A unifying view of synchronization for data assimilation in complex nonlinear networks.

Networks of nonlinear systems contain unknown parameters and dynamical degrees of freedom that may not be observable with existing instruments. From observable state variables, we want to estimate the connectivity of a model of such a network and determine the full state of the model at the termination of a temporal observation window during which measurements transfer information to a model of the network. The model state at the termination of a measurement window acts as an initial condition for predicting the future behavior of the network. This allows the validation (or invalidation) of the model as a representation of the dynamical processes producing the observations. Once the model has been tested against new data, it may be utilized as a predictor of responses to innovative stimuli or forcing. We describe a general framework for the tasks involved in the "inverse" problem of determining properties of a model built to represent measured output from physical, biological, or other processes when the measurements are noisy, the model has errors, and the state of the model is unknown when measurements begin. This framework is called statistical data assimilation and is the best one can do in estimating model properties through the use of the conditional probability distributions of the model state variables, conditioned on observations. There is a very broad arena of applications of the methods described. These include numerical weather prediction, properties of nonlinear electrical circuitry, and determining the biophysical properties of functional networks of neurons. Illustrative examples will be given of (1) estimating the connectivity among neurons with known dynamics in a network of unknown connectivity, and (2) estimating the biophysical properties of individual neurons in vitro taken from a functional network underlying vocalization in songbirds.

Basin structure of optimization based state and parameter estimation.

Most data based state and parameter estimation methods require suitable initial values or guesses to achieve convergence to the desired solution, which typically is a global minimum of some cost function. Unfortunately, however, other stable solutions (e.g., local minima) may exist and provide suboptimal or even wrong estimates. Here, we demonstrate for a 9-dimensional Lorenz-96 model how to characterize the basin size of the global minimum when applying some particular optimization based estimation algorithm. We compare three different strategies for generating suitable initial guesses, and we investigate the dependence of the solution on the given trajectory segment (underlying the measured time series). To address the question of how many state variables have to be measured for optimal performance, different types of multivariate time series are considered consisting of 1, 2, or 3 variables. Based on these time series, the local observability of state variables and parameters of the Lorenz-96 model is investigated and confirmed using delay coordinates. This result is in good agreement with the observation that correct state and parameter estimation results are obtained if the optimization algorithm is initialized with initial guesses close to the true solution. In contrast, initialization with other exact solutions of the model equations (different from the true solution used to generate the time series) typically fails, i.e., the optimization procedure ends up in local minima different from the true solution. Initialization using random values in a box around the attractor exhibits success rates depending on the number of observables and the available time series (trajectory segment).

Tin(IV) Oxide Electron Transport Layer via Industrial-Scale Pulsed Laser Deposition for Planar Perovskite Solar Cells.

Electron transport layers (ETL) based on tin(IV) oxide (SnO2) are recurrently employed in perovskite solar cells (PSCs) by many deposition techniques. Pulsed laser deposition (PLD) offers a few advantages for the fabrication of such layers, such as being compatible with large scale, patternable, and allowing deposition at fast rates. However, a precise understanding of how the deposition parameters can affect the SnO2 film, and as a consequence the solar cell performance, is needed. Herein, we use a PLD tool equipped with a droplet trap to minimize the number of excess particles (originated from debris) reaching the substrate, and we show how to control the PLD chamber pressure to obtain surfaces with very low roughness and how the concentration of oxygen in the background gas can affect the number of oxygen vacancies in the film. Using optimized deposition conditions, we obtained solar cells in the n-i-p configuration employing methylammonium lead iodide perovskite as the absorber layer with power conversion efficiencies exceeding 18% and identical performance to devices having the more typical atomic layer deposited SnO2 ETL.

Simple approach for an electron extraction layer in an all-vacuum processed n-i-p perovskite solar cell.

Vacuum processing is considered to be a promising method allowing the scalable fabrication of perovskite solar cells (PSCs). In vacuum processed PSCs, the n-i-p structure employing organic charge transport layers is less common than the p-i-n structure due to limited options to achieve an efficient electron extraction layer (EEL) on indium tin oxide (ITO) with vacuum thermal evaporation. There are a number of specific applications where an n-i-p structure is required and therefore, it is of interest to have alternative solutions for the n-type contact in vacuum processed PSCs. In this work, we report an efficient vacuum deposited EEL using a mixture of conventional organic small molecules, C60 and bathocuproine (BCP). Incorporation of BCP into C60 does not result in conventional n-doping; however, we observed enhanced charge extraction, which significantly increased the power conversion efficiency (PCE) from 13.1% to 18.1% in all-vacuum processed PSCs. The C60:BCP mixed (co-sublimated) film most likely results in shifted energy levels leading to better alignment with the electrodes.

To what extent the traffic restriction policies applied in Barcelona city can improve its air quality?

Barcelona city (Spain) is applying a series of traffic restriction measures that aim at renewing and reducing the amount of circulating vehicles to improve air quality. The measures include changes in the built environment to reduce private vehicle space in specific areas through the so-called "superblocks" and tactical urban planning actions, along with the implementation of a city-wide Low Emission Zone (LEZ) that restricts the entry of the most polluting vehicles to the city. Our study quantifies the impact of these measures in the greater area of Barcelona combining a coupled macroscopic traffic and pollutant emission model with a multi-scale air quality model. Our modelling system allows estimating the effect of different traffic restrictions upon traffic and the associated emissions and air quality levels at a very high resolution (20 m). The measures were evaluated both individually and collectively to assess both their relative and overall impact upon emissions and air quality. We show that in the absence of traffic demand reductions, the application of isolated measures that reduce private vehicle space, either through superblocks or tactical urban planning, have no overall emission impacts; only localized street-level NOx positive and negative changes (±17%) are found due to traffic re-routing and the generation of new bottlenecks. It is only when these measures are combined with optimistic fleet renewal as a result of the LEZ implementation and demand reductions, that relevant global emission reductions in NOx are obtained (-13% and -30%, respectively) with estimated NO2 reductions of -36% and -23% at the two traffic air quality monitoring stations. Despite the potential improvements, our simulations suggest that current measures are insufficient to comply with EU air quality standards and that further traffic restriction policies to reduce traffic demand are needed.

A multianalyte assay panel with cell-bound complement activation products demonstrates clinical utility in systemic lupus erythematosus.

OBJECTIVE: To evaluate the clinical utility of the multianalyte assay panel (MAP), commercially known as AVISE Lupus test (Exagen Inc.), in patients suspected of SLE. METHODS: A systematic review of medical records of ANA-positive patients with a positive (>0.1) or negative (<-0.1) MAP score was conducted when the MAP was ordered (T0), when the test results were reviewed (T1) and at a later time (T2, ≥8 months after T1). Confidence in the diagnosis of SLE and initiation of hydroxychloroquine (HCQ) were assessed. RESULTS: A total of 161 patient records from 12 centres were reviewed at T0 and T1. T2 occurred for 90 patients. At T0, low, moderate and high confidence in SLE diagnosis was reported for 58%, 30% and 12% patients, respectively. Confidence in SLE diagnosis increased for the MAP positive, while MAP negative made SLE less likely. Odds of higher confidence in SLE diagnosis increased by 1.74-fold for every unit of increase of the MAP score (p<0.001). Using the MAP-negative/anti-double-stranded DNA-negative patients as reference, the HR of assigning an International Classification of Diseases, Tenth Revision lupus code was 7.02-fold, 11.2-fold and 14.8-fold higher in the low tier-2, high tier-2 and tier-1 positive, respectively (p<0.001). The HR of initiating HCQ therapy after T0 was 2.90-fold, 4.22-fold and 3.98-fold higher, respectively (p<0.001). CONCLUSION: The MAP helps increase the confidence in ruling-in and ruling-out SLE in patients suspected of the disease and informs on appropriate treatment decisions.

Laparoscopic port-site metastasis as the manifestation of neuroendocrine prostate cancer: Case report and literature review.

INTRODUCTION: The neuroendocrine differentiation in prostate cancer is a rare entity that may occur as de novo, or as a result of treatment with androgen deprivation. It is characterized by its rapid progression and poor prognosis, without elevation of the prostate specific antigen (PSA), which is why it is often diagnosed by biopsy of a site of metastasis; there are no established treatment regimens. In this case, metastasis was presented as implantation to a laparoscopic port. These implantations subsequent to laparoscopic procedures in prostate cancer are very rare, with an incidence between 0.09 and 0.7%. The exact pathogenesis of the tumor implantation at the insertion site is not clear, there are several theories. MATERIALS AND METHODS: We describe the case of a 53-year-old patient with a diagnosis of prostate adenocarcinoma who underwent laparoscopic radical prostatectomy plus lymphadenectomy, staged as PT3BN0 (0/6) M0R1 Gleason 4 + 5. The patient never had negative PSA levels after the treatment, and presented elevation of the same, so radiotherapy was performed at a dose of 66 Gy plus antiandrogen deprivation therapy with leuprolide acetate for 30 months, with a decrease in PSA to 0.011 ng/ml, which remained stable. After 3 months of hormonal therapy, he presented with an umbilical mass on the scar of the laparoscopic port; ultrasound and computed tomography were performed, showing a solid mass dependent of the umbilical upper edge with a defect in the abdominal wall of 3 cm, as well as hepatic nodules suggestive of metastatic lesions and peritoneal implantations. RESULTS: A biopsy of the abdominal wall lesion was performed, documenting poorly differentiated carcinoma with an immune-profile consistent with neuroendocrine carcinoma; immunohistochemistry showed strong and diffuse positivity with cytokeratin cocktail and chromogranin. In conjunction with oncology, treatment with chemotherapy was decided. He received six cycles of cisplatin and etoposide, with progression of his disease and death seven months after diagnosis. CONCLUSIONS: Prostate cancer with neuroendocrine differentiation is a rare entity, usually occurring in the castration resistance stage, with poor prognosis and survival of less than 1 year. It presents as clinical and radiological progression without elevation of the PSA. Although it is very rare, the possible causes include tumor implantation in laparoscopic ports and/or open surgery scars, so caution and certain precautions must be taken when performing radical prostatectomy. In case of suspecting a tumor with neuroendocrine differentiation, biopsy and immunohistochemistry studies should be performed in order to clarify the diagnosis and provide a multimodal treatment based on surgery, radiotherapy and chemotherapy.

Factors influencing erythrocyte sedimentation rate in adults: New evidence for an old test.

The erythrocyte sedimentation rate (ESR) is a routine test for inflammation. Few studies have investigated the potential influence of lifestyle factors and common metabolic abnormalities on the ESR. This study investigates the influence of demographic factors, alcohol consumption, smoking, physical activity, obesity, and metabolic syndrome on the ESR in adults.This cross-sectional study covered 1472 individuals (44.5% males; age range, 18-91 years) randomly selected from the population of a Spanish municipality. The ESR was measured using a standardized method. We assessed habitual alcohol consumption in standard drinking units, along with tobacco smoking, regular physical exercise (by questionnaire), body mass index, and variables defining metabolic syndrome. Multivariate analyses were performed, including mean corpuscular volume and hemoglobin concentration in the models.The ESR was higher in females than in males, and increased steadily with age. Median ESR of females was 2-fold higher than that of males, and median ESR of individuals aged >65 years was 2-fold higher than that of individuals in the youngest category (ages 18-35 years). Body mass index, presence of metabolic syndrome, and smoking were independently and positively associated with higher ESR values. Light alcohol drinkers and individuals with high regular physical activity displayed lower ESR values than did alcohol abstainers and individuals with low physical activity, respectively.ESR varies greatly with age and sex, and corresponding reference values are proposed. Lifestyle factors (physical activity, smoking, and alcohol consumption) and common metabolic abnormalities (obesity and related metabolic syndrome) may also influence ESR values.

Room-Temperature Cubic Phase Crystallization and High Stability of Vacuum-Deposited Methylammonium Lead Triiodide Thin Films for High-Efficiency Solar Cells.

Methylammonium lead triiodide (MAPI) has emerged as a high-performance photovoltaic material. Common understanding is that at room temperature, it adopts a tetragonal phase and it only converts to the perfect cubic phase around 50-60 °C. Most MAPI films are prepared using a solution-based coating process, yet they can also be obtained by vapor-phase deposition methods. Vapor-phase-processed MAPI films have significantly different characteristics than their solvent-processed analogous, such as relatively small crystal-grain sizes and short excited-state lifetimes. However, solar cells based on vapor-phase-processed MAPI films exhibit high power-conversion efficiencies. Surprisingly, after detailed characterization it is found that the vapor-phase-processed MAPI films adopt a cubic crystal structure at room temperature that is stable for weeks, even in ambient atmosphere. Furthermore, it is demonstrated that by tuning the deposition rates of both precursors during codeposition it is possible to vary the perovskite phase from cubic to tetragonal at room temperature. These findings challenge the common belief that MAPI is only stable in the tetragonal phase at room temperature.

Short Photoluminescence Lifetimes in Vacuum-Deposited CH3NH3PbI3 Perovskite Thin Films as a Result of Fast Diffusion of Photogenerated Charge Carriers.

It is widely accepted that a long photoluminescence (PL) lifetime in metal halide perovskite films is a crucial and favorable factor, as it ensures a large charge diffusion length leading to a high power conversion efficiency (PCE) in solar cells. It has been recently found that vacuum-evaporated CH3NH3PbI3 (eMAPI) films show very short PL lifetimes of several nanoseconds. The corresponding solar cells, however, have high photovoltage (>1.1 V) and PCEs (up to 20%). We rationalize this apparent contradiction and show that eMAPI films are characterized by a very high diffusion coefficient D, estimated from modeling the PL kinetics to exceed 1 cm2/s. Such high D values are favorable for long diffusion length as well as fast transport of carriers to film surfaces, where they recombine nonradiatively with surface recombination velocity S ∼ 104 cm/s. Possible physical origins leading to the high D values are also discussed.

Consistent Device Simulation Model Describing Perovskite Solar Cells in Steady-State, Transient, and Frequency Domain.

A variety of experiments on vacuum-deposited methylammonium lead iodide perovskite solar cells are presented, including JV curves with different scan rates, light intensity-dependent open-circuit voltage, impedance spectra, intensity-modulated photocurrent spectra, transient photocurrents, and transient voltage step responses. All these experimental data sets are successfully reproduced by a charge drift-diffusion simulation model incorporating mobile ions and charge traps using a single set of parameters. While previous modeling studies focused on a single experimental technique, we combine steady-state, transient, and frequency-domain simulations and measurements. Our study is an important step toward quantitative simulation of perovskite solar cells, leading to a deeper understanding of the physical effects in these materials. The analysis of the transient current upon voltage turn-on in the dark reveals that the charge injection properties of the interfaces are triggered by the accumulation of mobile ionic defects. We show that the current rise of voltage step experiments allow for conclusions about the recombination at the interface. Whether one or two mobile ionic species are used in the model has only a minor influence on the observed effects. A delayed current rise observed upon reversing the bias from +3 to -3 V in the dark cannot be reproduced yet by our drift-diffusion model. We speculate that a reversible chemical reaction of mobile ions with the contact material may be the cause of this effect, thus requiring a future model extension. A parameter variation is performed in order to understand the performance-limiting factors of the device under investigation.

Efficient Vacuum Deposited P-I-N Perovskite Solar Cells by Front Contact Optimization.

Hole transport layers (HTLs) are of fundamental importance in perovskite solar cells (PSCs), as they must ensure an efficient and selective hole extraction, and ohmic charge transfer to the corresponding electrodes. In p-i-n solar cells, the ITO/HTL is usually not ohmic, and an additional interlayer such as MoO3 is usually placed in between the two materials by vacuum sublimation. In this work, we evaluated the properties of the MoO3/TaTm (TaTm is the HTL N4,N4,N4″,N4″-tetra([1,1'-biphenyl]-4-yl)-[1,1':4',1″-terphenyl]-4,4″-diamine) hole extraction interface by selectively annealing either MoO3 (prior to the deposition of TaTm) or the bilayer MoO3/TaTm (without pre-treatment on the MoO3), at temperature ranging from 60 to 200°C. We then used these p-contacts for the fabrication of a large batch of fully vacuum deposited PSCs, using methylammonium lead iodide as the active layer. We show that annealing the MoO3/TaTm bilayers at high temperature is crucial to obtain high rectification with low non-radiative recombination, due to an increase of the electrode work function and the formation of an ohmic interface with TaTm.

Phosphomolybdic acid as an efficient hole injection material in perovskite optoelectronic devices.

Efficient perovskite devices consist of a perovskite film sandwiched between charge selective layers, in order to avoid non-radiative recombination. A common metal oxide used as a p-type or hole transport layer is molybdenum oxide. MoO3 is of particular interest for its very large work function, which allows it to be used both as an interfacial charge transfer material and a dopant for organic semiconductors. However, high quality and high work function MoO3 is typically thermally evaporated in a vacuum. An alternative solution-processable high work function material is phosphomolybdic acid (PMA), which is stable, commercially available and environmentally friendly. In this Communication, we show the first application of PMA in efficient vacuum processed perovskite devices. We found that the direct growth of perovskite films onto PMA leads to strong charge carrier recombination, hindering the solar cell photovoltage. Using an energetically suitable selective transport layer placed between PMA and the perovskite film, solar cells with efficiency >13% as well as LEDs with promising quantum efficiency can be obtained.

Interfacial Modification for High-Efficiency Vapor-Phase-Deposited Perovskite Solar Cells Based on a Metal Oxide Buffer Layer.

Vacuum deposition is one of the most technologically relevant techniques for the fabrication of perovskite solar cells. The most efficient vacuum-based devices rely on doped organic contacts, compromising the long-term stability of the system. Here, we introduce an inorganic electron-transporting material to obtain power conversion efficiencies matching the best performing vacuum-deposited devices, with open-circuit potential close to the thermodynamic limit. We analyze the leakage current reduction and the interfacial recombination improvement upon use of a thin (<10 nm) interlayer of C60, as well as a more favorable band alignment after a bias/ultraviolet light activation process. This work presents an alternative for organic contacts in highly efficient vacuum-deposited perovskite solar cells.

A theoretical model to estimate the oil burial depth on sandy beaches: A new oil spill management tool.

In oiled sandy beaches, unrecovered fuel can be buried up to several metres. This study proposes a theoretical approach to oil burial estimation along the intertidal area. First, our results revealed the existence of two main patterns in seasonal beach profile behaviour. Type A is characterized by intertidal slopes of time-constant steepness which advance/recede parallel to themselves in response to changing wave conditions. Type B is characterized by slopes of time-varying steepness which intersect at a given point in the intertidal area. This finding has a direct influence on the definition of oil depth. Type A pattern exhibits oil burial along the entire intertidal area following decreasing wave energy, while the type B pattern combines burial in high intertidal and exhumation in mid and/or low intertidal zones, depending on the position of the intersection point. These outcomes should be incorporated as key tools in future oil spill management programs.

Strontium Insertion in Methylammonium Lead Iodide: Long Charge Carrier Lifetime and High Fill-Factor Solar Cells.

The addition of Sr2+ in CH3 NH3 PbI3 perovskite films enhances the charge carrier collection efficiency of solar cells leading to very high fill factors, up to 85%. The charge carrier lifetime of Sr2+ -containing perovskites is in excess of 40 µs, longer than those reported for perovskite single crystals.

Functional genomics and expression analysis of the Corynebacterium glutamicum fpr2-cysIXHDNYZ gene cluster involved in assimilatory sulphate reduction.

BACKGROUND: Corynebacterium glutamicum is a high-GC Gram-positive soil bacterium of great biotechnological importance for the production of amino acids. To facilitate the rational design of sulphur amino acid-producing strains, the pathway for assimilatory sulphate reduction providing the necessary reduced sulfur moieties has to be known. Although this pathway has been well studied in Gram-negative bacteria like Escherichia coli and low-GC Gram-positives like Bacillus subtilis, little is known for the Actinomycetales and other high-GC Gram-positive bacteria. RESULTS: The genome sequence of C. glutamicum was searched for genes involved in the assimilatory reduction of inorganic sulphur compounds. A cluster of eight candidate genes could be identified by combining sequence similarity searches with a subsequent synteny analysis between C. glutamicum and the closely related C. efficiens. Using mutational analysis, seven of the eight candidate genes, namely cysZ, cysY, cysN, cysD, cysH, cysX, and cysI, were demonstrated to be involved in the reduction of inorganic sulphur compounds. For three of the up to now unknown genes possible functions could be proposed: CysZ is likely to be the sulphate permease, while CysX and CysY are possibly involved in electron transfer and cofactor biosynthesis, respectively. Finally, the candidate gene designated fpr2 influences sulphur utilisation only weakly and might be involved in electron transport for the reduction of sulphite. Real-time RT-PCR experiments revealed that cysIXHDNYZ form an operon and that transcription of the extended cluster fpr2 cysIXHDNYZ is strongly influenced by the availability of inorganic sulphur, as well as L-cysteine. Mapping of the fpr2 and cysIXHDNYZ promoters using RACE-PCR indicated that both promoters overlap with binding-sites of the transcriptional repressor McbR, suggesting an involvement of McbR in the observed regulation. Comparative genomics revealed that large parts of the extended cluster are conserved in 11 of 17 completely sequenced members of the Actinomycetales. CONCLUSION: The set of C. glutamicum genes involved in assimilatory sulphate reduction was identified and four novel genes involved in this pathway were found. The high degree of conservation of this cluster among the Actinomycetales supports the hypothesis that a different metabolic pathway for the reduction of inorganic sulphur compounds than that known from the well-studied model organisms E. coli and B. subtilis is used by members of this order, providing the basis for further biochemical studies.

Systematic variational method for statistical nonlinear state and parameter estimation.

In statistical data assimilation one evaluates the conditional expected values, conditioned on measurements, of interesting quantities on the path of a model through observation and prediction windows. This often requires working with very high dimensional integrals in the discrete time descriptions of the observations and model dynamics, which become functional integrals in the continuous-time limit. Two familiar methods for performing these integrals include (1) Monte Carlo calculations and (2) variational approximations using the method of Laplace plus perturbative corrections to the dominant contributions. We attend here to aspects of the Laplace approximation and develop an annealing method for locating the variational path satisfying the Euler-Lagrange equations that comprises the major contribution to the integrals. This begins with the identification of the minimum action path starting with a situation where the model dynamics is totally unresolved in state space, and the consistent minimum of the variational problem is known. We then proceed to slowly increase the model resolution, seeking to remain in the basin of the minimum action path, until a path that gives the dominant contribution to the integral is identified. After a discussion of some general issues, we give examples of the assimilation process for some simple, instructive models from the geophysical literature. Then we explore a slightly richer model of the same type with two distinct time scales. This is followed by a model characterizing the biophysics of individual neurons.