Dilute gas viscosity of n-alkanes represented by rigid Lennard-Jones chains

The shear viscosity in the dilute gas limit has been calculated by means of the classical trajectory method for a gas consisting of chain-like molecules. The molecules were modelled as rigid chains made up of spherical segments that interact through a combination of site-site Lennard-Jones 12-6 potentials. Results are reported for chains consisting of 2, 3, 4, 6, 8, 12 and 16 segments in the reduced temperature range of 0.3 – 50 for site-site separations of 0.25 , 0.333 , 0.40 , 0.60 and 0.80 , where is the Lennard-Jones length scaling parameter. The results were used to determine the shear viscosity of n-alkanes in the zerodensity limit by representing an n-alkane molecule as a rigid linear chain consisting of c − 1 spherical segments, where c is the number of carbon atoms. We show that for a given n-alkane molecule, the scaling parameters ε and σ are not unique and not transferable from one molecule to another. The commonly used site-site Lennard-Jones 12-6 potential in combination with a rigid-chain molecular representation can only accurately mimic the viscosity if the scaling parameters are fitted. If the scaling parameters are estimated from the scaling parameters of other n-alkanes, the predicted viscosity values have an unacceptably high uncertainty

Remote peering: More peering without internet flattening

The trend toward more peering between networks is commonly conflated with the trend of Internet flattening, i.e., reduction in the number of intermediary organizations on Internet paths. Indeed, direct peering interconnections bypass layer-3 transit providers and make the Internet flatter. This paper studies an emerging phenomenon that separates the two trends: we present the first systematic study of remote peering, an interconnection where remote networks peer via a layer-2 provider. Our measurements reveal significant presence of remote peering at IXPs (Internet eXchange Points) worldwide. Based on ground truth traffic, we also show that remote peering has a substantial potential to offload transit traffic. Generalizing the empirical results, we analytically derive conditions for economic viability of remote peering versus transit and direct peering. Because remote-peering services are provided on layer 2, our results challenge the traditional reliance on layer-3 topologies in modeling the Internet economic structure. We also discuss broader implications of remote peering for reliability, security, accountability, and other aspects of Internet research

SERS study of thiocarbonyl compounds adsorbed on metal nanoparticles

Thiocarbonyl compounds have been reported to exhibit interesting biological and pharmacological properties but they are many often characterized by their toxicological effects. However the chemistry of thiobenzoic acid (TBA) and thiobenzamide (TB) has not been fully studied yet. Some of the biological studies of TBA are related to the tautomerism of thiocarboxylic acids and the important role that the -C(=O)-S and -C(=S)-O functional groups play in the catalytic activities of enzymes such as cysteine or serine proteases.1 On the other hand, TB and derivatives are well known hepatotoxins and have been used as inhibitor in enzymatic reactions and in pharmacy due to their microbial activity.2 From a chemical point of view, thiocarboxylates are an interesting type of molecules having two different donor atoms, a soft sulfur donor atom and a hard oxygen donor one. The presence of these unlike groups can lead to the bonding with metal surfaces. Likewise the interaction of thiobenzamide and their derivatives with metals is of great interest because both the sulfur and nitrogen atoms are also able to coordinate with the surface. Therefore the high affinity of these molecules for metal surfaces makes them suitable SERS target adsorbates. Taking advantage of the fact that SERS spectroscopy is both surface selective and highly sensitive we have attempted to determine the molecular structure of TBA and TB once they are adsorbed on the metal. The main objective of this work is focussed on discussing the observed vibrational wavenumber shifts of TBA and TB upon adsorption on silver nanoparticles. In this work the SERS substrates have been prepared by using different colloidal silver solutions according to the method described by Creighton et al.3 and Leopold and Lendl.4 The analysis of the vibrational wavenumbers shifts of the Raman and SERS spectra allow us to know the adsorption process (Figure 1). In the case of TBA, the wavenumber of the SERS band assigned to (C=O) vibrational mode shows an important blue shift up to 40 cm-1 with respect to the Raman whereas the (C-S) band undergoes a red shift up to 40 cm-1. These results suggest a unidentate coordination of TBA to the silver surface through the sulfur atom. On the other hand, the SERS band assigned in the case of TB to Amide III (mainly (CN)) exhibits a significant blueshift up to 41 cm-1, and the SERS band assigned to Amide I (mainly (CS)) shows a red shift up to 11 cm-1. These wavenumber shifts indicate that TB interacts to the silver surface through the sulfur atom. Interestingly, in previous SERS studies of pyridinecarboxamides and benzamide we have observed that some SERS bands assigned to 1;ring, Amide I (mainly (C=O)) and Amide III (mainly C-N)) show wavenumber shifts of +50, -50 and +10 cm-1, respectively, which were attributed to the deprotonation of carboxamide group.5,6 Finally, in order to verify experimental results DFT calculations have been carried out for different silver complexes of TBA and TB concluding that the unidentate coordination is the most likely interaction of both of them.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Early elimination of cyclosporine in kidney transplant recipients receiving sirolimus prevents progression of chronic pathologic allograft lesions

Cyclosporine elimination in a regimen including sirolimus has been shown to be a safe and effective approach to improve graft function. Nevertheless, it is still unknown whether the functional benefit of CyA withdrawal coincides with a subsequent reduction in histologic lesions of chronic damage or development of chronic allograft nephropathy. This consideration would forecast a reduction in the rate of long-term graft loss. We analyzed 114 graft biopsies from a subgroup of 57 patients that had been included in a randomized study to eliminate CyA at 3 months posttransplant from a regimen including sirolimus either in group A CyA + SRL vs group B of SRL with CyA elimination at 3 months. Every patient had two biopsies, one at transplantation and another at 1 year. The biopsy reading was performed in a blinded manner by a central pathologist using the Banff 1997 and the CADI classifications. A significantly lower rate of progression of tubular and interstitial chronic lesions between basal and 1-year biopsies was observed for group B patients. In addition, the incidence of new cases of chronic allograft nephropathy during the first year was significantly lower in the group in which CyA had been eliminated at 3 months posttransplant. We conclude that early elimination of CyA in the first months posttransplant, when SRL is used as the main immunosuppressant, reduces the appearance or worsening of chronic histologic lesions, probably as a consequence of long-term CyA toxicity prevention

Extending cognitive load theory to incorporate working memory resource depletion: Evidence from the spacing effect

© 2017, Springer Science+Business Media, LLC. Depletion of limited working memory resources may occur following extensive mental effort resulting in decreased performance compared to conditions requiring less extensive mental effort. This “depletion effect” can be incorporated into cognitive load theory that is concerned with using the properties of human cognitive architecture, especially working memory, when designing instruction. Two experiments were carried out on the spacing effect that occurs when learning that is spaced by temporal gaps between learning episodes is superior to identical, massed learning with no gaps between learning episodes. Using primary school students learning mathematics, it was found that students obtained lower scores on a working memory capacity test (Experiments 1 and 2) and higher ratings of cognitive load (Experiment 2) after massed than after spaced practice. The reduction in working memory capacity may be attributed to working memory resource depletion following the relatively prolonged mental effort associated with massed compared to spaced practice. An expansion of cognitive load theory to incorporate working memory resource depletion along with instructional design implications, including the spacing effect, is discussed

Undesirable difficulty effects in the learning of high-element interactivity materials

© 2018 Chen, Castro-Alonso, Paas and Sweller. According to the concept of desirable difficulties, introducing difficulties in learning may sacrifice short-term performance in order to benefit long-term retention of learning. We describe three types of desirable difficulty effects: testing, generation, and varied conditions of practice. The empirical literature indicates that desirable difficulty effects are not always obtained and we suggest that cognitive load theory may be used to explain many of these contradictory results. Many failures to obtain desirable difficulty effects may occur under conditions where working memory is already stressed due to the use of high element interactivity information. Under such conditions, the introduction of additional difficulties may be undesirable rather than desirable. Empirical evidence from diverse experiments is used to support this hypothesis

Oxidative Coupling of Methane for Ethylene Production: Reviewing Kinetic Modelling Approaches, Thermodynamics and Catalysts

Ethylene production via oxidative coupling of methane (OCM) represents an interesting route for natural gas upscaling, being the focus of intensive research worldwide. Here, OCM developments are analysed in terms of kinetic mechanisms and respective applications in chemical reactor models, discussing current challenges and directions for further developments. Furthermore, some thermodynamic aspects of the OCM reactions are also revised, providing achievable olefins yields in a wide range of operational reaction conditions. Finally, OCM catalysts are reviewed in terms of respective catalytic performances and thermal stability, providing an executive summary for future studies on OCM economic feasibility

GABAA receptor dependent synaptic inhibition rapidly tunes KCC2 activity via the Cl--sensitive WNK1 kinase

This is the final version of the article. Available from the publisher via the DOI in this record.There is another ORE record for this publication: http://hdl.handle.net/10871/33406The K+-Cl-co-transporter KCC2 (SLC12A5) tunes the efficacy of GABAAreceptor-mediated transmission by regulating the intraneuronal chloride concentration [Cl-]i. KCC2 undergoes activity-dependent regulation in both physiological and pathological conditions. The regulation of KCC2 by synaptic excitation is well documented; however, whether the transporter is regulated by synaptic inhibition is unknown. Here we report a mechanism of KCC2 regulation by GABAAreceptor (GABAAR)-mediated transmission in mature hippocampal neurons. Enhancing GABAAR-mediated inhibition confines KCC2 to the plasma membrane, while antagonizing inhibition reduces KCC2 surface expression by increasing the lateral diffusion and endocytosis of the transporter. This mechanism utilizes Cl-as an intracellular secondary messenger and is dependent on phosphorylation of KCC2 at threonines 906 and 1007 by the Cl--sensing kinase WNK1. We propose this mechanism contributes to the homeostasis of synaptic inhibition by rapidly adjusting neuronal [Cl-]ito GABAAR activity.This work was supported in part by Inserm, Sorbonne Université-UPMC, as well as the Fondation pour la Recherche Médicale (Equipe FRM DEQ20140329539 to J.C.P.), the Human Frontier Science Program (RGP0022/2013 to J.C.P.) and the Fondation pour la Recherche sur le Cerveau (to S.L.). Equipment at the IFM was also supported by DIM NeRF from Région Ile-de-France and by the FRC/Rotary ‘Espoir en tête’. M.H. was the recipient of a doctoral fellowship from the Université Pierre and Marie Curie, as well as from Bio-Psy Laboratory of excellence. K.T.K. is supported by the National Institutes of Health, the Simons Foundation, and the March of Dimes Foundation Basil O’Connor Award. The Poncer/Lévi lab is affiliated with the Paris School of Neuroscience (ENP) and the Bio-Psy Laboratory of excellence

Modelling the chemical recycling of crosslinked poly (methyl methacrylate): kinetics of depolymerisation

Whereas increasing plastic solid waste production constitutes one of the main challenges of modern society, mainly due to the lack of suitable recycling technologies, chemical recycling represents an attractive solution for the conversion of plastic solid waste into valuable chemical intermediates. Herein, a kinetic model for the pyrolysis of a dental industry waste, ethylene glycol dimethacrylate (EGDMA) crosslinked poly (methyl methacrylate) (PMMA), is presented for the first time. Kinetics parameters and their statistical significance have been estimated from eight non-isothermal thermogravimetric analysis (TGA) experiments with heating rates varying between 5 and 50 °C·min-1 by using nonlinear regression. Our analysis indicates that the mechanism of depolymerisation of EGDMA crosslinked PMMA is likely to involve a consecutive reaction pathway involving two steps. The developed kinetic model - containing five kinetic parameters only - was able to predict well all non-isothermal TGA runs, and was validated against isothermal TGA experiments at 400 °C