One-Step Wet-Spinning Process of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) Fibers and the Origin of Higher Electrical Conductivity

A simplified wet-spinning process for the production of continuous poly (3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) fibers is reported. Conductivity enhancement of PEDOT:PSS fibers up to 223 S cm−1 has been demonstrated when these fibers are exposed to ethylene glycol as a post-synthesis processing step. In a new spinning approach it is shown that by employing a spinning formulation consisting of an aqueous blend of PEDOT:PSS and poly(ethlylene glycol), the need for post-spinning treatment with ethylene glycol is eliminated. With this approach, 30-fold conductivity enhancements from 9 to 264 S cm−1 are achieved with respect to an untreated fiber. This one-step approach also demonstrates a significant enhancement in the redox properties of the fibers. These improvements are attributed to an improved molecular ordering of the PEDOT chains in the direction of the fiber axis and the consequential enrichment of linear (or expanded-coil like) conformation to preference bipolaronic electronic structures as evidenced by Raman spectroscopy, solid-state electron spin resonance (ESR) and in situ electrochemical ESR studies.

New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).

11B nuclear magnetic resonance study of boron nitride nanotubes prepared by mechano-thermal method

We reported ¹¹B nuclear magnetic resonance studies of boron nitride (BN) nanotubes prepared by mechano-thermal route. The NMR lineshape obtained at 192.493 MHz (14.7 T) was fitted with two Gaussian functions, and the ¹¹B nuclear magnetization relaxations were satisfied with the stretched–exponential function, exp[-(tlT₁)^(D+1)/6] (D: space dimension) at all temperatures. In addition, the temperature dependence of spin–lattice relaxation rates was well described by T_i^-1 = aT (a: constant, T: temperature) and could be understood in terms of direct phonon process. All the 11BNMR results were explained by considering the inhomogeneous distribution of the paramagnetic metal catalysts, such as α-Fe, Fe–N, and Fe₂ B, that were incorporated during the process of high-energy ball milling of boron powder and be synthesized during subsequent thermal annealing. X-ray powder diffraction as well as electron paramagnetic resonance (EPR) on BN nanotubes were also conducted and the results obtained supported these conclusions.

13C Nuclear magnetic resonance spectroscopic study of plasticization in solid polymer electrolytes

Preliminary results are presented on the correlation between enhanced solvent mobility and ionic conductivity in plasticized polyether–urethane solid polymer electrolytes using ¹³C nuclear magnetic resonance spectroscopic spin–lattice relaxation time measurements to probe polymer mobility.

Design and analysis of a multilayer localized surface plasmon resonance graphene biosensor

This paper describes a multilayer localized surface plasmon resonance (LSPR) graphene biosensor that includes a layer of graphene sheet on top of the gold layer, and the use of different coupled configuration of a laser beam. The study also investigates the enhancement of the sensitivity and detection accuracy of the biosensor through monitoring biomolecular interactions of biotin-streptavidin with the graphene layer on the gold thin film. Additionally, the role of thin films of gold, silver, copper and aluminum in the performance of the biosensor is separately investigated for monitoring the binding of streptavidin to the biotin groups. The performance of the LSPR graphene biosensor is theoretically and numerically assessed in terms of sensitivity, adsorption efficiency, and detection accuracy under varying conditions, including the thickness of biomolecule layer, number of graphene layers and operating wavelength. Enhanced sensitivity and improved adsorption efficiency are obtained for the LSPR graphene biosensor in comparison with its conventional counterpart; however, detection accuracy under the same resonance condition is reduced by 5.2% with a single graphene sheet. This reduction in detection accuracy (signal to noise ratio) can be compensated for by introducing an additional layer of silica doped B2O3 (sdB2O3) placed under the graphene layer. The role of prism configuration, prism angle and the interface medium (air and water) is also analyzed and it is found that the LSPR graphene biosensor has better sensitivity with triangular prism, higher prism angle, lower operating wavelength and larger number of graphene layers. The approach involves a plot of a reflectivity curve as a function of the incidence angle. The outcomes of this investigation highlight the ideal functioning condition corresponding to the best design parameters.

Measuring miscible fluid displacement in porous media with magnetic resonance imaging

The development of new quantitative magnetic resonance imaging (MRI) technologies open new opportunities for measurements of mass transport in porous media. The current work examines a simple miscible displacement process of H2O and D2O in porous media samples. Laboratory measurements of dispersion in porous media traditionally monitor the effluent intensity of an injected tracer. We employ MRI to obtain quantitative water saturation profiles, and to measure dispersion in rock core plugs. The saturation profiles are modeled with PHREEQC, a fluid transport modeling program. We demonstrate how independent magnetic resonance measurements can be employed to estimate three important input parameters for PHREEQC, mobile porosity, immobile porosity, and dispersivity. Bulk Carr Purcell Meiboom Gill (CPMG) T2 distribution measurements were undertaken to estimate mobile and immobile porosity. Bulk alternating-pulsed-gradient-stimulated-echo (APGSTE) measurements were undertaken to measure dispersivity. The imaging method employed, T2 mapping Spin Echo Single Point Imaging (SE-SPI), also provides information about the pore size distributions in the rock cores, and how the fluid occupancy of the pores changes during the displacement process.

New opportunities for quantitative and time efficient 3D MRI of liquid and solid electrochemical cell components: Sectoral Fast Spin Echo and SPRITE.

The ability to image electrochemical processes in situ using nuclear magnetic resonance imaging (MRI) offers exciting possibilities for understanding and optimizing materials in batteries, fuel cells and supercapacitors. In these applications, however, the quality of the MRI measurement is inherently limited by the presence of conductive elements in the cell or device. To overcome related difficulties, optimal methodologies have to be employed. We show that time-efficient three dimensional (3D) imaging of liquid and solid lithium battery components can be performed by Sectoral Fast Spin Echo and Single Point Imaging with T1 Enhancement (SPRITE), respectively. The former method is based on the generalized phase encoding concept employed in clinical MRI, which we have adapted and optimized for materials science and electrochemistry applications. Hard radio frequency pulses, short echo spacing and centrically ordered sectoral phase encoding ensure accurate and time-efficient full volume imaging. Mapping of density, diffusivity and relaxation time constants in metal-containing liquid electrolytes is demonstrated. 1, 2 and 3D SPRITE approaches show strong potential for rapid high resolution (7)Li MRI of lithium electrode components.

Sparse coding for improved signal-to-noise ratio in MRI

Magnetic Resonance images (MRI) do not only exhibit sparsity but their sparsity take a certain predictable shape which is common for all kinds of images. That region based localised sparsity can be used to de-noise MR images from random thermal noise. This paper present a simple framework to exploit sparsity of MR images for image de-noising. As, noise in MR images tends to change its shape based on contrast level and signal itself, the proposed method is independent of noise shape and type and it can be used in combination with other methods.

Loss and re-adaptation of lumbar intervertebral disc water signal intensity after prolonged bedrest

© 2015, International Society of Musculoskeletal and Neuronal Interactions. All right reserved. The adaptation and re-adaptation process of the intervertebral disc (IVD) to prolonged bedrest is important for understanding IVD physiology and IVD herniations in astronauts. Little information is available on changes in IVD composition. In this study, 24 male subjects underwent 60-day bedrest and In/Out Phase magnetic resonance imaging sequences were performed to evaluate IVD shape and water signal intensity. Scanning was performed before bedrest (baseline), twice during bedrest, and three, six and twenty-four months after bedrest. Area, signal intensity, average height, and anteroposterior diameter of the lumbar L3/4 and L4/5 IVDs were measured. At the end of bedrest, disc height and area were significantly increased with no change in water signal intensity. After bedrest, we observed reduced IVD signal intensity three months (p=0.004 versus baseline), six months (p=0.003 versus baseline), but not twenty-four months (p=0.25 versus baseline) post-bedrest. At these same time points post-bedrest, IVD height and area remained increased. The reduced lumbar IVD water signal intensity in the first months after bedrest implies a reduction of glycosaminoglycans and/or free water in the IVD. Subsequently, at two years after bedrest, IVD hydration status returned towards pre-bedrest levels, suggesting a gradual, but slow, re-adaptation process of the IVD after prolonged bedrest.

Cerebral responses to innocuous somatic pressure stimulation following aerobic exercise rehabilitation in chronic pain patients: a functional magnetic resonance imaging study

Objective: The purpose of this research was to assess the functional brain activity and perceptual rating of innocuous somatic pressure stimulation before and after exercise rehabilitation in patients with chronic pain.

Materials and methods: Eleven chronic pain patients and eight healthy pain-free controls completed 12 weeks of supervised aerobic exercise intervention. Perceptual rating of standardized somatic pressure stimulation (2 kg) on the right anterior mid-thigh and brain responses during functional magnetic resonance imaging (fMRI) were assessed at pre- and postexercise rehabilitation.

Results: There was a significant difference in the perceptual rating of innocuous somatic pressure stimulation between the chronic pain and control groups (P=0.02) but no difference following exercise rehabilitation. Whole brain voxel-wise analysis with correction for multiple comparisons revealed trends for differences in fMRI responses between the chronic pain and control groups in the superior temporal gyrus (chronic pain > control, corrected P=0.30), thalamus, and caudate (control > chronic, corrected P=0.23). Repeated measures of the regions of interest (5 mm radius) for blood oxygen level-dependent signal response revealed trend differences for superior temporal gyrus (P=0.06), thalamus (P=0.04), and caudate (P=0.21). Group-by-time interactions revealed trend differences in the caudate (P=0.10) and superior temporal gyrus (P=0.29).

Conclusion: Augmented perceptual and brain responses to innocuous somatic pressure stimulation were shown in the chronic pain group compared to the control group; however, 12-weeks of exercise rehabilitation did not significantly attenuate these responses.