficient chemo-photothermal therapeutic nanoagent to treat cancer.