Influence of chain topology (cyclic versus linear) on the nucleation and isothermal crystallization of poly(L-lactide) and poly(D-lactide)

In this paper, ring closure click chemistry methods have been used to produce cyclic c-PLLA and c-PDLA of a number average molecular weight close to 10 kg/mol. The effects of stereochemistry of the polymer chains and their topology on their structure, nucleation and crystallization were studied in detail employing Wide Angle X-ray Scattering (WAXS), Small Angle X-ray Scattering (SAXS), Polarized Light Optical Microscopy (PLOM) and standard and advanced Differential Scanning Calorimetry (DSC). The crystal structures of linear and cyclic PLAs are identical to each other and no differences in superstructural morphology could be detected. Cyclic PLA chains are able to nucleate much faster and to produce a higher number of nuclei in comparison to linear analogues, either upon cooling from the melt or upon heating from the glassy state. In the samples prepared in this work, a small fraction of linear or higher molecular weight cycles was detected (according to SEC analyses). The presence of such “impurities” retards spherulitic growth rates of c-PLAs making them nearly the same as those of l-PLAs. On the other hand, the overall crystallization rate determined by DSC was much larger for c-PLAs, as a consequence of the enhanced nucleation that occurs in cyclic chains. The equilibrium melting temperatures of cyclic chains were determined and found to be 5 ºC higher in comparison with values for l-PLAs. This result is a consequence of the lower entropy of cyclic chains in the melt. Self-nucleation studies demonstrated that c-PLAs have a shorter crystalline memory than linear analogues, as a result of their lower entanglement density. Successive self-nucleation and annealing (SSA) experiments reveal the remarkable ability of cyclic molecules to thicken, even to the point of crystallization with extended collapsed ring conformations. In general terms, stereochemistry had less influence on the results obtained in comparison with the dominating effect of chain topology.“UPV/EHU Infrastructure: INF 14/38”; “Mineco/FEDER: SINF 130I001726XV1/Ref: UNPV13–4E–1726” and “Mineco MAT2014-53437-C2-P”, 'Ministerio de Economia y Competitividad (MINECO), code: MAT2015-63704-P (MINECO/FEDER, UE) and by the Eusko Jaurlaritza (Basque Government), code: IT-654-13. O.C acknowledges financial support from the European Commission and Région Wallonne FEDER program (Materia Nova) and OPTI²MAT program of excellence, by the Interuniversity Attraction Pole Program (P7/05) initiated by the Belgian Science Policy office and by the FNRS-FRFC. OC is Research Associate of the F.R.S.-FNRS. Organic Synthesis and Mass Spectrometry Laboratory thanks F.R.S.-FNRS for the financial support for the acquisition of the Waters QToF Premier and Synapt-G2Si mass spectrometers and for continuing support. Finally, all authors would like to acknowledge Research and Innovation Staff Exchange (RISE) H2020-MSCA-RISE-2017-778092, project BIODEST for promoting cooperation between the Mons team and the UPV/EHU team

Productivity change using growth accounting and frontier-based approaches – Evidence from a Monte Carlo analysis

This study presents some quantitative evidence from a number of simulation experiments on the accuracy of the productivity growth estimates derived from growth accounting (GA) and frontier-based methods (namely Data envelopment Analysis-, Corrected ordinary least squares-, and Stochastic Frontier Analysis-based Malmquist indices) under various conditions. These include the presence of technical inefficiency, measurement error, misspecification of the production function (for the GA and parametric approaches) and increased input and price volatility from one period to the next. The study finds that the frontier-based methods usually outperform GA, but the overall performance varies by experiment. Parametric approaches generally perform best when there is no functional form misspecification, but their accuracy greatly diminishes otherwise. The results also show that the deterministic approaches perform adequately even under conditions of (modest) measurement error and when measurement error becomes larger, the accuracy of all approaches (including stochastic approaches) deteriorates rapidly, to the point that their estimates could be considered unreliable for policy purposes.

Ab Initio Molecular Dynamics on the Electronic Boltzmann Equilibrium Distribution

We prove that for a combined system of classical and quantum particles, it is possible to write a dynamics for the classical particles that incorporates in a natural way the Boltzmann equilibrium population for the quantum subsystem. In addition, these molecular dynamics do not need to assume that the electrons immediately follow the nuclear motion (in contrast to any adiabatic approach), and do not present problems in the presence of crossing points between different potential energy surfaces (conical intersections or spin-crossings). A practical application of this molecular dynamics to study the effect of temperature in molecular systems presenting (nearly) degenerate states - such as the avoided crossing in the ring-closure process of ozone - is presented.Comment: published in New J. Phy

Patterns of impact resulting from a 'sit less, move more' web-based program in sedentary office employees.

PURPOSE: Encouraging office workers to 'sit less and move more' encompasses two public health priorities. However, there is little evidence on the effectiveness of workplace interventions for reducing sitting, even less about the longer term effects of such interventions and still less on dual-focused interventions. This study assessed the short and mid-term impacts of a workplace web-based intervention (Walk@WorkSpain, W@WS; 2010-11) on self-reported sitting time, step counts and physical risk factors (waist circumference, BMI, blood pressure) for chronic disease. METHODS: Employees at six Spanish university campuses (n=264; 42±10 years; 171 female) were randomly assigned by worksite and campus to an Intervention (used W@WS; n=129; 87 female) or a Comparison group (maintained normal behavior; n=135; 84 female). This phased, 19-week program aimed to decrease occupational sitting time through increased incidental movement and short walks. A linear mixed model assessed changes in outcome measures between the baseline, ramping (8 weeks), maintenance (11 weeks) and follow-up (two months) phases for Intervention versus Comparison groups. RESULTS: A significant 2 (group) × 2 (program phases) interaction was found for self-reported occupational sitting (F[3]=7.97, p=0.046), daily step counts (F[3]=15.68, p=0.0013) and waist circumference (F[3]=11.67, p=0.0086). The Intervention group decreased minutes of daily occupational sitting while also increasing step counts from baseline (446±126; 8,862±2,475) through ramping (+425±120; 9,345±2,435), maintenance (+422±123; 9,638±3,131) and follow-up (+414±129; 9,786±3,205). In the Comparison group, compared to baseline (404±106), sitting time remained unchanged through ramping and maintenance, but decreased at follow-up (-388±120), while step counts diminished across all phases. The Intervention group significantly reduced waist circumference by 2.1cms from baseline to follow-up while the Comparison group reduced waist circumference by 1.3cms over the same period. CONCLUSIONS: W@WS is a feasible and effective evidence-based intervention that can be successfully deployed with sedentary employees to elicit sustained changes on "sitting less and moving more"

Doubts and equilibria

In real life strategic interactions decision-makers are likely to entertain doubts about the degree of optimality of their play. To capture this feature of real choice-making, we present here a model based on the doubts felt by an agent about how well is playing a game. The doubts are coupled with (and mutually reinforced by) imperfect discrimination capacity, which we model here by means of similarity relations. We assume that each agent builds procedural preferences defined on the space of expected payoffsstrategy frequencies attached to his current strategy. These preferences, together with an adaptive learning process lead to doubt-based selection dynamic systems. We introduce the concepts of Mixed Strategy Doubt Equilibria, Mixed Strategy Doubt-Full Equilibria and Mixed Strategy Doubtless Equilibria and show the theoretical and the empirical relevance of these concept

Fault-Tolerant Exact State Transmission

We show that a category of one-dimensional XY-type models may enable high-fidelity quantum state transmissions, regardless of details of coupling configurations. This observation leads to a fault- tolerant design of a state transmission setup. The setup is fault-tolerant, with specified thresholds, against engineering failures of coupling configurations, fabrication imperfections or defects, and even time-dependent noises. We propose the implementation of the fault-tolerant scheme using hard-core bosons in one-dimensional optical lattices.Comment: 5 pages and 4 figure

Historical Evolution of theWave Resource and Energy Production off the Chilean Coast over the 20th Century

The wave energy resource in the Chilean coast shows particularly profitable characteristics for wave energy production, with relatively high mean wave power and low inter-annual resource variability. This combination is as interesting as unusual, since high energetic locations are usually also highly variable, such as the west coast of Ireland. Long-term wave resource variations are also an important aspect when designing wave energy converters (WECs), which are often neglected in resource assessment. The present paper studies the long-term resource variability of the Chilean coast, dividing the 20th century into five do-decades and analysing the variations between the different do-decades. To that end, the ERA20C reanalysis of the European Centre for Medium-Range Weather Forecasts is calibrated versus the ERA-Interim reanalysis and validated against buoy measurements collected in different points of the Chilean coast. Historical resource variations off the Chilean coast are compared to resource variations off the west coast in Ireland, showing a significantly more consistent wave resource. In addition, the impact of historical wave resource variations on a realistic WEC, similar to the Corpower device, is studied, comparing the results to those obtained off the west coast of Ireland. The annual power production off the Chilean coast is demonstrated to be remarkably more regular over the 20th century, with variations of just 1% between the different do-decades.The authors with the Centre for Ocean Energy Research in Maynooth University are supported by Science Foundation Ireland under Grant No. 13/IA/1886. It is also supported by grant CGL2016-76561-R, MINECO/ERDF, UE. Additional funding was received from the University of Basque Country (UPV/EHU, GIU17/002)

Evaluación de la satisfacción del turista y la congestión en la práctica de observación de ballenas jorobadas, el caso de Puerto López – Ecuador

[EN] The effect of crowding on tourist satisfaction is a widely studied aspect. Its knowledge is valuable not only to guide ordering of tourism activity but also to ensure a satisfactory experience that contributes to its economic sustainability. However, studies of this type are scarce in the context of whale watching tourism. Therefore, this research aims to evaluate tourist satisfaction and crowding in the practice of humpback whale - watching in Puerto López - Ecuador. At the methodological level, a survey was applied to 340 tourists who observed whales in the June-September 2017 season. Data analysis was based on descriptive record, the structuring of an importance-performance analysis matrix, principal components analysis and binary logistic regression model. Unlike others, this research incorporated the calculation of a perceived crowding threshold and the analysis of the relationship between perceived crowding of boats and people on board. Among main results, the study finds that crowding influences tourist satisfaction when four or more boats coincide at a sighting site. In that sense, the activity in Puerto López is satisfactory in the face of a reported crowding scenario of 3.7 boats and 16.3 people per boat, on average. The limitations of this study are its exploratory nature because it is based on a non-probabilistic sampling and the questionnaire application exclusively in standard capacity boats, without considering those of 35 passengers.[ES] El efecto de la congestión sobre la satisfacción del turista constituye un aspecto ampliamente estudiado. Su conocimiento resulta valioso no solo para orientar el ordenamiento de la actividad turística sino además para asegurar una experiencia satisfactoria que contribuya a su sostenibilidad económica. Sin embargo, son escasos los estudios de este tipo en el contexto del turismo de observación de ballenas. Por tanto, esta investigación tiene como objetivo evaluar la satisfacción del turista y la congestión en la práctica de observación de ballenas jorobadas en Puerto López – Ecuador. A nivel metodológico se aplicó una encuesta a 340 turistas que observaron ballenas en la temporada junio-septiembre de 2017. El análisis de datos se apoyó en el registro descriptivo, la estructuración de una matriz de análisis importancia-desempeño, el análisis de componentes principales y un modelo de regresión logística binaria. A diferencia de otras, esta investigación incorporó el cálculo de un umbral de congestión percibida y el análisis de la relación entre congestión percibida de botes y de personas a bordo. Como resultado, el estudio encuentra que la congestión influye en la satisfacción del turista cuando cuatro o más embarcaciones coinciden en un sitio de avistamiento. En ese sentido, la actividad en Puerto López es satisfactoria frente a un escenario de congestión reportada de 3,7 botes y 16,3 personas por bote, en promedio. Constituyen limitaciones del estudio su carácter exploratorio por basarse en un muestreo no probabilístico y la aplicación exclusiva del cuestionario en botes de capacidad estándar, sin considerar aquellos de 35 pasajeros

Degree of Quantumness in Quantum Synchronization

We introduce the concept of degree of quantumness in quantum synchronization, a measure of the quantum nature of synchronization in quantum systems. Following techniques from quantum information, we propose the number of non-commuting observables that synchronize as a measure of quantumness. This figure of merit is compatible with already existing synchronization measurements, and it captures different physical properties. We illustrate it in a quantum system consisting of two weakly interacting cavity-qubit systems, which are coupled via the exchange of bosonic excitations between the cavities. Moreover, we study the synchronization of the expectation values of the Pauli operators and we propose a feasible superconducting circuit setup. Finally, we discuss the degree of quantumness in the synchronization between two quantum van der Pol oscillators

Thin-Wall Machining of Light Alloys: A Review of Models and Industrial Approaches

Thin-wall parts are common in the aeronautical sector. However, their machining presents serious challenges such as vibrations and part deflections. To deal with these challenges, di erent approaches have been followed in recent years. This work presents the state of the art of thin-wall light-alloy machining, analyzing the problems related to each type of thin-wall parts, exposing the causes of both instability and deformation through analytical models, summarizing the computational techniques used, and presenting the solutions proposed by di erent authors from an industrial point of view. Finally, some further research lines are proposed