Exciton spin dynamics and photoluminescence polarization of CdSe/CdS dot-in-rod nanocrystals in high magnetic fields

The exciton spin dynamics and polarization properties of the related emission are investigated in colloidal CdSe/CdS dot-in-rod (DiR) and spherical core/shell nanocrystal (NC) ensembles by magneto-optical photoluminescence (PL) spectroscopy in magnetic fields up to 15 T. It is shown that the degree of circular polarization (DCP) of the exciton emission induced by the magnetic field is affected by the NC geometry as well as the exciton fine structure and can provide information on nanorod orientation. A theory to describe the circular and linear polarization properties of the NC emission in magnetic field is developed. It takes into account phonon mediated coupling between the exciton fine structure states as well as the dielectric enhancement effect resulting from the anisotropic shell of DiR NCs. This theoretical approach is used to model the experimental results and allows us to explain most of the measured features. The spin dynamics of the dark excitons is investigated in magnetic fields by time-resolved photoluminescence. The results highlight the importance of confined acoustic phonons in the spin relaxation of dark excitons. The bare core surface as well as the core/shell interface give rise to an efficient spin relaxation channel, while the surface of core/shell NCs seems to play only a minor role.Comment: 18 pages, 15 figure

Eulerian CFD modeling of nozzle geometry effects on ECN Sprays A and D: assessment and analysis

This is the author's version of a work that was accepted for publication in International Journal of Engine Research. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published as https://doi.org/10.1177/1468087419882500.[EN] Diesel spray modeling is a multi-scale problem with complex interactions between different flow regions, that is, internal nozzle flow, near-nozzle region and developed spray, including evaporation and combustion. There are several modeling approaches that have proven particularly useful for some spray regions although they have struggled at other areas, while Eulerian modeling has shown promise in dealing with all characteristics at a reasonable computational effort for engineering calculations. In this work, the sigma -Y single-fluid diffuse-interface model, based on scale separation assumptions at high Reynolds and Weber numbers, is used to simulate the engine combustion network Sprays A and D within a Reynolds-averaged Navier-Stokes turbulence modeling approach. The study is divided into two parts. First of all, the larger diameter Spray D is modeled from the nozzle flow till evaporative spray conditions, obtaining successful prediction of numerous spray metrics, paying special attention to the near-nozzle region where spray dispersion and interfacial surface area can be validated against measurements conducted at the Advanced Photon Source at Argonne National Laboratory, including both the ultra-small-angle X-ray scattering and the X-ray radiography. Afterwards, an analysis of the modeling predictions is made in comparison with previous results obtained for Spray A, considering the nozzle geometry effects in the modeling behavior.The authors thank the freely shared X-ray radiography and ultra-small-angle X-ray scattering measurements performed at Argonne National Laboratory by the following authors: Daniel J. Duke, Jan Ilavsky, Katarzyna E. Matusik., Brandon A. Sforzo., Alan L. Kastengren and Christopher F. Powell. They also thankfully acknowledge the computer resources at Picasso and the technical support provided by Universidad de Malaga (UMA; RES-FI-2018-1-0039).Pandal, A.; García-Oliver, JM.; Pastor Enguídanos, JM. (2020). Eulerian CFD modeling of nozzle geometry effects on ECN Sprays A and D: assessment and analysis. International Journal of Engine Research. 21(1):73-88. https://doi.org/10.1177/1468087419882500S7388211PAYRI, R., GARCIA, J., SALVADOR, F., & GIMENO, J. (2005). Using spray momentum flux measurements to understand the influence of diesel nozzle geometry on spray characteristics. Fuel, 84(5), 551-561. doi:10.1016/j.fuel.2004.10.009Payri, R., Salvador, F. J., Gimeno, J., & Zapata, L. D. (2008). Diesel nozzle geometry influence on spray liquid-phase fuel penetration in evaporative conditions. Fuel, 87(7), 1165-1176. doi:10.1016/j.fuel.2007.05.058Payri, R., Salvador, F. J., Gimeno, J., & de la Morena, J. (2009). Effects of nozzle geometry on direct injection diesel engine combustion process. Applied Thermal Engineering, 29(10), 2051-2060. doi:10.1016/j.applthermaleng.2008.10.009Payri, F., Payri, R., Salvador, F. J., & Martínez-López, J. (2012). A contribution to the understanding of cavitation effects in Diesel injector nozzles through a combined experimental and computational investigation. Computers & Fluids, 58, 88-101. doi:10.1016/j.compfluid.2012.01.005Kastengren, A. L., Powell, C. F., Wang, Y., Im, K.-S., & Wang, J. (2009). X-RAY RADIOGRAPHY MEASUREMENTS OF DIESEL SPRAY STRUCTURE AT ENGINE-LIKE AMBIENT DENSITY. Atomization and Sprays, 19(11), 1031-1044. doi:10.1615/atomizspr.v19.i11.30Pickett, L. M., Manin, J., Kastengren, A., & Powell, C. (2014). Comparison of Near-Field Structure and Growth of a Diesel Spray Using Light-Based Optical Microscopy and X-Ray Radiography. SAE International Journal of Engines, 7(2), 1044-1053. doi:10.4271/2014-01-1412Dahms, R. N., Manin, J., Pickett, L. M., & Oefelein, J. C. (2013). Understanding high-pressure gas-liquid interface phenomena in Diesel engines. Proceedings of the Combustion Institute, 34(1), 1667-1675. doi:10.1016/j.proci.2012.06.169Arienti, M., & Sussman, M. (2017). A numerical study of the thermal transient in high-pressure diesel injection. International Journal of Multiphase Flow, 88, 205-221. doi:10.1016/j.ijmultiphaseflow.2016.09.017Vallet, A., Burluka, A. A., & Borghi, R. (2001). DEVELOPMENT OF A EULERIAN MODEL FOR THE «ATOMIZATION» OF A LIQUID JET. Atomization and Sprays, 11(6), 24. doi:10.1615/atomizspr.v11.i6.20Siebers, D. L. (2008). Recent Developments on Diesel Fuel Jets Under Quiescent Conditions. Flow and Combustion in Reciprocating Engines, 257-308. doi:10.1007/978-3-540-68901-0_5Oefelein, J., Dahms, R., & Lacaze, G. (2012). Detailed Modeling and Simulation of High-Pressure Fuel Injection Processes in Diesel Engines. SAE International Journal of Engines, 5(3), 1410-1419. doi:10.4271/2012-01-1258Demoulin, F.-X., Reveillon, J., Duret, B., Bouali, Z., Desjonqueres, P., & Menard, T. (2013). TOWARD USING DIRECT NUMERICAL SIMULATION TO IMPROVE PRIMARY BREAK-UP MODELING. Atomization and Sprays, 23(11), 957-980. doi:10.1615/atomizspr.2013007439Desantes, J. M., Garcia-Oliver, J. M., Pastor, J. M., & Pandal, A. (2016). A COMPARISON OF DIESEL SPRAYS CFD MODELING APPROACHES: DDM VERSUS E-Y EULERIAN ATOMIZATION MODEL. Atomization and Sprays, 26(7), 713-737. doi:10.1615/atomizspr.2015013285Desantes, J. M., García-Oliver, J. M., Pastor, J. M., Pandal, A., Baldwin, E., & Schmidt, D. P. (2016). Coupled/decoupled spray simulation comparison of the ECN spray a condition with the -Y Eulerian atomization model. International Journal of Multiphase Flow, 80, 89-99. doi:10.1016/j.ijmultiphaseflow.2015.12.002Garcia-Oliver, J. M., Pastor, J. M., Pandal, A., Trask, N., Baldwin, E., & Schmidt, D. P. (2013). DIESEL SPRAY CFD SIMULATIONS BASED ON THE Σ-Υ EULERIAN ATOMIZATION MODEL. Atomization and Sprays, 23(1), 71-95. doi:10.1615/atomizspr.2013007198Navarro-Martinez, S. (2014). Large eddy simulation of spray atomization with a probability density function method. International Journal of Multiphase Flow, 63, 11-22. doi:10.1016/j.ijmultiphaseflow.2014.02.013Pandal, A., Pastor, J. M., García-Oliver, J. M., Baldwin, E., & Schmidt, D. P. (2016). A consistent, scalable model for Eulerian spray modeling. International Journal of Multiphase Flow, 83, 162-171. doi:10.1016/j.ijmultiphaseflow.2016.04.003Pandal, A., Payri, R., García-Oliver, J. M., & Pastor, J. M. (2017). Optimization of spray break-up CFD simulations by combining Σ-Y Eulerian atomization model with a response surface methodology under diesel engine-like conditions (ECN Spray A). Computers & Fluids, 156, 9-20. doi:10.1016/j.compfluid.2017.06.022Pandal, A., García-Oliver, J. M., Novella, R., & Pastor, J. M. (2018). A computational analysis of local flow for reacting Diesel sprays by means of an Eulerian CFD model. International Journal of Multiphase Flow, 99, 257-272. doi:10.1016/j.ijmultiphaseflow.2017.10.010Payri, R., Ruiz, S., Gimeno, J., & Martí-Aldaraví, P. (2015). Verification of a new CFD compressible segregated and multi-phase solver with different flux updates-equations sequences. Applied Mathematical Modelling, 39(2), 851-861. doi:10.1016/j.apm.2014.07.011Salvador, F. J., Gimeno, J., Pastor, J. M., & Martí-Aldaraví, P. (2014). Effect of turbulence model and inlet boundary condition on the Diesel spray behavior simulated by an Eulerian Spray Atomization (ESA) model. International Journal of Multiphase Flow, 65, 108-116. doi:10.1016/j.ijmultiphaseflow.2014.06.003Demoulin, F.-X., Beau, P.-A., Blokkeel, G., Mura, A., & Borghi, R. (2007). A NEW MODEL FOR TURBULENT FLOWS WITH LARGE DENSITY FLUCTUATIONS: APPLICATION TO LIQUID ATOMIZATION. Atomization and Sprays, 17(4), 315-345. doi:10.1615/atomizspr.v17.i4.20Pandal, A., Pastor, J. M., Payri, R., Kastengren, A., Duke, D., Matusik, K., … Schmidt, D. (2017). Computational and Experimental Investigation of Interfacial Area in Near-Field Diesel Spray Simulation. SAE International Journal of Fuels and Lubricants, 10(2), 423-431. doi:10.4271/2017-01-0859Weller, H. G., Tabor, G., Jasak, H., & Fureby, C. (1998). A tensorial approach to computational continuum mechanics using object-oriented techniques. Computers in Physics, 12(6), 620. doi:10.1063/1.168744Faeth, G. M. (1983). Evaporation and combustion of sprays. Progress in Energy and Combustion Science, 9(1-2), 1-76. doi:10.1016/0360-1285(83)90005-9Pitzer, K. S., Lippmann, D. Z., Curl, R. F., Huggins, C. M., & Petersen, D. E. (1955). The Volumetric and Thermodynamic Properties of Fluids. II. Compressibility Factor, Vapor Pressure and Entropy of Vaporization1. Journal of the American Chemical Society, 77(13), 3433-3440. doi:10.1021/ja01618a002Lebas, R., Menard, T., Beau, P. A., Berlemont, A., & Demoulin, F. X. (2009). Numerical simulation of primary break-up and atomization: DNS and modelling study. International Journal of Multiphase Flow, 35(3), 247-260. doi:10.1016/j.ijmultiphaseflow.2008.11.005Duret, B., Reveillon, J., Menard, T., & Demoulin, F. X. (2013). Improving primary atomization modeling through DNS of two-phase flows. International Journal of Multiphase Flow, 55, 130-137. doi:10.1016/j.ijmultiphaseflow.2013.05.004Gimeno, J., Bracho, G., Martí-Aldaraví, P., & Peraza, J. E. (2016). Experimental study of the injection conditions influence over n-dodecane and diesel sprays with two ECN single-hole nozzles. Part I: Inert atmosphere. Energy Conversion and Management, 126, 1146-1156. doi:10.1016/j.enconman.2016.07.077Kastengren, A., Ilavsky, J., Viera, J. P., Payri, R., Duke, D. J., Swantek, A., … Powell, C. F. (2017). Measurements of droplet size in shear-driven atomization using ultra-small angle x-ray scattering. International Journal of Multiphase Flow, 92, 131-139. doi:10.1016/j.ijmultiphaseflow.2017.03.005Kastengren, A. L., Tilocco, F. Z., Powell, C. F., Manin, J., Pickett, L. M., Payri, R., & Bazyn, T. (2012). ENGINE COMBUSTION NETWORK (ECN): MEASUREMENTS OF NOZZLE GEOMETRY AND HYDRAULIC BEHAVIOR. Atomization and Sprays, 22(12), 1011-1052. doi:10.1615/atomizspr.2013006309Matusik, K. E., Duke, D. J., Kastengren, A. L., Sovis, N., Swantek, A. B., & Powell, C. F. (2017). High-resolution X-ray tomography of Engine Combustion Network diesel injectors. International Journal of Engine Research, 19(9), 963-976. doi:10.1177/1468087417736985Payri, R., Gimeno, J., Cuisano, J., & Arco, J. (2016). Hydraulic characterization of diesel engine single-hole injectors. Fuel, 180, 357-366. doi:10.1016/j.fuel.2016.03.083Naber, J., & Siebers, D. L. (1996). Effects of Gas Density and Vaporization on Penetration and Dispersion of Diesel Sprays. SAE Technical Paper Series. doi:10.4271/960034Pope, S. B. (1978). An explanation of the turbulent round-jet/plane-jet anomaly. AIAA Journal, 16(3), 279-281. doi:10.2514/3.7521Battistoni, M., Magnotti, G. M., Genzale, C. L., Arienti, M., Matusik, K. E., Duke, D. J., … Marti-Aldaravi, P. (2018). Experimental and Computational Investigation of Subcritical Near-Nozzle Spray Structure and Primary Atomization in the Engine Combustion Network Spray D. SAE International Journal of Fuels and Lubricants, 11(4), 337-352. doi:10.4271/2018-01-0277Chesnel, J., Reveillon, J., Menard, T., & Demoulin, F.-X. (2011). LARGE EDDY SIMULATION OF LIQUID JET ATOMIZATION. Atomization and Sprays, 21(9), 711-736. doi:10.1615/atomizspr.2012003740Devassy, B. M., Habchi, C., & Daniel, E. (2015). ATOMIZATION MODELLING OF LIQUID JETS USING A TWO-SURFACE-DENSITY APPROACH. Atomization and Sprays, 25(1), 47-80. doi:10.1615/atomizspr.2014011350García-Oliver, J. M., Malbec, L.-M., Toda, H. B., & Bruneaux, G. (2017). A study on the interaction between local flow and flame structure for mixing-controlled Diesel sprays. Combustion and Flame, 179, 157-171. doi:10.1016/j.combustflame.2017.01.023Han, D., & Mungal, M. . (2001). Direct measurement of entrainment in reacting/nonreacting turbulent jets. Combustion and Flame, 124(3), 370-386. doi:10.1016/s0010-2180(00)00211-xHill, B. J. (1972). Measurement of local entrainment rate in the initial region of axisymmetric turbulent air jets. Journal of Fluid Mechanics, 51(4), 773-779. doi:10.1017/s0022112072001351Post, S., Iyer, V., & Abraham, J. (1999). A Study of Near-Field Entrainment in Gas Jets and Sprays Under Diesel Conditions. Journal of Fluids Engineering, 122(2), 385-395. doi:10.1115/1.48326

Phosphorus bioavailability in soil profiles of a long-term fertilizer experiment: The evaluation of their bioaccessibility

Global agricultural productivity depends on the use of finite phosphorus (P) resources of which not only the topsoil, but also subsoil, can hold immense reserves. To assess potential soil contribution to plant nutrition, we compared the P status of Stagnic Cambisol profiles in experimental plots that received different P fertilizer applications (control, triple superphosphate (TSP), compost, compost+TSP) for 16 years. Sequential fractionation was combined with P K-edge X-ray absorption near edge structure (XANES) spectroscopy to identify the chemical P speciation. Fertilized topsoils (21 to 69 kg P ha-1 a-1) showed P reserves larger by a factor of 1.2 to 1.4, and subsoil P reserves larger by a factor of 1.3 to 1.5 than those of the control. P-XANES revealed the predominance of inorganic P species such as moderately labile Fe- (46 to 92%), Al- (0 to 40%), and Ca- (0 to 15%) P compounds besides organic P (0 to 13%) in all treatments. The fertilizer application slightly altered P speciation throughout the profiles, but the type of fertilizer had no significant effect on it. Optimal plant growth requirements are restricted by the exchangeable P from the solid phase within the soil solution. Therefore, ongoing research focuses on the accessibility of P from P loaded amorphous Fe- and Al-hydroxides, previously identified as the predominant abiotic P forms. To assess their P desorption potential, P-33 rhizotron experiments combined with P-33 isotopic exchange kinetics (IEK) are underway. Preliminary results indicated that besides differences in P binding capacity of soil hydroxides, physical soil parameters, such as the matric potential, strongly control soil P availability, thus plant P acquisition rates can vary among different soil types. Our results gained new detailed information about P bioavailability under agricultural practice. The investigations towards P bioaccessibility may contribute to improved interpretation of soil P tests and reduced fertilizer recommendations

Towards the development of a simulator for investigating the impact of people management practices on retail performance

               \ud           \ud 

Modelling the emergence of cities and urban patterning using coupled integro-differential equations

Human residential population distributions show patterns of higher density clustering around local services such as shops and places of employment, displaying characteristic length scales; Fourier transforms and spatial autocorrelation show the length scale between UK cities is around 45 km. We use integro-differential equations to model the spatio-temporal dynamics of population and service density under the assumption that they benefit from spatial proximity, captured via spatial weight kernels. The system tends towards a well mixed homogeneous state or a spatial pattern. Linear stability analysis around the homogeneous steady state predicts a modelled length scale consistent with that observed in the data. Moreover, we show that spatial instability occurs only for perturbations with a sufficiently long wavelength and only where there is a sufficiently strong dependence of service potential on population density. Within urban centres, competition for space may cause services and population to be out of phase with one another, occupying separate parcels of land. By introducing competition, along with a preference for population to be located near, but not too near, to high service density areas, secondary out-of-phase patterns occur within the model, at a higher density and with a shorter length scale than in phase patterning. Thus, we show that a small set of core behavioural ingredients can generate aggregations of populations and services, and pattern formation within cities, with length scales consistent with real-world data. The analysis and results are valid across a wide range of parameter values and functional forms in the model

Investigation of the ignition and combustion processes of a dual-fuel spray under diesel-like conditions using computational fluid dynamics (CFD) modeling

Recent research activities in the field of diesel engines have shown the potential to reduce pollutant emissions and improve the thermal efficiency by controlling the fuel reactivity. However, understanding the impact of blending fuels with different physical and especially chemical properties on diesel-like spray mixing and combustion processes is still a challenge. Since the experimental techniques are still far from providing detailed temporal and spatial information about local spray conditions, computational fluid dynamics (CFD) modeling tools have become the key source of information for investigating the characteristics of these dual-fuel sprays. In this frame, the present research focuses on modeling a dual-fuel spray in diesel-like conditions, comparing different gasoline and diesel blends in terms of ignition characteristics and flame structure. The results confirm the suitability of the state of the art computational CFD modeling tools for reproducing the complex phenomena associated to dual-fuel sprays. Moreover, the important benefits provided by dual-fuel blends, considering the expected reduction in pollutant emissions as a consequence of the differences observed in terms of flame structure, are confirmed.The authors thank Dr. Jose Manuel Pastor for his support during this work and for sharing his profound knowledge and experience. Support for this research was provided by the Universitat Politecnica de Valencia inside the program Programas de Apoyo a la I + D + I, Primeros proyectos de investigacion (reference PAID-06-11 2033) and by the Ministerio de Ciencia e Innovacion inside the VeLoSoot project (TRA 2008_06448), which is gratefully acknowledged.López Sánchez, JJ.; Novella Rosa, R.; García Martínez, A.; Winklinger, JF. (2011). Investigation of the ignition and combustion processes of a dual-fuel spray under diesel-like conditions using computational fluid dynamics (CFD) modeling. Mathematical and Computer Modelling. 57:1897-1906. https://doi.org/10.1016/j.mcm.2011.12.030S189719065

Discovering novel hydrolases from hot environments

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this recordNovel hydrolases from hot and other extreme environments showing appropriate performance and/or novel functionalities and new approaches for their systematic screening are of great interest for developing new processes, for improving safety, health and environment issues. Existing processes could benefit as well from their properties. The workflow, based on the HotZyme project, describes a multitude of technologies and their integration from discovery to application, providing new tools for discovering, identifying and characterizing more novel thermostable hydrolases with desired functions from hot terrestrial and marine environments. To this end, hot springs worldwide were mined, resulting in hundreds of environmental samples and thousands of enrichment cultures growing on polymeric substrates of industrial interest. Using high-throughput sequencing and bioinformatics, 15 hot spring metagenomes, as well as several sequenced isolate genomes and transcriptomes were obtained. To facilitate the discovery of novel hydrolases, the annotation platform Anastasia and a whole-cell bioreporter-based functional screening method were developed. Sequence-based screening and functional screening together resulted in about 100 potentially new hydrolases of which more than a dozen have been characterized comprehensively from a biochemical and structural perspective. The characterized hydrolases include thermostable carboxylesterases, enol lactonases, quorum sensing lactonases, gluconolactonases, epoxide hydrolases, and cellulases. Apart from these novel thermostable hydrolases, the project generated an enormous amount of samples and data, thereby allowing the future discovery of even more novel enzymes.European CommissionEuropean Union FP

WHO systematic review of maternal mortality and morbidity: methodological issues and challenges

BACKGROUND: Reducing maternal mortality and morbidity are among the key international development goals. A prerequisite for monitoring the progress towards attainment of these goals is accurate assessment of the levels of mortality and morbidity. In order to contribute to mapping the global burden of reproductive ill-health, we are conducting a systematic review of incidence and prevalence of maternal mortality and morbidity. METHODS: We followed the standard methodology for systematic reviews. We prepared a protocol and a form for data extraction that identify key characteristics on study and reporting quality. An extensive search was conducted for the years 1997–2002 including electronic and hand searching. RESULTS: We screened the titles and abstracts of about 65,000 citations identified through 11 electronic databases as well as various other sources. Four thousand six hundred and twenty-six full-text reports were critically appraised and 2443 are included in the review so far. Approximately one third of the studies were conducted in Asia and Africa. The reporting quality was generally low with definitions for conditions and the diagnostic methods often not reported. CONCLUSIONS: There are unique challenges and issues regarding the search, critical appraisal and summarizing epidemiological data in this systematic review of prevalence/incidence studies. More methodological studies and discussion to advance the field will be useful. Considerable efforts including leadership, consensus building and resources are required to improve the standards of monitoring burden of disease

Towards an improved understanding of biogeochemical processes across surface-groundwater interactions in intermittent rivers and ephemeral streams

Surface-groundwater interactions in intermittent rivers and ephemeral streams (IRES), waterways which do not flow year-round, are spatially and temporally dynamic because of alternations between flowing, non-flowing and dry hydrological states. Interactions between surface and groundwater often create mixing zones with distinct redox gradients, potentially driving high rates of carbon and nutrient cycling. Yet a complete understanding of how underlying biogeochemical processes across surface-groundwater flowpaths in IRES differ among various hydrological states remains elusive. Here, we present a conceptual framework relating spatial and temporal hydrological variability in surface water-groundwater interactions to biogeochemical processing hotspots in IRES. We combine a review of theIRES biogeochemistry literature with concepts of IRES hydrogeomorphology to: (i) outline common distinctions among hydrological states in IRES; (ii) use these distinctions, together with considerations of carbon, nitrogen, and phosphorus cycles within IRES, to predict the relative potential for biogeochemical processing across different reach-scale processing zones (flowing water, fragmented pools, hyporheic zones, groundwater, and emerged sediments); and (iii) explore the potential spatial and temporal variability of carbon and nutrient biogeochemical processing across entire IRES networks. Our approach estimates the greatest reach-scale potential for biogeochemical processing when IRES reaches are fragmented into isolated surface water pools, and highlights the potential of relatively understudied processing zones, such as emerged sediments. Furthermore, biogeochemical processing in fluvial networks dominated by IRES is likely more temporally than spatially variable. We conclude that biogeochemical research in IRES would benefit from focusing on interactions between different nutrient cycles, surface-groundwater interactions in non-flowing states, and consideration of fluvial network architecture. Our conceptual framework outlines opportunities to advance studies and expand understanding of biogeochemistry in IRES