Sulfonated poly(ether ether ketone)/polypyrrole core–shell nanofibers : a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form onedimensional polymeric adsorbent/conducting polymer core−shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH3 can facilitate the mass diffusion of NH3 through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH3 (20 ppb) at room temperature.

Stable anode performance of an Sb–carbon nanocomposite in lithium-ion batteries and the effect of ball milling mode in the course of its preparation

Materials that alloy with lithium (Si, Ge, Sn, Sb, and P) are considered as alternatives to graphitic anodes in lithium-ion batteries. Their practical use is precluded by large volume changes (200–370%) during cycling. Embedding nanoparticles into carbon is being investigated as a way to tackle that, and ball milling is emerging as a technique to prepare nanocomposites with enhanced capacity and cyclic stability. Using Sb as a model system, we investigate the preparation of Sb–carbon nanocomposites using a reconfigurable ball mill. Four distinctive milling modes are compared. The structure of the composites varies depending on the mode. Frequent strong ball impacts are required for the optimal electrochemical performance of the nanocomposite. An outstanding stable capacity of 550 mA h g−1 for 250 cycles at a current rate of 230 mA g−1 is demonstrated in a thin electrode (1 mg cm−2) and a capacity of [similar]400 mA h g−1 can be retained at 1.15 A g−1. Some capacity fade is observed in a thicker electrode (2.5 mg cm−2), i.e. the performance is sensitive to mass loading. The electrochemical stability originates from the nanocomposite structure containing Sb nanoparticles (5–15 nm) dispersed in a carbon component.

Polymeric colorants: Statistical copolymers of indigo building blocks with defined structures

Statistical copolymers of indigo (1a) and N-acetylindigo (1b) building blocks with defined structures were studied. They belong to the class of polymeric colorants. The polymers consist of 5,5′-connected indigo units with keto structure and N-acetylindigo units with uncommon tautomeric indoxyl/indolone (=1H-indol-3-ol/3H-indol-3-one) structure (see 2a and 2b in Fig. 1). They formed amorphous salts of elongated monomer lengths as compared to monomeric indigo. The polymers were studied by various spectroscopic and physico-chemical methods in solid state and in solution. As shown by small-angle-neutron scattering (SANS) and transmission-electron microscopy (TEM), disk-like polymeric aggregates were present in concentrated solutions (DMSO and aq. NaOH soln.). Their thickness and radii were determined to be ca. 0.4 and ca. 80 nm, respectively. From the disk volumes and by a Guinier analysis, the molecular masses of the aggregates were calculated, which were in good agreement with each other. Defined structural changes of the polymer chains were observed during several-weeks storage in concentrated DMSO solutions. The original keto structure of the unsubstituted indigo building blocks reverted to the more flexible indoxyl/indolone structure. The new polymers were simultaneously stabilized by intermolecular H-bonds to give aggregates, preferentially dimers. Both aggregation and tautomerization were reversible upon dissolution. The polymers were synthesized by repeated oxidative coupling of 1,1′-diacetyl-3,3′-dihydroxybis-indoles 5 (from 1,1′-diacetyl-3,3′-bis(acetyloxy)bis-indoles 6) followed by gradual hydrolysis of the primarily formed poly(N,N′-diacetylindigos) 7 (Scheme). N,N′-Diacetylbis-anthranilic acids 9 were isolated as by-products.

RGO/ZnO nanocomposite: an efficient, sustainable, heterogeneous, amphiphilic catalyst for synthesis of 3-substituted indoles in water

A nanocomposite consisting of reduced graphene oxide and zinc oxide nanoparticles (RGO/ZnO) with unique structural features was developed as an efficient, sustainable, amphiphilic, heterogeneous catalyst for the synthesis of various 3-substituted indoles in water. The catalyst was recycled six times without significant loss in catalytic activity. The higher environmental compatibility and sustainability factors such as smaller E-factor and higher atom economy make the present methodology a true green and sustainable process for the synthesis of various biologically important 3-substituted indoles.

Crystalline Structures and α → β and γ polymorphs transformation induced by nanoclay in PVDF-based nanocomposite

Poly(vinylidene fluoride) (PVDF) nanocomposites were prepared by melt-mixing. The dispersion of clay platelets and rheology of nanocomposites were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and rheometric mechanical spectrometer (RMS). The transformation of α to β and γ phase in PVDF was induced by the addition of nanoclay and subsequently the isothermal crystallization kinetics of neat PVDF and its nanocomposite have been investigated. The interaction between clay nanofillers and PVDF macromolecular chains induced the change of conformation from trans-gauche to all-trans crystal structure in PVDF segment. The isothermal crystallization of PVDF/clay nanocomposites was carried out by Differential Scanning Calorimetry (DSC) technique. The influence of clay platelets on nucleation crystallization rate and Avrami exponent were studied. PVDF/clay nanocomposite showed higher crystallization rate indicating that nanoclay has acted as an effective nucleation agent. This nucleation effect of nanoclay increased the Avrami exponent and decreased the degree of crystallinity. © 2014 World Scientific Publishing Company.

Enhanced lithium storage in ZnFe2O4-C nanocomposite produced by a low-energy ball milling

Preparation of novel nanocomposite structure of ZnFe2O4-C is achieved by combining a sol-gel and a low energy ball milling method. The crucial feature of the composite's structure is that sol-gel synthesised ZnFe2O4 nanoparticles are dispersed and attached uniformly along the chains of Super P Li™ carbon black matrix by adopting a low energy ball milling. The composite ZnFe2O4-C electrodes are capable of delivering a very stable reversible capacity of 681 mAh g-1 (96% retention of the calculated theoretical capacity of ∼710 mAh g-1) at 0.1 C after 100 cycles with a remarkable Coulombic efficiency (82%) improvement in the first cycle. The rate capability of the composite is significantly improved and obtained capacity was as high as 702 at 0.1, 648 at 0.5, 582 at 1, 547 at 2 and 469 mAh g-1 at 4 C (2.85 A g-1), respectively. When cell is returned to 0.1 C, the capacity recovery was still ∼98%. Overall, the electrochemical performance (in terms of cycling stability, high rate capability, and capacity retention) is outstanding and much better than those of the related reported works. Therefore, our smart electrode design enables ZnFe2O4-C sample to be a high quality anode material for lithium-ion batteries.

Phosphorus-carbon nanocomposite anodes for lithium-ion and sodium-ion batteries

With the expected theoretical capacity of 2596 mA h g-1, phosphorus is considered to be the highest capacity anode material for sodium-ion batteries and one of the most attractive anode materials for lithium-ion systems. This work presents a comprehensive study of phosphorus-carbon nanocomposite anodes for both lithium-ion and sodium-ion batteries. The composite electrodes are able to display high initial capacities of approximately 1700 and 1300 mA h g-1 in lithium and sodium half-cells, respectively, when the cells are tested within a larger potential windows of 2.0-0.01 V vs. Li/Li+ and Na/Na+. The level of demonstrated capacity is underpinned by the storage mechanism, based on the transformation of phosphorus to Li3P phase for lithium cells and an incomplete transformation to Na3P phase for sodium cells. The capacity deteriorates upon cycling, which is shown to originate from disintegration of electrodes and their delamination from current collectors by post-cycling ex situ electron microscopy. Stable cyclic performance at the level of ∼700 and ∼350-400 mA h g-1 can be achieved if the potential windows are restricted to 2.0-0.67 V vs. Li/Li+ for lithium and 2-0.33 vs. Na/Na+ for sodium half-cells. The results are critically discussed in light of existing literature reports

Coiled polymeric growth factor gradients for multi-luminal neural chemotaxis

In the injured adult nervous system, re-establishment of growth-promoting molecular gradients is known to entice and guide nerve repair. However, incorporation of three-dimensional chemotactic gradients in nerve repair scaffolds, particularly in those with multi-luminal architectures, remains extremely challenging. We developed a method that establishes highly tunable three-dimensional molecular gradients in collagen-filled multi-luminal nerve guides by anchoring growth-factor releasing coiled polymeric fibers onto the walls of collagen-filled hydrogel microchannels. Differential pitch in the coiling of neurotrophin-eluting fibers generated sustained three-dimensional chemotactic gradients that appropriately induced the differentiation of Pheochromocytoma (PC12) cells into neural-like cells along an increasing concentration of nerve growth factor (NGF). Computer modeling estimated the stability of the molecular gradient within the luminal collagen, which we confirmed by observing the significant effects of neurotrophin gradients on axonal growth from dorsal root ganglia (DRG). Neurons growing in microchannels exposed to a NGF gradient showed a 60% increase in axonal length compared to those treated with a linear growth factor concentration. In addition, a two-fold increment in the linearity of axonal growth within the microchannels was observed and confirmed by a significant reduction in the turning angle ratios of individual axons. These data demonstrate the ability of growth factor-loaded polymeric coiled fibers to establish three-dimensional chemotactic gradients to promote and direct nerve regeneration in the nervous system and provides a unique platform for molecularly guided tissue repair.

Bio-inspired hydrogen-bond cross-link strategy toward strong and tough polymeric materials

It remains a huge challenge to create advanced polymeric materials combining high strength, great toughness, and biodegradability so far. Despite enhanced strength and stiffness, biomimetic materials and polymer nanocomposites suffer notably reduced extensibility and toughness when compared to polymer bulk. Silk displays superior strength and toughness via hydrogen bonds (H-bonds) assembly, while cuticles of mussels gain high hardness and toughness via metal complexation cross-linking. Here, we propose a H-bonds cross-linking strategy that can simultaneously strikingly enhance strength, modulus, toughness, and hardness relative to polymer bulk. The H-bond cross-linked poly(vinyl alcohol) exhibits high yield strength (140 MPa), reduced modulus (22.5 GPa) in nanoindention tests, hardness (0.5 GPa), and great extensibility (40%). More importantly, there exist semiquantitive linear relationships between the number of effective H-bond and macroscale properties. This work suggests a promising methodology of designing advanced materials with exceptional mechanical by adding low amounts (1.0 wt %) of small molecules multiamines serving as H-bond cross-linkers.