New insights into the structures of diorganotellurium Oxides. The first polymeric diorganotelluroxane[(p-MeOC6H4)2TEO]n

The characterization of the previously reported diorganotellurium oxides R₂TeO (R = Ph (1) and p-MeOC₆H₄ (2)) was revisited by osmometric molecular weight determinations, ¹²⁵Te NMR spectroscopy, and electrospray spectrometry (ESMS) in solution and by 125Te MAS NMR spectroscopy in the solid state. The single-crystal X-ray structure of 2 revealed a polymeric arrangement that features a zigzag configured Te-O backbone without any secondary Te···O interactions. In solution 1 and 2 exist predominantly as monomers but appear to be in equilibrium with higher oligomers to a minor extent.

Characterization of the moisture absorption and thermal ageing behaviour of polymeric composite systems using Raman spectroscopy

Advanced polymeric materials and their respective composites are fast becoming one of the world's most frequently used engineering materials. They find application in the manufacture of e.g. boat hulls, high performance motor vehicles, aircraft components and sports goods. Their high specific strength and specific stiffness give them the edge in applications where weight savings are critical, but their long-term durability is often questioned. These materials are susceptible to environmental conditions such as temperature and humidity. There is also a lack of relevant data, due to the long time-scales required for testing. In this study, the Raman technique has been used to monitor the degradation of two composite systems, namely: a rubber toughened vinylester material used in the marine industry and a high temperature bismaleimide/carbon fibre aerospace composite. Preliminary Raman studies show that the toughening rubber particles dispersed in the cured vinylester resin are leached out during hygrothermal ageing. The weight gain during ageing suggests that this leaching process occurs concurrently with the absorption of water molecules. An increase in the degree of cross-linking is observed when bismaleimide/carbon fibre composite is aged at high temperature. This cross- linking tendency decreases with increasing depth within the carbon fibre bundle.

Ionic conductivity studies of polymeric electrolytes containing lithium salt with plasticizer

New plasticized polymer electrolytes were synthesized based on poly ethylene oxide (PEO), Poly (N,N-dimethylamino-ethyl-methacrylate) (PDMAEMA), LiN(CF₃SO₂)₂ (LITFSI) as the salt and tetraethylene glycol dimethyl ether(tetraglyme) and EC + PC as plasticizers. The preparation and characterization of the polymer electrolytes were investigated as a function of temperature and various concentrations of LITFSI. Impedance spectroscopy and differential scanning calorimeter (DSC) were used to characterize the effects of various temperature, lithium salt concentration and two plasticizers on conductivity. The complex of PDMAEMA/PEO/LiTFSI/tetraglyme (S2) exhibits higher conductivity (4.74 × 10⁻⁴ S cm⁻¹at 25 °C) than PDMAEMA/PEO/LiTFSI/EC + PC (S1).

Shear-enhanced solution precipitation : a simple process to produce short polymeric nanofibers

The growing interest in polymeric nanofibers has been increasing the push for the development of simple and efficient nanofiber-preparation techniques. We herein describe how a conventional solution process is readapted to suit the needs for fast and efficient production of short polymeric nanofibers. Poly(ethylene-co-acrylic acid) (PEAA), a semi-crystalline polymer, was used as model. When a PEAA solution was injected into an alcoholic non-solvent while simultaneously applying high shear to the non-solvent system, PEAA nanofibers were obtained with average diameter as thin as 113 nm and length as short as 4.5 _m. The fiber diameter and length were also adjustable by varying the operating parameters. This one-step technique advances the currently available nanofabrication tools by adjusting a widely accepted concept to the nano-scale. It may constitute a viable method for large-scale production of short polymeric nanofibers.

One-dimensional polyelectrolyte/polymeric semiconductor core/shell structure : sulfonated poly(arylene ether ketone)/polyaniline nanofibers for organic field-effect transistors

A polyelectrolyte/polymeric semiconductor core/shell structure is developed for organic field-effect transistors (OFETs) based on sulfonated poly(arylene ether ketone)/polyaniline core/shell nanofibers via electrospinning and solution-phase selective polymerization. The polyelectrolyte does not work as a gate dielectric, but can provide an internal modulation from the nanointerface of the 1D core/shell nanostructure. The transistor devices display very high mobilities.

Polymeric materials with ordered nanostructures templated from hexagonal lyotropic liquid crystals

In this study, successful methods have been established to retain the ordered nanostructures in polymer materials templated from hexagonal lyotropic liquid crystals, which potentially renders broad applications as biomedical and membrane materials.

A controllable simple method for production of polymeric nanofiberous composite via single nozzle jet electrospinning

A special Micro-Nano fiberous composite structure composed of nano- and micro-scale fiber of Polycaprolactone (PCL) and Gelatin produced by using single nozzle electrospinning instrument. By controlling the solution (polymer concentration and polymer composition percent) and processing parameters of electrospinning (feed rate and electrostatic field), different portion of nano and micro fibers in the structure is achieved. This method can result a one-stage method of fabrication of Micro-Nano fiberous composite structure instead of previously used twostage process or using additional facility to produce structure near-similar to this composite structure. The resulting materials finely mingle nano- and micro fibers together, rather than simply juxtaposing them, as is commonly found in the literature. The results obtained from SEM, Flow Porosimetry, and DMA led the authors to confirm that the structure has very versatile and improved properties for many applications like cell culture scaffolds. These favourable mechanical and structural properties can provide easier opening of spaces for cell penetration to deeper levels of the scaffold and withstand to tensions during to clinical handling.

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.

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.

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.