Air-sea transfer of gas phase controlled compounds

Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ~30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the "zero bubble" waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer.

Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.

Jubilee and the Limits of African American Freedom after Emancipation

Scholarship generated in the post-civil rights US underpins a growing consensus that any honest confrontation with the American past requires an acknowledgment both of the nation’s foundations in racially-based slave labour and of the critical role that the enslaved played in ending that system. But scholars equally need to examine why the end of slavery did not deliver freedom, but instead – after a short-lived ‘jubilee’ during which freedpeople savoured their ‘brief moment in the sun’ – opened up a period of extreme repression and violence. This article traces the political trajectory of one prominent ex-slave and Republican party organiser, Elias Hill, to assess the constraints in which black grassroots activists operated. Though mainly concerned with the dashed hopes of African Americans, their experience of a steep reversal is in many ways the shared and profoundly significant legacy of ex-slaves across the former plantation societies of the Atlantic world.

PEG-based solid dispersions enhanced the solubility and dissolution of eprosartan mesylate in-vitro

Abstract - This study investigates the effect of solid dispersions prepared from of polyethylene glycol (PEG) 3350 and 6000 Da alone or combined with the non-ionic surfactant Tween 80 on the solubility and dissolution rate of a poorly soluble drug eprosartan mesylate (ESM) in attempt to improve its bioavailability following its oral administration.

INTRODUCTION

ESM is a potent anti-hypertension [1]. It has low water solubility and is classified as a Class II drug as per the Biopharmaceutical Classification Systems (BCS) leading to low and variable oral bioavailability (approximately 13%). [2]. Thus, improving ESM solubility and/or dissolution rate would eventually improve the drug bioavailability. Solid dispersion is widely used technique to improve the water solubility of poorly water-soluble drugs employing various biocompatible polymers. In this study, we aimed to enhance the solubility and dissolution of EMS employing solid dispersion (SD) formulated from two grades of poly ethylene glycol (PEG) polymers (i.e. PEG 3350 & PEG 6000 Da) either individually or in combination with Tween 80.

MATERIALS AND METHODS

ESM SDs were prepared by solvent evaporation method using either PEG 3350 or PEG 6000 at various (drug: polymer, w/w) ratios 1:1, 1:2, 1:3, 1:4, 1:5 alone or combined with Tween 80 added at fixed percentage of 0.1 of drug by weight?. Physical mixtures (PMs) of drug and carriers were also prepared at same ratios. Drug solid dispersions and physical mixtures were characterized in terms of drug content, drug dissolution using dissolution apparatus USP II and assayed using HPLC method. Drug dissolution enhancement ratio (ER %) from SD in comparison to the plain drug was calculated. Drug-polymer interactions were evaluated using Differential Scanning Calorimetry (DSC) and FT-IR.

RESULTS AND DISCUSSION

The in vitro solubility and dissolution studies showed SDs prepared using both polymers produced a remarkable improvement (p<0.05) in comparison to the plain drug which reached around 32% (Fig. 1). The dissolution enhancement ratio was polymer type and concentration-dependent. Adding Tween 80 to the SD did not show further dissolution enhancement but reduced the required amount of the polymer to get the same dissolution enhancement. The DSC and FT-IR studies indicated that using SD resulted in transformation of drug from crystalline to amorphous form.

CONCLUSIONS

This study indicated that SDs prepared by using both polymers i.e. PEG 3350 and PEG 6000 improved the in-vitro solubility and dissolution of ESM remarkably which may result in improving the drug bioavailability in vivo.

Acknowledgments

This work is a part of MSc thesis of O.M. Ali at the Faculty of Pharmacy, Aleppo University, Syria.

REFERENCES

[1] Ruilope L, Jager B: Eprosartan for the treatment of hypertension. Expert Opin Pharmacother 2003; 4(1):107-14

[2] Tenero D, Martin D, Wilson B, Jushchyshyn J, Boike S, Lundberg, D, et al. Pharmacokinetics of intravenously and orally administered Eprosartan in healthy males: absolute bioavailability and effect of food. Biopharm Drug Dispos 1998; 19(6): 351- 6.

Endothelial cell-derived Pentraxin 3 limits the vasoreparative therapeutic potential of Circulating Angiogenic Cells

AIMS: Circulating Angiogenic Cells (CACs) promote revascularization of ischemic tissues although their underlying mechanism of action and the consequences of delivering varying numbers of these cells for therapy remain unknown. This study investigates molecular mechanisms underpinning CAC modulation of blood vessel formation.

METHODS & RESULTS: CACs at low (2x10(5)cells/ml) and mid (2x10(6)cells/ml) cellular densities significantly enhanced endothelial cell (EC) tube formation in vitro, while high density CACs (2x10(7)cells/ml) significantly inhibited this angiogenic process. In vivo, Matrigel-based angiogenesis assays confirmed mid-density CACs as pro-angiogenic and high density CACs as anti-angiogenic. Secretome characterization of CAC-EC conditioned media identified pentraxin 3 (PTX3) as only present in the high density CAC-EC co-culture. Recombinant PTX3 inhibited endothelial tube formation in vitro and in vivo Importantly, our data revealed that the anti-angiogenic effect observed in high density CAC-EC co-cultures was significantly abrogated when PTX3 bioactivity was blocked using neutralizing antibodies or PTX3 siRNA in endothelial cells. We show evidence for an endothelial source of PTX3, triggered by exposure to high density CACs. In addition, we confirmed that PTX3 inhibits FGF2-mediated angiogenesis, and that the PTX3 N-terminus, containing the FGF-binding site, is responsible for such anti-angiogenic effects.

CONCLUSIONS: Endothelium, when exposed to high density CACs, releases PTX3 which markedly impairs the vascular regenerative response in an autocrine manner. Therefore, CAC density and accompanying release of angiocrine PTX3 are critical considerations when using these cells as a cell therapy for ischemic disease.

Misaligned and Polarity-Reversed Faces Determine Face-specific Capacity Limits

Previous research using flanker paradigms suggests that peripheral distracter faces are automatically processed when participants have to classify a single central familiar target face. These distracter interference effects disappear when the central task contains additional anonymous (non-target) faces that load the search for the face target, but not when the central task contains additional non-face stimuli, suggesting there are face-specific capacity limits in visual processing. Here we tested whether manipulating the format of non-target faces in the search task affected face-specific capacity limits. Experiment 1 replicated earlier findings that a distracter face is processed even in high load conditions when participants looked for a target name of a famous person among additional names (non-targets) in a central search array. Two further experiments show that when targets and non-targets were faces (instead of names), however, distracter interference was eliminated under high load—adding non-target faces to the search array exhausted processing capacity for peripheral faces. The novel finding was that replacing non-target faces with images that consisted of two horizontally misaligned face-parts reduced distracter processing. Similar results were found when the polarity of a non-target face image was reversed. These results indicate that face-specific capacity limits are not determined by the configural properties of face processing, but by face parts.

Inlärningseffekten på Limits of Stability på Transtibialt Amputerade Protesbrukare

Syftet med studien är att undersöka om det finns någon inlärningseffekt på testet Limits of Stability (LoS) för transtibialt amputerade protesbrukare och en kontrollgrupp. Sju transtibialt amputerade protesbrukare och en kontrollgrupp bestående av sju friska vuxna män upprepade testet LoS  fem gånger under fyra testtillfällen. Två kraftplattor och 69 reflexmarkörer användes för att samla in data. Testpersonerna placerades med en fot på varje kraftplatta och blev instruerade att förflytta sin center of pressure genom att luta kroppen från anklarna mot åtta mål som visades på en skärm tillsammans med deras center of pressure. Ordningen på målen var slumpvist utvalda. Datan analyserades med Friedmans test, eftersom den inte var normalfördelad, för att se om det fanns någon skillnad i resultatet mellan upprepningarna av testet och resultatet mellan testtillfällena. Det fanns några signifikanta skillnader mellan upprepningarna och mellan testtillfällena som tyder på att det finns en inlärningseffekt efter första upprepningen och första testtillfället, men resultatet var inte tillräckligt entydigt för att kunna dra några konkreta slutsatser. Vidare studier rekommenderas.

The role of glass modifiers in the solubility of Tm3+ ions in As2S3 glasses

Au cours des années une variété des compositions de verre chalcogénure a été étudiée en tant qu’une matrice hôte pour les ions Terres Rares (TR). Pourtant, l’obtention d’une matrice de verre avec une haute solubilité des ions TR et la fabrication d’une fibre chalcogénure dopée au TR avec une bonne qualité optique reste toujours un grand défi. La présente thèse de doctorat se concentre sur l’étude de nouveaux systèmes vitreux comme des matrices hôtes pour le dopage des ions TR, ce qui a permis d’obtenir des fibres optiques dopées au TR qui sont transparents dans l’IR proche et moyenne. Les systèmes vitreux étudiés ont été basés sur le verre de sulfure d’arsenic (As2S3) co-dopé aux ions de Tm3+ et aux différents modificateurs du verre. Premièrement, l’addition de Gallium (Ga), comme un co-dopant, a été examinée et son influence sur les propriétés d’émission des ions de Tm a été explorée. Avec l’incorporation de Ga, la matrice d’As2S3 dopée au Tm a montré trois bandes d’émission à 1.2 μm (1H5→3H6), 1.4 μm (3H4→3F4) et 1.8 μm (3F4→3H6), sous l’excitation des longueurs d’onde de 698 nm et 800 nm. Les concentrations de Tm et de Ga ont été optimisées afin d’obtenir le meilleur rendement possible de photoluminescence. À partir de la composition optimale, la fibre Ga-As-S dopée au Tm3+ a été étirée et ses propriétés de luminescence ont été étudiées. Un mécanisme de formation structurale a été proposé pour ce système vitreux par la caractérisation structurale des verres Ga-As-S dopés au Tm3+, en utilisant la spectroscopie Raman et l’analyse de spectrométrie d’absorption des rayons X (EXAFS) à seuil K d’As, seuil K de Ga et seuil L3 de Tm et il a été corrélé avec les caractéristiques de luminescence de Tm. Dans la deuxième partie, la modification des verres As2S3 dopés au Tm3+, avec l’incorporation d’halogénures (Iode (I2)), a été étudiée en tant qu’une méthode pour l’adaptation des paramètres du procédé de purification afin d’obtenir une matrice de verre de haute pureté par distillation chimique. Les trois bandes d’émission susmentionnées ont été aussi bien observées pour ce système sous l’excitation à 800 nm. Les propriétés optiques, thermiques et structurelles de ces systèmes vitreux ont été caractérisées expérimentalement en fonction de la concentration d’I2 et de Tm dans le verre, où l’attention a été concentrée sur deux aspects principaux: l’influence de la concentration d’I2 sur l’intensité d’émission de Tm et les mécanismes responsables pour l’augmentation de la solubilité des ions de Tm dans la matrice d’As2S3 avec l’addition I2.

DEVELOPMENT OF A DECISION/DEPLOYMENT SUPPORT TOOL FOR VARIABLE SPEED LIMITS IN RECURRENT CONGESTION

Traffic demand increases are pushing aging ground transportation infrastructures to their theoretical capacity. The result of this demand is traffic bottlenecks that are a major cause of delay on urban freeways. In addition, the queues associated with those bottlenecks increase the probability of a crash while adversely affecting environmental measures such as emissions and fuel consumption. With limited resources available for network expansion, traffic professionals have developed active traffic management systems (ATMS) in an attempt to mitigate the negative consequences of traffic bottlenecks. Among these ATMS strategies, variable speed limits (VSL) and ramp metering (RM) have been gaining international interests for their potential to improve safety, mobility, and environmental measures at freeway bottlenecks. Though previous studies have shown the tremendous potential of variable speed limit (VSL) and VSL paired with ramp metering (VSLRM) control, little guidance has been developed to assist decision makers in the planning phase of a congestion mitigation project that is considering VSL or VSLRM control. To address this need, this study has developed a comprehensive decision/deployment support tool for the application of VSL and VSLRM control in recurrently congested environments. The decision tool will assist practitioners in deciding the most appropriate control strategy at a candidate site, which candidate sites have the most potential to benefit from the suggested control strategy, and how to most effectively design the field deployment of the suggested control strategy at each implementation site. To do so, the tool is comprised of three key modules, (1) Decision Module, (2) Benefits Module, and (3) Deployment Guidelines Module. Each module uses commonly known traffic flow and geometric parameters as inputs to statistical models and empirically based procedures to provide guidance on the application of VSL and VSLRM at each candidate site. These models and procedures were developed from the outputs of simulated experiments, calibrated with field data. To demonstrate the application of the tool, a list of real-world candidate sites were selected from the Maryland State Highway Administration Mobility Report. Here, field data from each candidate site was input into the tool to illustrate the step-by-step process required for efficient planning of VSL or VSLRM control. The output of the tool includes the suggested control system at each site, a ranking of the sites based on the expected benefit-to-cost ratio, and guidelines on how to deploy the VSL signs, ramp meters, and detectors at the deployment site(s). This research has the potential to assist traffic engineers in the planning of VSL and VSLRM control, thus enhancing the procedure for allocating limited resources for mobility and safety improvements on highways plagued by recurrent congestion.

Indications for and limits of conservative surgery in breast cancer

Improvements in diagnostic techniques and, above all, breast cancer screening campaigns - essential for early diagnosis - have enabled the objectives of conservative surgery to be pursued: disease control, no or low incidence of recurrences and an excellent esthetic result. However, to reach these objectives, it is essential to ensure a careful evaluation of the medical history of every patient, a detailed clinical examination and the correct interpretation of imaging. Particular attention should be paid to all factors influencing the choice of treatment and/or possible local recurrence: age, site, tumor volume, genetic predisposition, pregnancy, previous radiotherapy, pathological features, and surgical margins. The decision to undertake conservative treatment thus requires a multidisciplinary approach involving pathologists, surgeons and oncological radiologists, as well, of course, as the patient herself.

Approximation limits of linear programs (beyond hierarchies)

We develop a framework for proving approximation limits of polynomial size linear programs (LPs) from lower bounds on the nonnegative ranks of suitably defined matrices. This framework yields unconditional impossibility results that are applicable to any LP as opposed to only programs generated by hierarchies. Using our framework, we prove that O(n^1/2-ε)-approximations for CLIQUE require LPs of size 2^nΩ(ε). This lower bound applies to LPs using a certain encoding of CLIQUE as a linear optimization problem. Moreover, we establish a similar result for approximations of semidefinite programs by LPs. Our main technical ingredient is a quantitative improvement of Razborov's [38] rectangle corruption lemma for the high error regime, which gives strong lower bounds on the nonnegative rank of shifts of the unique disjointness matrix.

Humankindness: Illness, Animality, and the Limits of the Human in the Victorian Novel

This project posits a link between representations of animals or animality and representations of illness in the Victorian novel, and examines the narrative uses and ideological consequences of such representations. Figurations of animality and illness in Victorian fiction have been examined extensively as distinct phenomena, but examining their connection allows for a more complex view of the role of sympathy in the Victorian novel. The commonplace in novel criticism is that Victorian authors, whether effectively or not, constructed their novels with a view to the expansion of sympathy. This dissertation intervenes in the discussion of the Victorian novel as a vehicle for sympathy by positing that texts and scenes in which representations of illness and animality are conjoined reveal where the novel draws the boundaries of the human, and the often surprising limits it sets on sympathetic feeling. In such moments, textual cues train or direct readerly sympathies in ways that suggest a particular definition of the human, but that direction of sympathy is not always towards an enlarged sympathy, or an enlarged definition of the human. There is an equally (and increasingly) powerful antipathetic impulse in many of these texts, which estranges readerly sympathy from putatively deviant, degenerate, or dangerous groups. These two opposing impulses—the sympathetic and the antipathetic—often coexist in the same novel or even the same scene, creating an ideological and affective friction, and both draw on the same tropes of illness and animality. Examining the intersection of these different discourses—sympathy, illness, and animality-- in these novels reveals the way that major Victorian debates about human nature, evolution and degeneration, and moral responsibility shaped the novels of the era as vehicles for both antipathy and sympathy. Focusing on the novels of the Brontës and Thomas Hardy, this dissertation examines in depth the interconnected ways that representations of animals and animality and representations of illness function in the Victorian novel, as they allow authors to explore or redefine the boundary between the human and the non-human, the boundary between sympathy and antipathy, and the limits of sympathy itself.