pH-Responsive Polyketone/5,10,15,20-Tetrakis-(Sulfonatophenyl)Porphyrin Supramolecular Submicron Colloidal Structures

In this work, we prepared color-changing colloids by using the electrostatic self-assembly approach. The supramolecular structures are composed of a pH-responsive polymeric surfactant and the water-soluble porphyrin 5,10,15,20-tetrakis-(sulfonatophenyl)porphyrin (TPPS). The pH-responsive surfactant polymer was achieved by the chemical modification of an alternating aliphatic polyketone (PK) via the Paal-Knorr reaction with N-(2-hydroxyethyl)ethylenediamine (HEDA). The resulting polymer/dye supramolecular systems form colloids at the submicron level displaying negative zeta potential at neutral and basic pH, and, at acidic pH, flocculation is observed. Remarkably, the colloids showed a gradual color change from green to pinky-red due to the protonation/deprotonation process of TPPS from pH 2 to pH 12, revealing different aggregation behavior

An easy synthetic way to exfoliate and stabilize MWCNTs in a thermoplastic pyrrole-containing matrix assisted by hydrogen bonds

This work focuses on the design of an engineered thermoplastic polymer containing pyrrole units in the main chain and hydroxyl pendant groups (A-PPy-OH), which help in achieving nanocomposites containing well-distributed, exfoliated and undamaged MWCNTs. The thermal annealing at 100 °C of the pristine nanocomposite promotes the redistribution of the nanotubes in terms of a percolative network, thus converting the insulating material in a conducting soft matrix (60 μΩ m). This network remains unaltered after cooling to r.t. and successive heating cycles up to 100 °C thanks to the effective stabilization of MWCNTs provided by the functional polymer matrix. Notably, the resistivity-temperature profile is very reproducible and with a negative temperature coefficient of -0.002 K-1, which suggests the potential application of the composite as a temperature sensor. Overall, the industrial scale by which A-PPy-OH can be produced offers a straightforward alternative for the scale-up production of suitable polymers to generate multifunctional nanocomposites

Self-Healing Polymer Nanocomposite Materials by Joule Effect

Nowadays, the self-healing approach in materials science mainly relies on functionalized polymers used as matrices in nanocomposites. Through different physicochemical pathways and stimuli, these materials can undergo self-repairing mechanisms that represent a great advantage to prolonging materials service-life, thus avoiding early disposal. Particularly, the use of the Joule effect as an external stimulus for self-healing in conductive nanocomposites is under-reported in the literature. However, it is of particular importance because it incorporates nanofillers with tunable features thus producing multifunctional materials. The aim of this review is the comprehensive analysis of conductive polymer nanocomposites presenting reversible dynamic bonds and their energetical activation to perform self-healing through the Joule effect

One-step functionalization of mildly and strongly reduced graphene oxide with maleimide: An experimental and theoretical investigation of the Diels-Alder [4+2] cycloaddition reaction

For large-scale graphene applications, such as the production of polymer-graphene nanocomposites, exfoliated graphene oxide (GO) and its reduced form (rGO) are presently considered to be very suitable starting materials, showing enhanced chemical reactivity with respect to pristine graphene, in addition to suitable electronic properties (i.e., tunable band gap). Among other chemical processes, a suitable way to obtain surface decoration of graphene is through a direct one-step Diels-Alder (DA) reaction, e.g. through the use of dienophile or diene moieties. However, the feasibility and extent of decoration largely depends on the specific graphene microstructure that in the case of rGO sheets is not easy to control and generally presents a high degree of inhomogeneity owing to various on-plane functionalization (e.g., epoxide and hydroxyl groups) or in-plane lattice defects. In an effort to gain some insights into the covalent functionalization of variably reduced GO samples, we present a combined experimental and theoretical study on the DA cycloaddition reaction of maleimide, a dienophile functional unit well-suited for chemical conjugation of polymers and macromolecules. In particular, we considered both mildly and strongly reduced GOs. Using thermogravimetry, Raman and X-Ray photoelectron spectroscopy, and elemental analysis we show evidence of variable chemical reactivity of rGO as a function of the residual oxygen content. Moreover, from quantum mechanical calculations carried out at the DFT level on different graphene reaction sites, we provide a more detailed molecular view to interpret experimental findings and to assess the reactivity series of different graphene modifications. This journal i

Chemical and Temperature Sensors Based on Functionalized Reduced Graphene Oxide

In this work, we investigated the functionalization of reduced graphene oxide (rGO) with 2-(dodecen-1-yl) succinic anhydride (TPSA) to increase the rGO effective interactions with organic solvents both in liquid and vapor phases. Thermogravimetric analysis, STEM, XPS, FTIR-ATR, and Raman spectroscopy confirmed the effective functionalization of rGO with about the 30 wt% of grafted TPSA without affecting the structural characteristics of graphene but successfully enhancing its dispersibility in the selected solvent except for the apolar hexane. Solid TPSA-rGO dispersions displayed a reproducible semiconducting (activated) electrical transport with decreased resistance when heated from 20 degrees C to 60 degrees C and with a negative temperature coefficient of 10(-3) K-1, i.e., comparable in absolute value with temperature coefficient in metals. It is worth noting that the same solid dispersions showed electrical resistance variation upon exposure to vapors with a detection limit in the order of 10 ppm and sensitivity alpha of about 10(-4) ppm(-1)

Synthesis of poly(1-vinylimidazole)-block-poly(9-vinylcarbazole) copolymers via RAFT and their use in chemically responsive graphitic composites

This study reports the synthesis of novel poly(1-vinylimidazole)-b-poly(9-vinylcarbazole) (PVI-b-PVK) block copolymers with varying monomer ratios using reversible addition-fragmentation chain-transfer (RAFT) polymerization and their incorporation in responsive composite materials. Specifically, non-covalent exfoliation of two different conductive fillers, multi-walled carbon nanotubes (MWCNTs) or reduced graphene oxide (rGO), was studied. The percolation threshold of the synthesized nanocomposites was dependent on the polymer used for dispersion, showing a better affinity of the fillers for block copolymers with higher relative carbazole content. Resistivity measurements showed selective variation in the resistance signal when the materials were exposed to various organic solvents and acids, providing a good basis for the design of sensing devices

Valorization of seashell waste in polypropylene composites: An accessible solution to overcome marine landfilling

Waste mussel (Mytilus galloprovencis) and clam (Ruditapes philippinarum) shells can be used as a bio-filler in polymeric composites. In this work, powdered shell wastes were incorporated into a polypropylene (PP) matrix. The powdered shell wastes were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy equipped with an energy dispersive spectrometer (SEM-EDS). DSC analysis of the PP composites indicates that both fillers did not act as nucleating agents but partially interfere with the formation of the crystalline phase of the polymer matrix. Moreover, by increasing the filler content, the elastic modulus of PP enhanced from ∼450 to ∼510 MPa. Finally, it was evidenced that mussels and clams shell powders enhanced the solar reflectance features of PP

Thermally switchable electrically conductive thermoset rgo/pk self-healing composites

Among smart materials, self-healing is one of the most studied properties. A self-healing polymer can repair the cracks that occurred in the structure of the material. Polyketones, which are high-performance thermoplastic polymers, are a suitable material for a self-healing mechanism: a furanic pendant moiety can be introduced into the backbone and used as a diene for a temperature reversible Diels-Alder reaction with bismaleimide. The Diels-Alder adduct is formed at around 50 °C and broken at about 120 °C, giving an intrinsic, stimuli-responsive self-healing material triggered by temperature variations. Also, reduced graphene oxide (rGO) is added to the polymer matrix (1.6–7 wt%), giving a reversible OFF-ON electrically conductive polymer network. Remarkably, the electrical conductivity is activated when reaching temperatures higher than 100 °C, thus suggesting applications as electronic switches based on self-healing soft devices

Fibrous Materials Made of Poly(ε-caprolactone)/Poly(ethylene oxide)-b-Poly(ε-caprolactone) Blends Support Neural Stem Cells Differentiation

In this work, we design and produce micron-sized fiber mats by blending poly(ε-caprolactone) (PCL) with small amounts of block copolymers poly(ethylene oxide)m-block-poly(ε-caprolactone)n (PEOm-b-PCLn) using electrospinning. Three different PEOm-b-PCLn block copolymers, with different molecular weights of PEO and PCL, were synthesized by ring opening polymerization of ε-caprolactone using PEO as initiator and stannous octoate as catalyst. The polymer blends were prepared by homogenous solvent mixing using dichloromethane for further electrospinning procedures. After electrospinning, it was found that the addition to PCL of the different block copolymers produced micron-fibers with smaller width, equal or higher hydrophilicity, lower Young modulus, and rougher surfaces, as compared with micron-fibers obtained only with PCL. Neural stem progenitor cells (NSPC), isolated from rat brains and grown as neurospheres, were cultured on the fibrous materials. Immunofluorescence assays showed that the NSPC are able to survive and even differentiate into astrocytes and neurons on the synthetic fibrous materials without any growth factor and using the fibers as guidance. Disassembling of the cells from the NSPC and acquisition of cell specific molecular markers and morphology progressed faster in the presence of the block copolymers, which suggests the role of the hydrophilic character and porous topology of the fiber mats

Intrinsic self-healing thermoset through covalent and hydrogen bonding interactions

The intrinsic self-healing ability of polyketone (PK) chemically modified into furan and/or OH groups containing derivatives is presented. Polymers bearing different ratios of both functional groups were cross-linked via furan/bis-maleimide (Diels-Alder adducts) and hydrogen bonding interactions (aliphatic and aromatic OH groups). The resulting thermosets display tuneable softening points (peak of tan (delta)) from 90 to 137 degrees C as established by DMTA. It is found that the cross-linked system containing only furan groups shows the highest softening temperature. On the other hand, systems displaying the combination of Diels-Alder adducts and hydrogen bonding (up to 60 mol % of -OH groups) do not show any change in modulus between heating cycles (i.e. factually a quantitative recovery of the mechanical behaviour). It is believed that the novelty of these tuneable thermosets can offer significant advantages over conventional reversible covalent systems. The synergistic reinforcement of both interactions resists multiple heating/healing cycles without any loss of mechanical properties even for thermally healed broken samples. (C) 2016 Elsevier Ltd. All rights reserved