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.

Structural characterization of conducting polypyrrole using 13C cross-polarization/magic-angle spinning solid-state nuclear magnetic resonance spectroscopy

¹³C nuclear magnetic resonance (n.m.r.) has been used to study polypyrrole and N-substituted polypyrrole in the solid state. The extent of oxidation appears to be counterion-dependent; in particular, the quinoid structure appears favoured in the films prepared with dodecyl sulfate. Resonances associated with the quinoid unit are lost upon reduction of the polypyrrole film, which supports the idea that the quinoid structure is associated with the oxidized form of polypyrrole. N-substituted polypyrroles have a more distinct resonance at 110 ppm, which is linked to lower degrees of oxidation or charge delocalization in these systems. The decrease in conductivity of polypyrrole upon thermal ageing in air is associated with both the loss of counterion (‘thermal dedoping’) and the decomposition of the quinoid structure in the polymer backbone. There is no indication of carbonyl formation in the solid-state n.m.r. spectra obtained in the present study.

A nuclear magnetic resonance study of 7Li dynamics in polyether-urethane based solid polymer electrolytes

Nuclear magnetic resonance (NMR) is a technique that allows the probing of the dynamics of specific magnetically active nuclei. In the present study a polyethylene glycol network containing varying concentrations of LiClO₄ have been studied using ⁷Li NMR relaxation techniques. A plasticiser, tetraglyme, has been added to several samples to improve the mobility of the polymer and thus of the ionic species. The effects of tetraglyme and salt concentration on the cationic mobility and environment have been investigated using T₁ and T₂ relaxation experiments, with the presence of two cationic species of differing relaxation times (and possibly mobility) reported. The results are discussed with relevance to conductivity measurements made on similar samples.

Visualisation of chemical processes during corrosion of zinc using magnetic resonance imaging

Compositional and structural changes within an electrolyte solution above an electrochemically active metal surface have been visualised using magnetic resonance imaging (MRI) for the first time. In these proof-of-concept experiments, zinc metal was galvanically corroded in a saturated lithium chloride solution. Magnetic resonance relaxation maps were taken during the corrosion process and spatial variations in both T₁ and T₂ relaxation times were observed to change with time. These changes were attributed to changes in the speciation of zinc ions in the electrolyte.

Synthesis of silica-coated ZnO nanocomposite : the resonance structure of polyvinyl pyrrolidone (PVP) as a coupling agent

Abstract The preparation of silica-coated ZnO nanocomposite using polyvinyl pyrrolidone (PVP) as a coupling agent was investigated. Transmission electron microscopy analysis revealed that silica has been deposited on the surface of PVP-capped ZnO nanoparticles as a continuous thin layer. Two-dimensional correlation analysis based on the time-dependent UV–vis spectra was introduced to study the interaction governing the deposition of silica on to PVP-capped ZnO. Strong hydrogen bonds formed between the amphiphilic PVP molecules and silica in the silicacoated PVP-capped ZnO composites. The reduced photocatalytic activity of silica-coated ZnO nanoparticles will enhance their performance as durable, safe, and nonreactive UV blockers in plastics, paints, and coating for outdoor textile and timber products.

Identification of a by-product of nitric oxide synthase activity in human acute brain injury with in vivo proton magnetic resonance spectroscopy

BACKGROUND AND PURPOSE: Laboratory studies have been used to identify nitric oxide as a notable mediator in neuronal death after acute brain injury. To our knowledge, this has not previously been confirmed with in vivo study in humans. Our purpose was to seek in vivo evidence for the induction of nitric oxide synthase (NOS) in human acute brain injury by using proton MR spectroscopy.

METHODS: In vitro proton MR spectra were obtained in neural extracts from 30 human cadavers, and in vivo spectra were obtained in 20 patients with acute brain injury and in a similar number of control subjects.

RESULTS: We identified a unique peak at 3.15 ppm by using in vivo proton MR spectroscopy in eight of 20 patients with acute brain injury but not in 20 healthy volunteers (P < .002). On the basis of in vitro data, we have tentatively assigned this peak to citrulline, a NOS by-product.

CONCLUSION: To our knowledge, our findings suggest, for the first time, that excitotoxicity may occur in human acute brain injury. Confirmation with the acquisition of spectra in very early acute cerebral injury would provide a rationale for the use of neuroprotective agents in these conditions, as well as a new noninvasive method for quantification.

Analysis of dynamic strains in tibia during human locomotion based on flexible multibody approach integrated with magnetic resonance imaging technique

Bone is known to adapt to the prevalent strain environment while the variation in strains, e.g., due to mechanical loading, modulates bone remodeling, and modeling. Dynamic strains rather than static strains provide the primary stimulus of bone functional adaptation. The finite element method can be generally used for estimating bone strains, but it may be limited to the static analysis of bone strains since the dynamic analysis requires expensive computation. Direct in vivo strain measurement, in turn, is an invasive procedure, limited to certain superficial bone sites, and requires surgical implementation of strain gauges and thus involves risks (e.g., infection). Therefore, to overcome difficulties associated with the finite element method and the in vivo strain measurements, the flexible multibody simulation approach has been recently introduced as a feasible method to estimate dynamic bone strains during physical activity. The purpose of the present study is to further strengthen the idea of using the flexible multibody approach for the analysis of dynamic bone strains. Besides discussing the background theory, magnetic resonance imaging is integrated into the flexible multibody approach framework so that the actual bone geometry could be better accounted for and the accuracy of prediction improved.

Comparison of performance parameters for conventional and localized surface plasmon resonance graphene biosensors

This paper investigates the enhancement of the sensitivity and adsorption efficiency of a localized surface plasmon resonance (LSPR) biosensor that includes a layer of graphene sheet on top of the gold layer. For this purpose, biomolecular interactions of biotin-streptavidin with the graphene layer on the gold thin film are monitored. The performance of the LSPR graphene biosensor is theoretically and numerically assessed in terms of sensitivity and adsorption efficiency 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. It is found that the LSPR graphene biosensor has better sensitivity with lower operating wavelength and larger number of graphene layers.

Variable incidence angle localized surface plasmon resonance graphene biosensor

This paper investigates the enhancement of sensitivity of variable incidence angle LSPR biosensor by monitoring biomolecular interactions of biotin-streptavidin with gold thin film. The investigation is carried out by means of introducing an additional layer of graphene sheet on top of gold layer (graphene biosensor) and using different coupling configuration of laser beam. The sensitivity, which is indicated by the shift of plasmon resonance angle, increases with graphene deposited onto the gold layers and is linearly related with the number of graphene layers. In addition, an investigation of the shift of plasmon dip is carried out for two different analyte interfaces: air and water. It is found that graphene biosensor has better sensitivity for triangular prism, higher prism angle, and water interface. The evaluation approach involves a plot of a reflectivity curve as a function of the angle of incidence while the operating wavelength is kept fixed.

Two-dimensional correlation localized surface plasmon resonance spectroscopy for analysis of the interaction between metal nanoparticles and bovine serum albumin

Time-resolved extinction spectra assisted with two-dimensional correlation spectroscopy (2DCOS) analysis and principal component analysis (PCA) were employed to investigate the interaction between bovine serum albumin (BSA) and metal nanoparticles (NPs). A series of localized surface plasmon resonance (LSPR) spectra of metal NPs were measured just after a small amount of BSA was added into metal colloids. Through 2DCOS analysis, remarkable changes in the intensities of the LSPR were observed. The interaction process was totally divided into three periods according to the PCA. Transmission electron microscopy, dynamic light scattering, and ζ-potential measurements were also employed to characterize the interaction between BSA and metal NPs. The addition of BSA brings silver NPs to aggregate through the electrostatic interaction between them, but it has less effect on gold NPs. In a gold and silver mixed system, gold NPs can affect the interaction of silver NPs and BSA, leading it to weaken. The combination of 2DCOS analysis and LSPR spectroscopy is powerful for exploring the LSPR spectra of the metal NP involved systems. This combined technique holds great potential in LSPR sensing through analysis of slight, slim spectral changes of metal colloids