LiI-doped N,N-dimethyl-pyrrolidinium iodide, an archetypal rotator-phase ionic conductor

N,N-Dimethyl-pyrrolidinium iodide, and the effect of doping with LiI, has been investigated using DSC, NMR, and impedance spectroscopy. It was found that the addition of a small amount of LiI enhances the ionic conductivity by LIP to 3 orders of magnitude for this ionic solid. Furthermore, a slight decrease in phase transition onset temperatures, as well as the appearance of a superimposed narrow line in the H-1 NMR spectra with dopant, suggest that the LiI facilitates the mobility of the matrix material, possibly by the introduction of vacancies within the lattice. Li-7 NMR line width measurements reveal a narrow Li line width, decreasing in width and increasing in intensity with temperature, indicating mobile Li ions.

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 (Me(4)NDCA) has been examined via differential scanning calorimetry (DSC), thermogravimetric analysis, conductivity, single crystal X-ray diffraction and H-1 nuclear magnetic resonance (NMR) analyses, and was found to be highly conductive in the solid state (sigma = 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, H-1 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 H-1 NMR analysis of the Me4N+ cation shows that a variety of rotational motions become active at low (

Crystal phases and glassy dynamics in monodisperse hard ellipsoids

We have performed Monte Carlo and molecular dynamics simulations of suspensions of monodisperse, hard ellipsoids of revolution. Hard-particle models play a key role in statistical mechanics. They are conceptually and computationally simple, and they offer insight into systems in which particle shape is important, including atomic, molecular, colloidal, and granular systems. In the high density phase diagram of prolate hard ellipsoids we have found a new crystal, which is more stable than the stretched FCC structure proposed previously . The new phase, SM2, has a simple monoclinic unit cell containing a basis of two ellipsoids with unequal orientations. The angle of inclination is very soft for length-to-width (aspect) ratio l/w=3, while the other angles are not. A symmetric state of the unit cell exists, related to the densest-known packings of ellipsoids; it is not always the stable one. Our results remove the stretched FCC structure for aspect ratio l/w=3 from the phase diagram of hard, uni-axial ellipsoids. We provide evidence that this holds between aspect ratios 3 and 6, and possibly beyond. Finally, ellipsoids in SM2 at l/w=1.55 exhibit end-over-end flipping, warranting studies of the cross-over to where this dynamics is not possible. Secondly, we studied the dynamics of nearly spherical ellipsoids. In equilibrium, they show a first-order transition from an isotropic phase to a rotator phase, where positions are crystalline but orientations are free. When over-compressing the isotropic phase into the rotator regime, we observed super-Arrhenius slowing down of diffusion and relaxation, and signatures of the cage effect. These features of glassy dynamics are sufficiently strong that asymptotic scaling laws of the Mode-Coupling Theory of the glass transition (MCT) could be tested, and were found to apply. We found strong coupling of positional and orientational degrees of freedom, leading to a common value for the MCT glass-transition volume fraction. Flipping modes were not slowed down significantly. We demonstrated that the results are independent of simulation method, as predicted by MCT. Further, we determined that even intra-cage motion is cooperative. We confirmed the presence of dynamical heterogeneities associated with the cage effect. The transit between cages was seen to occur on short time scales, compared to the time spent in cages; but the transit was shown not to involve displacements distinguishable in character from intra-cage motion. The presence of glassy dynamics was predicted by molecular MCT (MMCT). However, as MMCT disregards crystallization, a test by simulation was required. Glassy dynamics is unusual in monodisperse systems. Crystallization typically intervenes unless polydispersity, network-forming bonds or other asymmetries are introduced. We argue that particle anisometry acts as a sufficient source of disorder to prevent crystallization. This sheds new light on the question of which ingredients are required for glass formation.

Thermal analysis, nuclear magnetic resonance spectroscopy, and impedance spectroscopy of N,N-dimethyl-pyrrolidinium iodide: An ionic solid exhibiting rotator phases

N,N-dimethyl-pyrrolidinium iodide has been investigated using differential scanning calorimetry, nuclear magnetic resonance (NMR) spectroscopy, second moment calculations, and impedance spectroscopy. This pyrrolidinium salt exhibits two solid-solid phase transitions, one at 373 K having an entropy change, Delta S, of 38 J mol(-1) K-1 and one at 478 K having Delta S of 5.7 J mol(-1) K-1. The second moment calculations relate the lower temperature transition to a homogenization of the sample in terms of the mobility of the cations, while the high temperature phase transition is within the temperature region of isotropic tumbling of the cations. At higher temperatures a further decrease in the H-1 NMR linewidth is observed which is suggested to be due to diffusion of the cations. (C) 2005 American Institute of Physics.

Retrospective study of sonographic findings in bone involvement associated with rotator cuff calcific tendinopathy: preliminary results of a case series

Abstract Objective: The present study was aimed at investigating bone involvement secondary to rotator cuff calcific tendonitis at ultrasonography. Materials and Methods: Retrospective study of a case series. The authors reviewed shoulder ultrasonography reports of 141 patients diagnosed with rotator cuff calcific tendonitis, collected from the computer-based data records of their institution over a four-year period. Imaging findings were retrospectively and consensually analyzed by two experienced musculoskeletal radiologists looking for bone involvement associated with calcific tendonitis. Only the cases confirmed by computed tomography were considered for descriptive analysis. Results: Sonographic findings of calcific tendinopathy with bone involvement were observed in 7/141 (~ 5%) patients (mean age, 50.9 years; age range, 42-58 years; 42% female). Cortical bone erosion adjacent to tendon calcification was the most common finding, observed in 7/7 cases. Signs of intraosseous migration were found in 3/7 cases, and subcortical cysts in 2/7 cases. The findings were confirmed by computed tomography. Calcifications associated with bone abnormalities showed no acoustic shadowing at ultrasonography, favoring the hypothesis of resorption phase of the disease. Conclusion: Preliminary results of the present study suggest that ultrasonography can identify bone abnormalities secondary to rotator cuff calcific tendinopathy, particularly the presence of cortical bone erosion.

Shrimp-shape domains in a dissipative kicked rotator

Some dynamical properties for a dissipative kicked rotator are studied. Our results show that when dissipation is taken into account a drastic change happens in the structure of the phase space in the sense that the mixed structure is modified and attracting fixed points and chaotic attractors are observed. A detailed numerical investigation in a two-dimensional parameter space based on the behavior of the Lyapunov exponent is considered. Our results show the existence of infinite self-similar shrimp-shaped structures corresponding to periodic attractors, embedded in a large region corresponding to the chaotic regime. (C) 2011 American Institute of Physics. [doi:10.1063/1.3657917]

Statistical and dynamical properties of a dissipative kicked rotator

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Leukocyte- and Platelet-Rich Fibrin (L-PRF) for Long-Term Delivery of Growth Factor in Rotator Cuff Repair: Review, Preliminary Results and Future Directions

Surgical repair of the rotator cuff repair is one of the most common procedures in orthopedic surgery. Despite it being the focus of much research, the physiological tendon-bone insertion is not recreated following repair and there is an anatomic non-healing rate of up to 94%. During the healing phase, several growth factors are upregulated that induce cellular proliferation and matrix deposition. Subsequently, this provisional matrix is replaced by the definitive matrix. Leukocyte- and platelet-rich fibrin (L-PRF) contain growth factors and has a stable dense fibrin matrix. Therefore, use of LPRF in rotator cuff repair is theoretically attractive. The aim of the present study was to determine 1) the optimal protocol to achieve the highest leukocyte content; 2) whether L-PRF releases growth factors in a sustained manner over 28 days; 3) whether standard/gelatinous or dry/compressed matrix preparation methods result in higher growth factor concentrations. 1) The standard L-PRF centrifugation protocol with 400 x g showed the highest concentration of platelets and leukocytes. 2) The L-PRF clots cultured in medium showed a continuous slow release with an increase in the absolute release of growth factors TGF-β1, VEGF and MPO in the first 7 days, and for IGF1, PDGF-AB and platelet activity (PF4=CXCL4) in the first 8 hours, followed by a decrease to close to zero at 28 days. Significantly higher levels of growth factor were expressed relative to the control values of normal blood at each culture time point. 3) Except for MPO and the TGFβ-1, there was always a tendency towards higher release of growth factors (i.e., CXCL4, IGF-1, PDGF-AB, and VEGF) in the standard/gelatinous- compared to the dry/compressed group. L-PRF in its optimal standard/gelatinous-type matrix can store and deliver locally specific healing growth factors for up to 28 days and may be a useful adjunct in rotator cuff repair.

Modifications in Early Rehabilitation Protocol after Rotator Cuff Repair : EMG Studies

La déchirure de la coiffe des rotateurs est une des causes les plus fréquentes de douleur et de dysfonctionnement de l'épaule. La réparation chirurgicale est couramment réalisée chez les patients symptomatiques et de nombreux efforts ont été faits pour améliorer les techniques chirurgicales. Cependant, le taux de re-déchirure est encore élevé ce qui affecte les stratégies de réhabilitation post-opératoire. Les recommandations post-chirurgicales doivent trouver un équilibre optimal entre le repos total afin de protéger le tendon réparé et les activités préconisées afin de restaurer l'amplitude articulaire et la force musculaire. Après une réparation de la coiffe, l'épaule est le plus souvent immobilisée grâce à une écharpe ou une orthèse. Cependant, cette immobilisation limite aussi la mobilité du coude et du poignet. Cette période qui peut durer de 4 à 6 semaines où seuls des mouvements passifs peuvent être réalisés. Ensuite, les patients sont incités à réaliser les exercices actifs assistés et des exercices actifs dans toute la mobilité articulaire pour récupérer respectivement l’amplitude complète de mouvement actif et se préparer aux exercices de résistance réalisés dans la phase suivante de la réadaptation. L’analyse électromyographique des muscles de l'épaule a fourni des évidences scientifiques pour la recommandation de beaucoup d'exercices de réadaptation au cours de cette période. Les activités sollicitant les muscles de la coiffe des rotateurs à moins de 20% de leur activation maximale volontaire sont considérés sécuritaires pour les premières phases de la réhabilitation. À partir de ce concept, l'objectif de cette thèse a été d'évaluer des activités musculaires de l'épaule pendant des mouvements et exercices qui peuvent théoriquement être effectués au cours des premières phases de la réhabilitation. Les trois questions principales de cette thèse sont : 1) Est-ce que la mobilisation du coude et du poignet produisent une grande activité des muscles de la coiffe? 2) Est-ce que les exercices de renforcement musculaire du bras, de l’avant-bras et du torse produisent une grande activité dans les muscles de la coiffe? 3) Au cours d'élévations actives du bras, est-ce que le plan d'élévation affecte l'activité de la coiffe des rotateurs? Dans notre première étude, nous avons évalué 15 muscles de l'épaule chez 14 sujets sains par électromyographie de surface et intramusculaire. Nos résultats ont montré qu’avec une orthèse d’épaule, les mouvements du coude et du poignet et même quelques exercices de renforcement impliquant ces deux articulations, activent de manière sécuritaire les muscles de ii la coiffe. Nous avons également introduit des tâches de la vie quotidienne qui peuvent être effectuées en toute sécurité pendant la période d'immobilisation. Ces résultats peuvent aider à modifier la conception d'orthèses de l’épaule. Dans notre deuxième étude, nous avons montré que l'adduction du bras réalisée contre une mousse à faible densité, positionnée pour remplacer le triangle d’une orthèse, produit des activations des muscles de la coiffe sécuritaires. Dans notre troisième étude, nous avons évalué l'électromyographie des muscles de l’épaule pendant les tâches d'élévation du bras chez 8 patients symptomatiques avec la déchirure de coiffe des rotateurs. Nous avons constaté que l'activité du supra-épineux était significativement plus élevée pendant l’abduction que pendant la scaption et la flexion. Ce résultat suggère une séquence de plan d’élévation active pendant la rééducation. Les résultats présentés dans cette thèse, suggèrent quelques modifications dans les protocoles de réadaptation de l’épaule pendant les 12 premières semaines après la réparation de la coiffe. Ces suggestions fournissent également des évidences scientifiques pour la production d'orthèses plus dynamiques et fonctionnelles à l’articulation de l’épaule.

Modifications in Early Rehabilitation Protocol after Rotator Cuff Repair : EMG Studies

La déchirure de la coiffe des rotateurs est une des causes les plus fréquentes de douleur et de dysfonctionnement de l'épaule. La réparation chirurgicale est couramment réalisée chez les patients symptomatiques et de nombreux efforts ont été faits pour améliorer les techniques chirurgicales. Cependant, le taux de re-déchirure est encore élevé ce qui affecte les stratégies de réhabilitation post-opératoire. Les recommandations post-chirurgicales doivent trouver un équilibre optimal entre le repos total afin de protéger le tendon réparé et les activités préconisées afin de restaurer l'amplitude articulaire et la force musculaire. Après une réparation de la coiffe, l'épaule est le plus souvent immobilisée grâce à une écharpe ou une orthèse. Cependant, cette immobilisation limite aussi la mobilité du coude et du poignet. Cette période qui peut durer de 4 à 6 semaines où seuls des mouvements passifs peuvent être réalisés. Ensuite, les patients sont incités à réaliser les exercices actifs assistés et des exercices actifs dans toute la mobilité articulaire pour récupérer respectivement l’amplitude complète de mouvement actif et se préparer aux exercices de résistance réalisés dans la phase suivante de la réadaptation. L’analyse électromyographique des muscles de l'épaule a fourni des évidences scientifiques pour la recommandation de beaucoup d'exercices de réadaptation au cours de cette période. Les activités sollicitant les muscles de la coiffe des rotateurs à moins de 20% de leur activation maximale volontaire sont considérés sécuritaires pour les premières phases de la réhabilitation. À partir de ce concept, l'objectif de cette thèse a été d'évaluer des activités musculaires de l'épaule pendant des mouvements et exercices qui peuvent théoriquement être effectués au cours des premières phases de la réhabilitation. Les trois questions principales de cette thèse sont : 1) Est-ce que la mobilisation du coude et du poignet produisent une grande activité des muscles de la coiffe? 2) Est-ce que les exercices de renforcement musculaire du bras, de l’avant-bras et du torse produisent une grande activité dans les muscles de la coiffe? 3) Au cours d'élévations actives du bras, est-ce que le plan d'élévation affecte l'activité de la coiffe des rotateurs? Dans notre première étude, nous avons évalué 15 muscles de l'épaule chez 14 sujets sains par électromyographie de surface et intramusculaire. Nos résultats ont montré qu’avec une orthèse d’épaule, les mouvements du coude et du poignet et même quelques exercices de renforcement impliquant ces deux articulations, activent de manière sécuritaire les muscles de ii la coiffe. Nous avons également introduit des tâches de la vie quotidienne qui peuvent être effectuées en toute sécurité pendant la période d'immobilisation. Ces résultats peuvent aider à modifier la conception d'orthèses de l’épaule. Dans notre deuxième étude, nous avons montré que l'adduction du bras réalisée contre une mousse à faible densité, positionnée pour remplacer le triangle d’une orthèse, produit des activations des muscles de la coiffe sécuritaires. Dans notre troisième étude, nous avons évalué l'électromyographie des muscles de l’épaule pendant les tâches d'élévation du bras chez 8 patients symptomatiques avec la déchirure de coiffe des rotateurs. Nous avons constaté que l'activité du supra-épineux était significativement plus élevée pendant l’abduction que pendant la scaption et la flexion. Ce résultat suggère une séquence de plan d’élévation active pendant la rééducation. Les résultats présentés dans cette thèse, suggèrent quelques modifications dans les protocoles de réadaptation de l’épaule pendant les 12 premières semaines après la réparation de la coiffe. Ces suggestions fournissent également des évidences scientifiques pour la production d'orthèses plus dynamiques et fonctionnelles à l’articulation de l’épaule.

Predictive Value Of Phase I Trials For Safety In Later Trials And Final Approved Dose: Analysis Of 61 Approved Cancer Drugs.

Phase I trials use a small number of patients to define a maximum tolerated dose (MTD) and the safety of new agents. We compared data from phase I and registration trials to determine whether early trials predicted later safety and final dose. We searched the U.S. Food and Drug Administration (FDA) website for drugs approved in nonpediatric cancers (January 1990-October 2012). The recommended phase II dose (R2PD) and toxicities from phase I were compared with doses and safety in later trials. In 62 of 85 (73%) matched trials, the dose from the later trial was within 20% of the RP2D. In a multivariable analysis, phase I trials of targeted agents were less predictive of the final approved dose (OR, 0.2 for adopting ± 20% of the RP2D for targeted vs. other classes; P = 0.025). Of the 530 clinically relevant toxicities in later trials, 70% (n = 374) were described in phase I. A significant relationship (P = 0.0032) between increasing the number of patients in phase I (up to 60) and the ability to describe future clinically relevant toxicities was observed. Among 28,505 patients in later trials, the death rate that was related to drug was 1.41%. In conclusion, dosing based on phase I trials was associated with a low toxicity-related death rate in later trials. The ability to predict relevant toxicities correlates with the number of patients on the initial phase I trial. The final dose approved was within 20% of the RP2D in 73% of assessed trials.

Assessment Of Robustness On Analysis Using Headspace Solid-phase Microextraction And Comprehensive Two-dimensional Gas Chromatography Through Experimental Designs.

Plackett-Burman experimental design was applied for the robustness assessment of GC×GC-qMS (Comprehensive Two-Dimensional Gas Chromatography with Fast Quadrupolar Mass Spectrometric Detection) in quantitative and qualitative analysis of volatiles compounds from chocolate samples isolated by headspace solid-phase microextraction (HS-SPME). The influence of small changes around the nominal level of six factors deemed as important on peak areas (carrier gas flow rate, modulation period, temperature of ionic source, MS photomultiplier power, injector temperature and interface temperature) and of four factors considered as potentially influential on spectral quality (minimum and maximum limits of the scanned mass ranges, ions source temperature and photomultiplier power). The analytes selected for the study were 2,3,5-trimethylpyrazine, 2-octanone, octanal, 2-pentyl-furan, 2,3,5,6-tetramethylpyrazine, and 2-nonanone e nonanal. The factors pointed out as important on the robustness of the system were photomultiplier power for quantitative analysis and lower limit of mass scanning range for qualitative analysis.

Chemical Immobilization Of Crosslinked Polymeric Ionic Liquids On Nitinol Wires Produces Highly Robust Sorbent Coatings For Solid-phase Microextraction.

Super elastic nitinol (NiTi) wires were exploited as highly robust supports for three distinct crosslinked polymeric ionic liquid (PIL)-based coatings in solid-phase microextraction (SPME). The oxidation of NiTi wires in a boiling (30%w/w) H2O2 solution and subsequent derivatization in vinyltrimethoxysilane (VTMS) allowed for vinyl moieties to be appended to the surface of the support. UV-initiated on-fiber copolymerization of the vinyl-substituted NiTi support with monocationic ionic liquid (IL) monomers and dicationic IL crosslinkers produced a crosslinked PIL-based network that was covalently attached to the NiTi wire. This alteration alleviated receding of the coating from the support, which was observed for an analogous crosslinked PIL applied on unmodified NiTi wires. A series of demanding extraction conditions, including extreme pH, pre-exposure to pure organic solvents, and high temperatures, were applied to investigate the versatility and robustness of the fibers. Acceptable precision of the model analytes was obtained for all fibers under these conditions. Method validation by examining the relative recovery of a homologous group of phthalate esters (PAEs) was performed in drip-brewed coffee (maintained at 60 °C) by direct immersion SPME. Acceptable recoveries were obtained for most PAEs in the part-per-billion level, even in this exceedingly harsh and complex matrix.

Elevated Cetp Activity During Acute Phase Of Myocardial Infarction Is Independently Associated With Endothelial Dysfunction And Adverse Clinical Outcome.

Recent data suggests that cholesteryl ester transfer protein (CETP) activity may interact with acute stress conditions via inflammatory-oxidative response and thrombogenesis. We investigated this assumption in patients with ST-elevation myocardial infarction (STEMI). Consecutive patients with STEMI (n = 116) were enrolled <24-h of symptoms onset and were followed for 180 days. Plasma levels of C-reactive protein (CRP), interleukin-2 (IL-2), tumor necrosis factor (TNFα), 8-isoprostane, nitric oxide (NOx) and CETP activity were measured at enrollment (D1) and at fifth day (D5). Flow-mediated dilation (FMD) was assessed by ultrasound and coronary thrombus burden (CTB) was evaluated by angiography. Neither baseline nor the change of CETP activity from D1 to D5 was associated with CRP, IL-2, TNFα, 8-isoprostane levels or CTB. The rise in NOx from D1 to D5 was inferior [3.5(-1; 10) vs. 5.5(-1; 12); p < 0.001] and FMD was lower [5.9(5.5) vs. 9.6(6.6); p = 0.047] in patients with baseline CETP activity above the median value than in their counterparts. Oxidized HDL was measured by thiobarbituric acid reactive substances (TBARS) in isolated HDL particles and increased from D1 to D5, and remaining elevated at D30. The change in TBARS content in HDL was associated with CETP activity (r = 0.72; p = 0.014) and FMD (r = -0.61; p = 0.046). High CETP activity at admission was associated with the incidence of sudden death and recurrent MI at 30 days (OR 12.8; 95% CI 1.25-132; p = 0.032) and 180 days (OR 3.3; 95% CI 1.03-10.7; p = 0.044). An enhanced CETP activity during acute phase of STEMI is independently associated with endothelial dysfunction and adverse clinical outcome.

Evaluation Of The Location Of Capsules Swallowed With Food During The Pharyngeal Phase Triggering In Asymptomatic Adults.

To assess the location of hard gelatin capsules in the pharyngeal phase triggering among asymptomatic adults. The location of the bolus during the pharyngeal phase triggering provides information about the sensorimotor model of the beginning of deglutition onset. To evaluate the location of hard gelatin capsules in the pharyngeal phase triggering among asymptomatic adults. A videofluoroscopy swallowing study was carried out in 60 subjects (14 male and 46 female participants) aged between 27 and 55 years, who were evaluated with hard gelatin capsules #00 and #3 containing barium sulfate, swallowed with liquid food and pudding, in free volume. The first laryngeal elevation movement was the criterion to locate the pharyngeal phase triggering. Statistical analysis was based on the McNemar test. Capsule #3 presented higher percentage of location in the tongue dorsum compared to capsule #00, and capsule #00 presented higher percentage of location in the tongue base and vallecula compared to capsule #3. There was a difference between different capsules swallowed with liquid (p=0.016) and pudding (p=0.037). The capsule size influenced the location of the pharyngeal phase triggering. Smaller capsules started pharyngeal phase in the most anterior region (tongue dorsum) compared to larger capsules.