Structure and transport properties in an N,N-substituted pyrrolidinium tetrafluoroborate plastic crystal system

The structure and transport of N-propyl-N-methylpyrrolidinium tetrafluoroborate (P₁₃BF₄) has been investigated over a wide temperature range in consequence to exhibiting properties suitable for potential solid-state superionic electrolyte applications. Prior to melting, the organic salt, P₁₃BF₄, transforms into a plastic crystal phase. Intrinsic conductivity in this solid, phase I (45–65 °C), is comparable to that in the melt (_~10⁻³ S cm⁻¹). Ionic motion and transport properties were investigated by ¹H and ¹¹B nuclear magnetic resonance (NMR) spectroscopy. Pressure-induced plastic flow in this system may accommodate volume changes in device application and to this extent, X-ray diffraction (XRD) has been used. Scanning electron microscopy (SEM) revealed complex surface morphology and lattice imperfections associated with the strong orientational disorder of the plastic state.

Lithium ion mobility in poly(vinyl alcohol) based polymer electrolytes as determined by 7Li NMR spectroscopy

Solvent-free polymer electrolytes based on poly(vinyl alcohol) (PVA) and LiCF₃SO₃ have shown relatively high conductivities (10⁻⁸-10⁻⁴ S cm⁻¹), with Arrhenius temperature dependence below the differential scanning calorimeter (DSC) glass transition temperature (343 K). This behaviour is in stark contrast to traditional polymer electrolytes in which the conductivity reflects VTF behaviour. ⁷Li nuclear magnetic resonance (NMR) spectroscopy has been employed to develop a better understanding of the conduction mechanism. Variable temperature NMR has indicated that, unlike traditional polymer electrolytes where the linewidth reaches a rigid lattice limit near T_g, the lithium linewidths show an exponential decrease with increasing temperature between 260 and 360 K. The rigid lattice limit appears to be below 260 K. Consequently, the mechanism for ion conduction appears to be decoupled from the main segmental motions of the PVA. Possible mechanisms include ion hopping, proton conduction or ionic motion assisted by secondary polymer relaxations.

Recent insights on the role of cryoprotective agents in vitrification

In recent efforts to produce cryoprotective solutions which cause either complete, or almost complete, vitrification of the cell or tissue material, increasingly complex cocktails of solutes have invariably been used. Why some of these solutes are so much more effective in suppressing ice formation than other, related solutes has never been clear. To begin to compare and contrast the role of the solute in aiding vitrification we have examined the nature of the hydrogen bonding interactions between the solute and water and between the solute molecules themselves, via proton nuclear magnetic resonance experiments. These experiments, carried out on neat samples of the solutions, show marked differences between solutes such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, the family of butanediol isomers, dimethylsulfoxide, and so on, at fixed concentration. The solutions also show marked trends in the NMR chemical shift as a function of concentration in any given solution. Thus it appears that, from the point of view of the physical suppression of ice in aqueous solutions, cryoprotective agents which can act as moderately strong bases are optimum. The mechanism by which the solute promotes glass formation was also investigated in a separate series of NMR experiments using more dilute solutions of the solute in water. These experiments indicate that the role of the solute is twofold in that it must (i) effectively suppress the anomalous structuring which occurs in supercooled water and is responsible for the rapid nucleation of ice and (ii) provide a decrease in molecular mobility at low temperatures such that the nucleation probability is decreased and glass formation occurs at a relatively high temperature. It is argued that both such effects can be brought about by the strong hydrogen bonding interactions between water and solutes such as 2,3-butanediol.

Plastic crystal electrolyte materials : new perspectives on solid state ionics

Plastic crystal materials have long been known but have only relatively recently become of interest as solid–state ion conductors. Their properties are often associated with dynamic orientational disorder or rotator motions in the crystalline lattice. This paper describes recent work in the field including the range of organic ionic compounds that exhibit ion conduction at room temperature. Conductivity in some cases is high enough to render the compounds of interest as electrolyte materials in all solid state electrochemical devices. Doping of the plastic crystal phase with a small ion such as Li+ in some cases produces an even higher conductivity. In this case the plastic crystal acts as a solid state “solvent” for the doped ion and supports the conductive motion of the dopant via motions of the matrix ions. These doped materials are also described in detail.

Solid state NMR analysis of polypyrrole grown in a phosphonium ionic liquid

³¹P, ¹⁹F and ¹³C solid state NMR analysis has been used to investigate the intercalation/de-intercalation of both anions and cations in electrochemically synthesized polypyrrole films. Use of a phosphonium-based ionic liquid, tri(hexyl)(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide, allows the separate detection of the cation and anion by analysis of the phosphorous and fluorine resonances, respectively. Initial results indicate the incorporation of both cations and anions during film growth in the ionic liquid. There is a notable change in the ³¹P chemical shift of the cation on incorporation into the film, consistent with a significant change in environment compared to the pure ionic liquid. Despite its large size, the phosphonium cation can be completely expelled from the film by oxidation.

Conductivity, NMR and crystallographic study of N,N,N,N-tetramethylammonium dicyanamide plastic crystal phases : an archetypal ambient temperature plastic electrolyte material

N,N,N,N-Tetramethylammonium dicyanamide (Me₄NDCA) has been examined via differential scanning calorimetry (DSC), thermogravimetric analysis, conductivity, single crystal X-ray diffraction and ¹H nuclear magnetic resonance (NMR) analyses, and was found to be highly conductive in the solid state (σ =10−3 S cm⁻² at 420 K) and to also exhibit unusual plastic crystal behaviour. To investigate the correlation between such behaviour and the occurrence of molecular rotations in the crystal, ¹H NMR second moment measurements are compared with calculated values predicted from the crystal structure. While DSC analysis indicates a number of solid–solid transitions at ambient temperatures, subsequent ¹H NMR analysis of the Me₄N⁺ cation shows that a variety of rotational motions become active at low (<240 K) temperatures, and that such transitions in rotational states occur over a range of temperatures rather than in a sharp transition. Conductivity analysis reveals that between 320 K and 420 K the conductivity increases by more than six orders of magnitude in the solid state, in line with the transition of the Me₄N⁺ cation to a diffusive state, and that other phase transitions observed in this temperature range have no marked effect on the conductivity. Conduction in this solid state is therefore envisaged to involve a vacancy-diffusion model, involving Me₄N⁺ cation vacancies.

Polyelectrolyte-in-ionic-liquid electrolytes

Novel polymer electrolyte materials based on a polyelectrolyte-in-ionic-liquid principle are described. A combination of a lithium 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSLi) and N,N′-dimethylacrylamide (DMMA) are miscible with the ionic liquid, 1-ethyl-3-methylimidazolium dicyanamide (EMIDCA). EMIDCA has remarkably high conductivity (≥ 2 · 10−2 S · cm−1) at room temperature and acts as a good solvating medium for the polyelectrolyte. At compositions of AMPSLi less than or equal to 75 mol-% in the copolymer (P(AMPSLi-co-DMAA)), the polyelectrolytes in EMIDCA are homogeneous, flexible elastomeric gel materials at 10 − 15 wt.-% of total polyelectrolyte. Conductivities higher than 8 · 10−3 S · cm−1 at 30 °C have been achieved. The effects of the monomer composition, polyelectrolyte concentration, temperature and lithium concentration on the ionic conductivity have been studied using thermal and conductivity analysis, and pulsed field gradient nuclear magnetic resonance techniques.

Towards elucidating microscopic structural changes in Li-ion conductors Li1+yTi2–yAly[PO4 ]3 and Li1+yTi2–yAly[PO4 ]3–x [MO4 ]x(M=V and Nb) : X-ray and27Al and31P NMR studies

A combination of X-ray powder diffraction (XRD) and nuclear magnetic resonance (NMR) studies has demonstrated that attempted substitutions of Al, V and Nb into the framework of LiTi₂(PO₄)₃ yield several impurity phases in addition to direct substitutions of Al into Ti and V, Nb into P sites. Direct substitutions were confirmed by changes in the unit cell dimensions as indicated by the peak shifts observed in the X-ray diffractographs and by analyses of the ²⁷Al and ³¹P magic angle spinning (MAS) spectra. A major impurity phase was identified as AlPO₄ (found in at least two polymorphs) and the amount present increases with increasing Al additions. The formation of AlPO₄ appeared to be enhanced by further V but suppressed by Nb substitution. These results suggest that the presence of AlPO₄ , together with the non-stoichiometric modified LTP, may be the cause for the observed densification of this material upon sintering and the increased ionic conductivity.

Why is it so? The 1H-NMR CH2 splitting in substituted propanes

Nuclear magnetic resonance (NMR) spectroscopy is an important tool in the structural analysis of both organic and inorganic molecules. Proton NMR spectra can yield information about the chemical or bonding environment surrounding various protons, the number of protons in those environments, and the number of neighbouring protons around each proton. However, there is a common misconception about the relationship between the splitting of signals due to the neighbouring protons and the (n+1) rule. This paper discusses how the appearance of deceptively simple spectra has led to this misconception and the correct interpretation and application of the (n+1) rule.

An inclusion complex of β-Cyclodextrin-L-Phenylalanine : 1H NMR and molecular docking studies

An inclusion host-guest complex between β-cyclodextrin (β-CD) and L-phenylalanine (LPhe) was investigated using ¹H nuclear magnetic resonance spectroscopy and molecular docking techniques. ¹H chemical shift changes of β-CD were used to calculate the stability constant (K_stb) of the complex. On the basis of the Hildebrand-Benesi method, the K_stb of the 1:1 complex in D₂O solution at 300 K, pD 7.6 was of 25.5 M^-1, implying a fast intermolecular exchange rate process. Interestingly, docking simulation indicates the toroidal space can be occupied by L-Phe with two favorable arrangements. For the predicted model with the higher probability score, the L-Phe aromatic ring is facing to the secondary hydroxyl groups of β-CD. Results from NMR and docking simulation are in good agreement with the x-ray structures of β-CD/L-phenylalanine derivatives.

Investigating the effect of solution pH on speciation of La(4OH-cin)3 with correlation to electrochemical behaviour and corrosion efficiency

The nature of the species in solution plays a major role on the effectiveness of the corrosion inhibitor on a steel substrate. The speciation of lanthanum 4-hydroxy cinnamate (La(4OHCin) ₃) in solution has been evaluated using experimental techniques composed of potentiodynamic polarisation, immersion tests, nuclear magnetic spectroscopy and mass spectroscopy. It is evident that the species in solution are dependent on pH and this impacts the corrosion inhibition mechanism and the efficiency. It was found that at a neutral pH of 5.5 the La(4OH-Cin)₃ behaves as a strong anodic inhibitor. Whereas, when the pH shifts to low (pH2.5) and/or high (pH8) the corrosion mechanism changes.

Associations between smoking status, lifestyle and lipoprotein subclasses

Background: Although the relationship between cigarette smoking and cardiovascular disease (CVD) is well-established, the underlying mechanisms remain unclear. Smokers have a more atherogenic lipid profile but this may be mediated by lifestyle-related factors. Because detailed analysis of lipoprotein subclasses using nuclear magnetic resonance spectroscopy (NMR) may improve characterisation of lipid abnormalities, we applied the technique to investigate the relationships between smoking status, other lifestyle-related risk factors and lipoproteins in a contemporary cohort.

Methods: A total of 612 participants (360 women) aged 40-69 years at baseline (1990-1994) enrolled in the community-based Melbourne Collaborative Cohort Study had plasma lipoproteins measured using NMR. Data were analysed separately for men and women.

Results: After adjusting for other lifestyle-related risk factors, mean total low-density lipoprotein (LDL) particle concentration was higher for female smokers than non-smokers. Both medium and small LDL particle concentrations contributed to this difference. Both total high-density lipoprotein (HDL) and large HDL particle concentrations were lower for female smokers than non-smokers. The proportion at increased risk (according to NMR-determined particle size and number) was higher for female smokers than non-smokers. For men, there were few differences in lipoprotein measures related to smoking.

Conclusions: Female smokers have a more atherogenic lipoprotein profile than non-smokers, and this difference is independent of lifestyle-related risk factors. Lipoprotein profiles did not differ greatly between male smokers and non-smokers. These data reinforce the importance for women of not smoking.

1H-NMR and mass spectrometric characterization of the metabolic response of juvenile Atlantic salmon (Salmo salar) to long-term handling stress

Stressors of various kinds constantly affect fish both in the wild and in culture, examples being acute water temperature and quality changes, predation, handling, and confinement. Known physiological responses of fish to stress such as increases in plasma cortisol and glucose levels, are considered to be adaptive, allowing the animal to cope in the short term. Prolonged exposure to stressors however, has the potential to affect growth, immune function, and survival. Nonetheless, little is known about the mechanisms underlying the long-term stress response. We have investigated the metabolic response of juvenile Atlantic salmon (Salmo salar) to long-term handling stress by analyzing fish plasma via ¹H nuclear magnetic resonance spectroscopy and ultra high performance liquid chromatography–mass spectrometry (UPLC–MS), and comparing results with controls. Analysis of NMR data indicated a difference in the metabolic profiles of control and stressed fish after 1 week of stress with a maximum difference observed after 2 weeks. These differences were associated with stress-induced increases in phosphatidyl choline, lactate, carbohydrates, alanine, valine and trimethylamine-N-oxide, and decreases in low density lipoprotein, very low density lipoprotein, and lipid. UPLC-MS data showed differences at week 2, associated with another set of compounds, tentatively identified on the basis of their mass/charge. Overall the results provided a multi-faceted view of the response of fish to long-term handling stress, indicating that the metabolic disparity between the control and stress groups increased to week 2, but declined by weeks 3 and 4, and revealed several new molecular indicators of long-term stress.

Spectroscopic techniques

Spectroscopic techniques are widely used in forensic laboratories for quantitative and qualitative analysis. This artictle provides an overview of the spectroscopic techniques most commonly encountered in forensic laboratories. Infrared spectroscopy, Raman spectroscopy, X-ray fluorescence, scanning electron microscopy energy dispersive X-ray spectroscopy, and nuclear magnetic resonance spectroscopy are used mainly for identification or characterization of substances. Visible and ultraviolet spectroscopy, atomic absorption spectroscopy and atomic emission spectroscopy are used mainly for measurement of substances or elements. Some techniques can be used for both identification and measurement. Related techniques such as molecular fluorescence, chemiluminescence and synchrotron techniques are also discussed.