Covalent cum Noncovalent Functionalizations of Carbon Nanotubes for Effective Reinforcement of a Solution Cast Composite Film

Although carbon nanotubes have impressive tensile properties, exploiting these properties in composites, especially those made by the common solution casting technique, seems to be elusive thus far. The reasons could be partly due to the poor nanotube dispersion and the weak nanotube/matrix interface. To solve this dual pronged problem, we combine noncovalent and covalent functionalizations of nanotubes in a single system by the design and application of a novel dispersant, hydroxyl polyimide-<i>graft</i>-bisphenol A diglyceryl acrylate (PI_OH-BDA), and use them with epoxidized single-walled carbon nanotubes (O-SWNTs). Our novel PI_OH-BDA dispersant functionalizes the nanotubes noncovalently to achieve good dispersion of the nanotubes because of the strong π–π interaction due to main chain and steric hindrance of the BDA side chain. PI_OH-BDA also functionalizes O-SWNTs covalently because it reacts with epoxide groups on the nanotubes, as well as the cyanate ester (CE) matrix used. The resulting solution-cast CE composites show 57%, 71%, and 124% increases in Young’s modulus, tensile strength, and toughness over neat CE. These values are higher than those of composites reinforced with pristine SWNTs, epoxidized SWNTs, and pristine SWNTs dispersed with PI_OH-BDA. The modulus and strength increase per unit nanotube weight fraction, i.e., d<i>E</i>/d<i>W</i>_NT and dσ/d<i>W</i>_NT, are 175 GPa and 7220 MPa, respectively, which are significantly higher than those of other nanotube/thermosetting composites (22–70 GPa and 140–3540 MPa, respectively). Our study indicates that covalent cum noncovalent functionalization of nanotubes is an effective tool for improving both the nanotube dispersion and nanotube/matrix interfacial interaction, resulting in significantly improved mechanical reinforcement of the solution-cast composites

High Internal Phase Emulsion Templating with Self-Emulsifying and Thermoresponsive Chitosan-<i>graft</i>-PNIPAM-<i>graft</i>-Oligoproline

High internal phase emulsion (HIPE)-templating is an attractive method of producing high porosity polymer foams with tailored pore structure, pore size and porosity. However, this method typically requires the use of large amounts of surfactants to stabilize the immiscible liquid phases, and polymerizable monomers/cross-linker in the continuous minority phase to solidify the HIPE, which may not be desirable in many applications. We show that polyHIPEs with a porosity of 73% can be formed solely using a copolymer of chitosan-<i>graft</i>-PNIPAM-<i>graft</i>-oligoproline (CSN-PRO), which acts simultaneously as emulsifier and thermoresponsive gelator, and forms upon removal of the liquid templating phases, the bulk structure of the resulting polyHIPE. With only a small amount of surfactant (1%v/v in the aqueous phase), and varying the polymer concentration and internal phase volume ratio, different polyHIPEs with porosities of up to 99%, surface areas in excess of 300 m²/g and controlled pore interconnectivity can be formed. The poly­(CSN-PRO)­HIPEs are also shown to be thermoresponsive and remained intact when immersed into water above 34 °C but dissolve below their LCST, which is useful for applications such as drug delivery and tissue engineering scaffolds

In Situ Charge-Transfer-Induced Transition from Metallic to Semiconducting Single-Walled Carbon Nanotubes

Single-walled carbon nanotubes (SWNTs) are regarded to be potential building blocks for future electronics, because of their exceptional electrical, physical, and mechanical properties. A major obstacle to their practical use for high-performance nanoelectronics is the presence of both metallic SWNTs (M-SWNT) and semiconducting SWNTs (S-SWNT) in as-grown SWNT samples. Most metallicity-based SWNT sorting techniques involve suspension of the nanotubes in solutions, which generally also result in nanotube defects. As-grown SWNTs typically have far superior conductivity or carrier mobility than solution-suspended SWNTs; however, thus far, there is no simple or reproducible method to remove the electronic inhomogeneity in these as-grown nanotubes. We present a simple in situ method using an organic electron-acceptor compound, Acid Yellow (AY), to convert SWNTs from metallic to semiconducting to improve device field-effect behavior. By simply immersing the as-synthesized SWNTs (still attached to a wafer) into an AY solution, the originally metallic nanotubes behave similar to semiconducting ones. Using Raman spectroscopy, atomic force microscopy and single nanotube transistor device measurements, we show that the charge-transfer interaction between SWNTs and the organic electron-acceptor compound AY is diameter-dependent; in the large-diameter regime (1.60–2.60 nm), modulated metallic SWNTs exhibit semiconducting behavior, as evidenced by a pronounced field effect in the current–voltage (<i>I</i>–<i>V</i>) characteristics and up to 3 orders of magnitude increase in the on/off ratio of single M-SWNT field-effect transistors. This method presents a simple viable route toward the fabrication of switchable transistors with as-synthesized SWNTs

High Interlaminar Shear Strength Enhancement of Carbon Fiber/Epoxy Composite through Fiber- and Matrix-Anchored Carbon Nanotube Networks

To improve the interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy composite, networks of multiwalled carbon nanotubes (MWNTs) were grown on micron-sized carbon fibers and single-walled carbon nanotubes (SWNTs) were dispersed into the epoxy matrix so that these two types of carbon nanotubes entangle at the carbon fiber (CF)/epoxy matrix interface. The MWNTs on the CF fiber (CF-MWNTs) were grown by chemical vapor deposition (CVD), while the single-walled carbon nanotubes (SWNTs) were finely dispersed in the epoxy matrix precursor with the aid of a dispersing agent polyimide-<i>graft</i>-bisphenol A diglyceryl acrylate (PI-BDA) copolymer. Using vacuum assisted resin transfer molding, the SWNT-laden epoxy matrix precursor was forced into intimate contact with the “hairy” surface of the CF-MWNT fiber. The tube density and the average tube length of the MWNT layer on CF was controlled by the CVD growth time. The ILSS of the CF-MWNT/epoxy resin composite was examined using the short beam shear test. With addition of MWNTs onto the CF surface as well as SWNTs into the epoxy matrix, the ILSS of CF/epoxy resin composite was 47.59 ± 2.26 MPa, which represented a ∼103% increase compared with the composite made with pristine CF and pristine epoxy matrix (without any SWNT filler). FESEM established that the enhanced composite did not fail at the CF/epoxy matrix interface

Chitosan-Based Peptidopolysaccharides as Cationic Antimicrobial Agents and Antibacterial Coatings

The rapid spread of multidrug-resistant bacteria has called for effective antimicrobial agents which work on a more direct mechanism of killing. Cationic peptidopolysaccharides are developed in the present work to mimic the peptidoglycan structure of bacteria and to enhance the membrane-compromising bactericidal efficacy. Antimicrobial CysHHC10 peptide was grafted to the C-2 (amino) or C-6 (hydroxyl) position of chitosan backbone via thiol-maleimide “click” conjugation, utilizing the maleimidohexanoic linkers. The peptidopolysaccharide with primary amino backbone intact (CSOHHC) exhibited higher bactericidal activity toward Gram-positive and Gram-negative bacteria, in comparison to that with amino backbone grafted with the peptide (CSNHHC). Both peptidopolysaccharides also exhibited lower hemolytic activity and cytotoxicity than free CysHHC10 peptide due to the moderation effect contributed by the chitosan backbone. For targeting the Gram-positive bacteria in particular, the CSOHHC expressed 4- and 2-fold increases in hemo- and cytoselectivity, respectively, as compared to the CysHHC10 peptide. In an extended application, peptidopolysaccharide antibacterial coatings were formed via layer-by-layer assembly with tannic acid. The peptidopolysaccharide coatings readily killed the adhered bacteria upon contact while being cytocompatible by maintaining more than 60% viability for the adhered fibroblasts. Therefore, the peptidoglycan-mimetic peptidopolysaccharides are potential candidates for anti-infective drugs in biomedical applications

Single-Cell Oral Delivery Platform for Enhanced Acid Resistance and Intestinal Adhesion

Oral delivery of cells, such as probiotics and vaccines, has proved to be inefficient since cells are generally damaged in an acidic stomach prior to arrival at the intestine to exert their health benefits. In addition, short retention in the intestine is another obstacle which affects inefficiency. To overcome these obstacles, a cell-in-shell structure was designed with pH-responsive and mucoadhesive properties. The pH-responsive shell consisting of three cationic layers of chitosan and three anionic layers of trans-cinnamic acid (t-CA) was made via layer-by-layer (LbL) assembly. t-CA layers are hydrophobic and impermeable to protons in acid, thus enhancing cell gastric resistance in the stomach, while chitosan layers endow strong interaction between the cell surface and the mucosal wall which facilitates cell mucoadhesion in the intestine. Two model cells, probiotic L. rhamnosus GG and dead Streptococcus iniae, which serve as inactivated whole-cell vaccine were chosen to test the design. Increased survival and retention during oral administration were observed for coated cells as compared with naked cells. Partial removal of the coating (20–60% removal) after acid treatment indicates that the coated vaccine can expose its surface immunogenic protein after passage through the stomach, thus facilitating vaccine immune stimulation in the intestine. As a smart oral delivery platform, this design can be extended to various macromolecules, thus providing a promising strategy to formulate oral macromolecules in the prevention and treatment of diseases at a cellular level

Three-Dimensional Macroporous Graphene Foam Filled with Mesoporous Polyaniline Network for High Areal Capacitance

Bicontinuous macroporous graphene foam composed of few-layered graphene sheets provides a highly conductive platform on which to deposit mesoporous polyaniline via incorporation of electrodeposition and inkjet techniques. The experimental results exhibit that the coating polyaniline thin layer on the surface of three-dimensional graphene foam via electrodeposition is of importance for changing the hydrophobic surface to a hydrophilic one and for the subsequent filling of the mesoporous polyaniline network into the macroporous graphene foam. The porous polyaniline network with high pseudocapacitance is highly efficient for adjusting the pore structure and capacitive properties of graphene foam. When used as electrode materials for supercapacitors, the resulted graphene foam–polyaniline network with high porosity renders a large areal capacitance of over 1700 mF cm^–2, which is over two times the enhancement in comparison with the pure graphene foam and polyaniline thin layer coated one. The ultrahigh areal capacitance benefits from the synergistic effect of the good conductive graphene backbone and high pseudocapacitive polyaniline

Macroporous and Monolithic Anode Based on Polyaniline Hybridized Three-Dimensional Graphene for High-Performance Microbial Fuel Cells

Microbial fuel cell (MFC) is of great interest as a promising green energy source to harvest electricity from various organic matters. However, low bacterial loading capacity and low extracellular electron transfer efficiency between the bacteria and the anode often limit the practical applications of MFC. In this work, a macroporous and monolithic MFC anode based on polyaniline hybridized three-dimensional (3D) graphene is demonstrated. It outperforms the planar carbon electrode because of its abilities to three-dimensionally interface with bacterial biofilm, facilitate electron transfer, and provide multiplexed and highly conductive pathways. This study adds a new dimension to the MFC anode design as well as to the emerging graphene applications

Charge Transfer between Metal Clusters and Growing Carbon Structures in Chirality-Controlled Single-Walled Carbon Nanotube Growth

Synthesis of single-walled carbon nanotubes (SWCNTs) with specific chirality has been a great challenge. The detailed role of catalyst clusters in chirality-selective growth of SWCNTs is still unclear. We studied armchair (5,5), chiral (6,5), and zigzag (9,0) nanotube growths on a relaxed Ni₅₅ cluster. Although adhesion energies and chemical potentials of growing carbon structures only show small differences, charges are evidently transferred (or redistributed) from Ni atoms to the growing end edges of nanotubes, which enhance the reactivity of carbon edges. Different chiral nanotubes exhibit distinct reaction active sites. (5,5) has five identical double-carbon active sites, while (9,0) has nine single-carbon active sites. (6,5) has a kink site with the highest reaction activity. These findings imply that the structures of metal clusters strongly correlate with nanotube growth sites through charge transfer (or redistribution). Potential opportunities exist in enabling (<i>n</i>,<i>m</i>) selective growth by engineering charge transfer between metal clusters and growing carbon structures

Conjugation of Polyphosphoester and Antimicrobial Peptide for Enhanced Bactericidal Activity and Biocompatibility

Enhancing the bactericidal activity and moderating the toxicity are two important challenges in the design of upcoming antimicrobial compounds. Herein, antimicrobial macromolecules were developed by conjugating CysHHC10 peptide and polyphosphoester for the modulation of microbiocidal activity and biocompatibility. The conjugation was carried out via thiol-yne “click” chemistry between the cysteine terminal of the peptide and the pendant propargyl moieties of the polyphosphoester. The bactericidal efficacy of the polyphosphoester–peptide conjugates were investigated by microbial growth inhibition toward the Gram-positive and Gram-negative bacteria. On the basis of peptide mass fraction, the polyphosphoester–peptide conjugates exhibited lower values of minimum inhibitory concentration than that of the free peptide. The polyphosphoester–peptide conjugates also exhibited ultralow hemolytic characteristic at a concentration of 4000 μg/mL, indicating significant improvement of erythrocytes compatibility as compared to the free peptide that readily caused lysis of 50% of red blood cells at 1000 μg/mL. Cytotoxicity of the polyphosphoester–peptide conjugates toward 3T3 fibroblast cells was also reduced in comparison to that of the free peptide. Conjugation of the polyphosphoester thus improves the bactericidal efficacy and biocompatibility of the antimicrobial peptide