Search

Electrolytes with a high lithium transference number linked with high ionic conductivity are urgently needed for high power battery operation. In this work, we present newly synthesized lithium tetra(trifluoromethanesulfonyl)propene as a salt-in-glyme-based "salt-in-solvent" electrolyte. We employ impedance spectroscopy in symmetric Li/electrolyte/Li cells and pulsed field gradient nuclear magnetic resonance spectroscopy to investigate the lithium conduction mechanism. We find predominant lithium conductivity with very high lithium transference numbers (∼70% from the polarization experiments) and three times higher ionic conductivity compared to well-known lithium triflate in diglyme electrolyte. This is a consequence of the reduced mobilities of large anions linked with improved ionic dissociation.

The unique proton conduction mechanism of phosphoric acid is important for the functions of complex phosphate containing biological and technological systems (e.g. phospholipid membranes and polybenzimidazole phosphoric acid membranes for high-temperature PEM fuel cells). In neat phosphoric acid structural proton diffusion, i.e. proton hopping between phosphoric acid molecules, is superimposed onto hydrodynamic diffusion of the molecules in the viscous liquid. In this study we separate the two dynamic contributions on the nanosecond timescale for the model systems phosphoric acid-water and phosphoric acid-benzimidazole. We demonstrate that 1 H NMR dipolar relaxation measurements are controlled by hydrodynamic diffusion for the investigated conditions, while 17 O NMR quadrupolar relaxation measurements reflect local proton displacement as part of structural diffusion. Quasielastic neutron scattering (QENS) applying high resolution backscattering spectroscopy (nBSS) confirms structural proton diffusion measurements using PFG-NMR in phosphoric acid-benzimidazole mixtures at different concentrations. With increasing benzimidazole content proton diffusion coefficients on the nanosecond scale decrease, thus following the trend of reduced hydrogen bond network frustration. The momentum transfer (Q) dependence of the width of the QENS spectra indicates the jump diffusion mechanism and can be scaled to a master plot both for different temperatures and different benzimidazole contents. This indicates a fundamentally unchanged structural proton diffusion process, however, with a lower probability of occurrence for successful intermolecular proton transfer with increasing benzimidazole content. Results of this work enable a better separation of different diffusion processes on short timescales also in more complex phosphoric acid containing systems.

Transport properties and hydration behavior of phosphoric acid/(benz)imidazole mixtures are investigated by diverse NMR techniques, thermogravimetric analysis (TGA) and conductivity measurements. The monomeric systems can serve as models for phosphoric acid/poly-benzimidazole membranes which are known for their exceptional performance in high temperature PEM fuel cells. 1 H- and 31 P-NMR data show benzimidazole acting as a strong Brønsted base with respect to neat phosphoric acid. Since benzimidazole's nitrogens are fully protonated with a low rate for proton exchange with phosphate species, proton diffusion and conduction processes must take place within the hydrogen bond network of phosphoric acid only. The proton exchange dynamics between phosphate and benzimidazole species pass through the intermediate exchange regime (with respect to NMR line separations) with exchange times being close to typical diffusion times chosen in PFG-NMR diffusion measurements (ms regime). The resulting effects, as described by the Kärger equation, are included into the evaluation of PFG-NMR data for obtaining precise proton diffusion coefficients. The highly reduced proton diffusion coefficient within the phosphoric acid part of the model systems compared to neat phosphoric acid is suggested to be the immediate consequence of proton subtraction from phosphoric acid. This reduces hydrogen bond network frustration (imbalance of the number of proton donors and acceptors) and therefore also the rate of structural proton diffusion, phosphoric acid's acidity and hygroscopicity. Reduced water uptake, shown by TGA, goes along with reduced electroosmotic water drag which is suggested to be the reason for PBI-phosphoric acid membranes performing better in fuel cells than other phosphoric-acid-containing electrolytes with higher protonic conductivity.

Ionic charge carrier formation and mobility, including the underlying conduction mechanisms, are investigated for phosphoric acid at water contents relevant for the acid's application as electrolyte in fuel cells. The high conductivity contribution from structural diffusion involving intermolecular proton transfer (∼97%) in neat phosphoric acid (H 3 PO 4 ) passes through a maximum at this composition. Hydrogen bond network frustration (imbalance of the number of proton donors and acceptors), which is closely related to the appearance of structural diffusion, decreases with both elimination and addition of water. Structural diffusion is virtually disappearing for H 3 PO 4 ·2H 2 O, yet, the overall conductivity increases with increasing water content and reaches a maximum at a composition of H 3 PO 4 ·5H 2 O. The conductivity increase is a consequence of the progressive de-coupling of the diffusion of aqueous species from that of phosphate species and the strongly enhanced acidity of phosphoric acid at low water contents. High concentrations of protonated aqueous species with high diffusivity then lead to high conductivity contributions from vehicular transport. The increased water transport associated with the change in transport mechanism is suggested to have severe implications for fuel cell applications. At low water contents the conductivity contribution of structural diffusion is also reduced, but it is accompanied by conductivity contributions from a high concentration of multiply charged condensation products (e.g. H 2 P 2 O 7 2- , H 3 P 3 O 10 2- and H 2 P 3 O 10 3- ). The results underline the singularity of structure diffusion in neat phosphoric acid (H 3 PO 4 ) and its sensitivity against any perturbation.

Diphosphoric acid (H4P2O7) is the first condensation product of phosphoric acid (H3PO4), the compound with the highest intrinsic proton conductivity in the liquid state. It exists at higher temperature (T > 200 °C) and lower relative humidity (RH ≈ 0.01%) and shows significant ionic conductivity under these conditions. In this work, ab initio molecular dynamics simulations of a pure H4P2O7 model system and NMR spectroscopy on nominal H4P2O7 (which contains significant amounts of ortho- and triphosphoric acid in thermodynamic equilibrium) were performed to reveal the nature and underlying mechanisms of the ionic conductivity. The central oxygen of the molecule is found to be excluded from any hydrogen bonding, which has two interesting consequences: (i) compared to H3PO4, the acidity of H4P2O7 is severely increased, and (ii) the condensation reaction only leads to a minor decrease in hydrogen bond network frustration, which is thought to be one of the features enabling high proton conductivity. A topological analysis of diphosphoric acid's hydrogen bond network shows remarkable similarities to that of phosphonic acid (H3PO3). The hydrogen bonding facilitates protonic polarization fluctuations (Zundel polarization) extending over several molecules (Grotthuss chains), the other important ingredient for efficient structural diffusion of protons. At T = 160 °C, this is estimated to make a conductivity contribution of about 0.1 S/cm, which accounts for half of the total ionic conductivity (σ ≈ 0.2 S/cm). The other half is suggested to result from diffusion of charged phosphate species (vehicle mechanism) that are present in high concentration, resembling conduction in ionic liquids.

Precise diffusion measurements of rhodamine 6G (Rh6G) dissolved in D2O at concentrations between 50 and 200 μM were carried out in the temperature range from 280 to 320 K using pulsed field gradient nuclear magnetic resonance (PFG-NMR). The obtained diffusion coefficients can be used as a calibration reference in fluorescence correlation spectroscopy (FCS). Besides measuring the diffusivity of Rh6G, the diffusion coefficient of the solvent in the same system could be determined in parallel by PFG-NMR as the resonances of water and Rh6G are well separated in the (1)H NMR spectrum. To analyze the differences due to the isotope effect of the solvent (D2O vs. H2O), the correlation time τD of Rh6G was measured by FCS in both D2O and H2O. The obtained isotopic correction factor, τD(D2O)/τD(H2O) = 1.24, reflects the isotope effect of the solvent´s self-diffusion coefficients as determined previously by PFG-NMR.

Ninety-three consecutive patients with chronic total coronary occlusion underwent an attempted mechanical des-obliteration by percutaneous coronary angioplasty with a balloon catheter. The global results were 55 p. 100 initial successes (residual stenosis less than 50 p. 100). The good prognostic factors were: 1) left coronary artery, especially left circumflex artery occlusion p less than 0.50, and 2) the proximity to the date of occlusion as assessed from the clinical history or by the occurrence of occlusion between the time of diagnostic coronary angiography and angioplasty. In cases of recent occlusion dating less than one month, the success rate was high: 69 p. 100. On the other hand, there were no successes in occlusions of over 6 months standing. The presence of myocardial infarction did not influence the results. There were few complications (7 p. 100) and these did not include any deaths or cases requiring emergency surgery. Exercise stress tests were carried out after the procedure and were negative in 28 out of 32 patients (88 p. 100). Forty-three patients successfully revascularised were followed up for 1 to 48 months (average 9 months) after angioplasty. Thirty-one patients were asymptomatic. Of the 12 symptomatic patients, 7 underwent exercise stress tests (6 positive) and all had control angiography which showed restenosis in 10 cases with 5 occlusions. Percutaneous coronary angioplasty of recent total coronary occlusions gives good initial results without major complications, and the medium term clinical results are satisfactory.

Experience is reported with 100 consecutive patients in whom percutaneous transluminal coronary angioplasty (PTCA) was attempted on chronically occluded coronary arteries that had no visible anterograde flow. Ninety-eight patients had angina and all had collateral vessels to the occluded artery on angiography. A movable guidewire/dilatation system was used in all cases. Overall initial PTCA success rate was 56% and was related to duration of occlusion (69% success rate for occlusions of 1 month or less, 50% for 1 to 6 months and 11% after 6 months). Complications were minor; no patient died or required emergency bypass operation. Of the 44 patients in whom PTCA failed, 20 underwent elective bypass surgery for relief of angina and 24 were treated medically. Follow-up at a mean of 8 months (range 1 to 48) was available for 49 of the 56 patients in whom PTCA was successful: 40 had subjective improvement, 6 no change and 3 felt worse. Control angiography was carried out in 40 of the 56 patients with primary success and showed long-term success in 18 and reocclusion or significant stenosis in 22. Of these 22, 11 were successfully treated by a second PTCA, 2 underwent operation and 9 were treated medically. Recanalization of totally occluded coronary arteries with no forward flow has a lower initial success rate (56%) than PTCA for stenoses and the recurrence rate is higher (55%), but effective relief of angina is achieved in successful cases. The risk of serious complications appears to be low.

Twenty patients with a chronic total coronary artery occlusion were studied before and 1 to 48 months (mean 9) after successful recanalization by angioplasty and compared with a group of 20 normal subjects. Before angioplasty, 19 of these 20 patients had angina. Collateral vessels to the distal part of the occluded vessel were visible in all 20 patients. A previous myocardial infarction was documented in 14 patients (9 with a Q wave and 5 with a non-Q wave infarction). At the time of follow-up, three patients were symptomatic: one had unstable angina and two had a positive stress test. The follow-up angiogram showed a significant restenosis in six patients and reocclusion in two. The mean ejection fraction had improved slightly from 59 +/- 11% to 63 +/- 9% (p less than 0.05). Left ventricular wall motion synchronism was studied using two variables for 128 shortening segments: the "time of peak contraction" and the "time of peak relaxation," as obtained from biharmonic Fourier transformation for each segment. Their respective standard deviations reflect the synchronism of contraction and relaxation. The mean standard deviations of the two variables expressed in degrees of one cardiac cycle (360 degrees) were respectively: 5.5 +/- 0.4 degrees for the time of peak contraction and 6.0 +/- 0.5 degrees for the time of peak relaxation in the 20 normal subjects, 11.7 +/- 1.7 degrees and 23.0 +/- 3.0 degrees before recanalization and 9.6 +/- 1.8 degrees and 12.5 +/- 2.2 degrees at follow-up in the group of 20 patients. These values were significantly higher (p less than 0.05) in the patients than in the normal group.(ABSTRACT TRUNCATED AT 250 WORDS)

We reviewed 600 consecutive percutaneous transluminal coronary angioplasty procedures in 530 patients. There were 475 men (89%) and 55 women (11%) with a mean age of 55 +/- 9 years. Primary success per patient was 87%. Major acute complications occurred in 58 patients (10%): 2 deaths, vessel or side branch occlusion in 44 patients and ventricular fibrillation in 12 patients. Clinical follow-up was available in 344 of the first 348 patients (99%) at 12 +/- 6 months. Of these, 242 patients (70%) underwent control angiography at 12 +/- 6 months. Including repeat angioplasty, 82% of patients (281/344) with primary success were improved by at least one New York Heart Association functional class. Coronary events among the patients with no improvement were one sudden death, one myocardial infarction, and 16 bypass operations. Four subgroups of special interest were analysed: multivessel angioplasty (100 patients), angioplasty for chronic total occlusion (100 patients), angioplasty for evolving myocardial infarction (50 patients), and repeat coronary angioplasty (70 patients). Primary success rates were 87, 56, 84 and 90%, complication rates 9, 0, 9, and 3%, and recurrence rates 41, 48, 23, and 48%, respectively. At follow-up, improvement by at least one New York Heart Association class was observed in 77, 85, 88, and 80% of patients, respectively. Successful coronary angioplasty including repeat procedures achieved a long-term clinical success in about 80% of patients.

Unlabelled: The diagnosis of valvular regurgitation (R) is usually based on clinical signs. Quantification conventionally requires catheterization (C). We have quantified R with cardiac blood pool scintigraphy (CBPS) and compared the results with those obtained by C. Regurgitant fraction (RF) determined by C was calculated with the technique of Dodge. Forward output was measured by thermodilution or cardiogreen dilution. The RF at CBPS was obtained by the stroke index ratio (SIR) minus 1.2 divided by SIR, where SIR is the ratio of the stroke counts of left ventricle over those of the right ventricle. Stroke counts are calculated directly from the time-activity curves. Each time-activity curve was obtained by drawing one region of interest around each diastolic image. The correction factor (1.2) was calculated from a large normal population. 22 patients had aortic R, 7 mitral R, 12 both, 8 patients had no evidence of regurgitation. RF of the patients with R varied from 27 to 71% (x = 42%) at C and from 26 to 74% (y = 41%) at CBPS. Linear regression shows a good correlation coefficient (r = 0.82). The regression equation is y = 0.93x + 1.8. No correlation was found between RF (CBPS or C) and the severity of R assessed visually from angiography., In Conclusion: CBPS, a non-invasive method, allows easy and repeatable determination of RF and correlates well with data obtained at catheterization.

To assess whether myocardial lipid metabolism is altered in the "stunned" myocardium we have studied the metabolism of (1-14C)-palmitate during reperfusion in a modified rat heart preparation. Hearts were perfused retrogradely at a physiological flow rate (2 ml/min) in a non-recirculating system with erythrocyte-enhanced Krebs-Henseleit buffer containing albumin 0.4 mM, glucose 11 mM, palmitate 0.4 mM and trace amounts of (1-14C)-palmitate. Left ventricular pressure was measured by a latex balloon in the left ventricular cavity. Control hearts were perfused at constant flow for 120 min. To achieve reversible ischaemic damage, myocardial perfusion was reduced by 95% for 40 min, followed by reperfusion at the control flow rate for 60 min (reperfusion group). For comparison, irreversible damage was produced by calcium free perfusion (calcium paradox group). In the reperfusion group, the developed pressure was severely depressed 5 min after reperfusion to 23% of the value in the control group (p less than 0.05) but recovered to 84% (NS) at 60 min. In the calcium paradox group, mechanical activity ceased completely without recovery. Myocardial uptake of (1-14C)-palmitate in the reperfusion group was similar to the control experiments for the entire reperfusion period, whereas a marked depression was observed in the calcium paradox group. 14CO2 production was severely depressed at the onset of reperfusion in both the reperfusion and calcium paradox group to 42% (p less than 0.05) and 29% (p less than 0.05) respectively. In contrast to the calcium paradox group, 14CO2 production in the reperfusion group recovered progressively to 70% (NS) of the control value during the 60 min of reperfusion.(ABSTRACT TRUNCATED AT 250 WORDS)