Photo-Responsive Control of Adsorption and Structure Formation at the Air-Water Interface with Arylazopyrazoles.

Smart interfaces that are responsive to external triggers such as light are of great interest for the development of responsive or adaptive materials and interfaces. Using alkyl-arylazopyrazole butyl sulfonate surfactants (alkyl-AAP) that can undergo E/Z photoisomerization when irradiated with green (E) and UV (Z) lights, we demonstrate through a combination of experiments and computer simulations that there can be surprisingly large changes in surface tension and in the molecular structure and order at air-water interfaces. Surface tensiometry, vibrational sum-frequency generation (SFG) spectroscopy, and neutron reflectometry (NR) are applied to the study of custom-synthesized AAP surfactants with octyl- and H-terminal groups at air-water interfaces as a function of their bulk concentration and E/Z configuration. Upon photoswitching, a drastic influence of the alkyl chain on both the surface activity and the responsiveness of interfacial surfactants is revealed from changes in the surface tension, γ, where the largest changes in γ are observed for octyl-AAP (Δγ ∼ 23 mN/m) in contrast to H-AAP with Δγ < 10 mN/m. Results from vibrational SFG spectroscopy and NR show that the interfacial composition and the molecular order of the surfactants drastically change with E/Z photoisomerization and surface coverage. Indeed, from analysis of the S-O (head group) and C-H vibrational bands (hydrophobic tail), a qualitative analysis of orientational and structural changes of interfacial AAP surfactants is provided. The experiments are complemented by resolution of thermodynamic parameters such as equilibrium constants from ultra-coarse-grained simulations, which also capture details like island formation and interaction parameters of interfacial molecules. Here, the interparticle interaction ("stickiness") and the interaction with the surface are adjusted, closely reflecting experimental conditions.

Effects of Charge Density on Spread Hyperbranched Polyelectrolyte/Surfactant Films at the Air/Water Interface.

The interfacial structure and morphology of films spread from hyperbranched polyethylene imine/sodium dodecyl sulfate (PEI/SDS) aggregates at the air/water interface have been resolved for the first time with respect to polyelectrolyte charged density. A recently developed method to form efficient films from the dissociation of aggregates using a minimal quantity of materials is exploited as a step forward in enhancing understanding of the film properties with a view to their future use in technological applications. Interfacial techniques that resolve different time and length scales, namely, ellipsometry, Brewster angle microscopy, and neutron reflectometry, are used. Extended structures of both components are formed under a monolayer of the surfactant with bound polyelectrolytes upon film compression on subphases adjusted to pH 4 or 10, corresponding to high and low charge density of the polyelectrolyte, respectively. A rigid film is related to compact conformation of the PEI in the interfacial structure at pH 4, while it is observed that aggregates remain embedded in mobile films at pH 10. The ability to compact surfactants in the monolayer to the same extent as its maximum coverage in the absence of polyelectrolyte is distinct from the behavior observed for spread films involving linear polyelectrolytes, and intriguingly evidence points to the formation of extended structures over the full range of surface pressures. We conclude that the molecular architecture and charge density can be important parameters in controlling the structures and properties of spread polyelectrolyte/surfactant films, which holds relevance to a range of applications, such as those where PEI is used, including CO2 capture, electronic devices, and gene transfection.

Evaluation of Child-Computer Interaction Using Fitts' Law: A Comparison between a Standard Computer Mouse and a Head Mouse.

This study evaluates and compares the suitability for child-computer interaction (CCI, the branch within human-computer interaction focused on interactive computer systems for children) of two devices: a standard computer mouse and the ENLAZA interface, a head mouse that measures the user's head posture using an inertial sensor. A multidirectional pointing task was used to assess the motor performance and the users' ability to learn such a task. The evaluation was based on the interpretation of the metrics derived from Fitts' law. Ten children aged between 6 and 8 participated in this study. Participants performed a series of pre- and post-training tests for both input devices. After the experiments, data were analyzed and statistically compared. The results show that Fitts' law can be used to detect changes in the learning process and assess the level of psychomotor development (by comparing the performance of adults and children). In addition, meaningful differences between the fine motor control (hand) and the gross motor control (head) were found by comparing the results of the interaction using the two devices. These findings suggest that Fitts' law metrics offer a reliable and objective way of measuring the progress of physical training or therapy.

Deepint.net: A Rapid Deployment Platform for Smart Territories.

This paper presents an efficient cyberphysical platform for the smart management of smart territories. It is efficient because it facilitates the implementation of data acquisition and data management methods, as well as data representation and dashboard configuration. The platform allows for the use of any type of data source, ranging from the measurements of a multi-functional IoT sensing devices to relational and non-relational databases. It is also smart because it incorporates a complete artificial intelligence suit for data analysis; it includes techniques for data classification, clustering, forecasting, optimization, visualization, etc. It is also compatible with the edge computing concept, allowing for the distribution of intelligence and the use of intelligent sensors. The concept of smart cities is evolving and adapting to new applications; the trend to create intelligent neighbourhoods, districts or territories is becoming increasingly popular, as opposed to the previous approach of managing an entire megacity. In this paper, the platform is presented, and its architecture and functionalities are described. Moreover, its operation has been validated in a case study where the bike renting service of Paris-Vélib' Métropole has been managed. This platform could enable smart territories to develop adapted knowledge management systems, adapt them to new requirements and to use multiple types of data, and execute efficient computational and artificial intelligence algorithms. The platform optimizes the decisions taken by human experts through explainable artificial intelligence models that obtain data from IoT sensors, databases, the Internet, etc. The global intelligence of the platform could potentially coordinate its decision-making processes with intelligent nodes installed in the edge, which would use the most advanced data processing techniques.

Segregating the true perturbation position from ghost energy points region in ϕ-OTDR systems.

ϕ-OTDR perturbation detection applications demand optimal precision of the perturbation location. Strategies for improving both signal-to-noise (SNR) and precision of the perturbation location in a laboratory environment may fail when applying to a very long fiber under test (FUT) in real-field environments. With this deployment, meaningful energy points representing the response of a certain perturbation can be located at random locations of the fiber other than the original location of the perturbation. These random locations are referred to as the ghost energy points that confuse the system to mistakenly consider the location of these points as the original perturbation location. We present in this paper a novel space-time scanning (ST-scan) method that segregates the ghost energy point locations from those of the real perturbation so that the original perturbation location estimation is improved.

Multiple Physiological Signals Fusion Techniques for Improving Heartbeat Detection: A Review.

This paper presents a review of the techniques found in the literature that aim to achieve a robust heartbeat detection from fusing multi-modal physiological signals (e.g., electrocardiogram (ECG), blood pressure (BP), artificial blood pressure (ABP), stroke volume (SV), photoplethysmogram (PPG), electroencephalogram (EEG), electromyogram (EMG), and electrooculogram (EOG), among others). Techniques typically employ ECG, BP, and ABP, of which usage has been shown to obtain the best performance under challenging conditions. SV, PPG, EMG, EEG, and EOG signals can help increase performance when included within the fusion. Filtering, signal normalization, and resampling are common preprocessing steps. Delay correction between the heartbeats obtained over some of the physiological signals must also be considered, and signal-quality assessment to retain the best signal/s must be considered as well. Fusion is usually accomplished by exploiting regularities in the RR intervals; by selecting the most promising signal for the detection at every moment; by a voting process; or by performing simultaneous detection and fusion using Bayesian techniques, hidden Markov models, or neural networks. Based on the results of the review, guidelines to facilitate future comparison of the performance of the different proposals are given and promising future lines of research are pointed out.

Positive and Negative Evidence Accumulation Clustering for Sensor Fusion: An Application to Heartbeat Clustering.

In this work, a new clustering algorithm especially geared towards merging data arising from multiple sensors is presented. The algorithm, called PN-EAC, is based on the ensemble clustering paradigm and it introduces the novel concept of negative evidence. PN-EAC combines both positive evidence, to gather information about the elements that should be grouped together in the final partition, and negative evidence, which has information about the elements that should not be grouped together. The algorithm has been validated in the electrocardiographic domain for heartbeat clustering, extracting positive evidence from the heartbeat morphology and negative evidence from the distances between heartbeats. The best result obtained on the MIT-BIH Arrhythmia database yielded an error of 1.44%. In the St. Petersburg Institute of Cardiological Technics 12-Lead Arrhythmia Database database (INCARTDB), an error of 0.601% was obtained when using two electrocardiogram (ECG) leads. When increasing the number of leads to 4, 6, 8, 10 and 12, the algorithm obtains better results (statistically significant) than with the previous number of leads, reaching an error of 0.338%. To the best of our knowledge, this is the first clustering algorithm that is able to process simultaneously any number of ECG leads. Our results support the use of PN-EAC to combine different sources of information and the value of the negative evidence.

Postfire nitrogen balance of Mediterranean shrublands: Direct combustion losses versus gaseous and leaching losses from the postfire soil mineral nitrogen flush.

Fire is a major factor controlling global carbon (C) and nitrogen (N) cycling. While direct C and N losses caused by combustion have been comparably well established, important knowledge gaps remain on postfire N losses. Here, we quantified both direct C and N combustion losses as well as postfire gaseous losses (N2 O, NO and N2 ) and N leaching after a high-intensity experimental fire in an old shrubland in central Spain. Combustion losses of C and N were 9.4 Mg C/ha and 129 kg N/ha, respectively, representing 66% and 58% of initial aboveground vegetation and litter stocks. Moreover, fire strongly increased soil mineral N concentrations by several magnitudes to a maximum of 44 kg N/ha 2 months after the fire, with N largely originating from dead soil microbes. Postfire soil emissions increased from 5.4 to 10.1 kg N ha-1  year-1 for N2 , from 1.1 to 1.9 kg N ha-1  year-1 for NO and from 0.05 to 0.2 kg N ha-1  year-1 for N2 O. Maximal leaching losses occurred 2 months after peak soil mineral N concentrations, but remained with 0.1 kg N ha-1  year-1 of minor importance for the postfire N mass balance. 15 N stable isotope labelling revealed that 33% of the mineral N produced by fire was incorporated in stable soil N pools, while the remainder was lost. Overall, our work reveals significant postfire N losses dominated by emissions of N2 that need to be considered when assessing fire effects on ecosystem N cycling and mass balance. We propose indirect N gas emissions factors for the first postfire year, equalling to 7.7% (N2 -N), 2.7% (NO-N) and 5.0% (N2 O-N) of the direct fire combustion losses of the respective N gas species.

A Novel Fiber Optic Based Surveillance System for Prevention of Pipeline Integrity Threats.

This paper presents a novel surveillance system aimed at the detection and classification of threats in the vicinity of a long gas pipeline. The sensing system is based on phase-sensitive optical time domain reflectometry (ϕ-OTDR) technology for signal acquisition and pattern recognition strategies for threat identification. The proposal incorporates contextual information at the feature level and applies a system combination strategy for pattern classification. The contextual information at the feature level is based on the tandem approach (using feature representations produced by discriminatively-trained multi-layer perceptrons) by employing feature vectors that spread different temporal contexts. The system combination strategy is based on a posterior combination of likelihoods computed from different pattern classification processes. The system operates in two different modes: (1) machine + activity identification, which recognizes the activity being carried out by a certain machine, and (2) threat detection, aimed at detecting threats no matter what the real activity being conducted is. In comparison with a previous system based on the same rigorous experimental setup, the results show that the system combination from the contextual feature information improves the results for each individual class in both operational modes, as well as the overall classification accuracy, with statistically-significant improvements.

Segregation of nitrogen use between ammonium and nitrate of ectomycorrhizas and beech trees.

Here, we characterized nitrogen (N) uptake of beech (Fagus sylvatica) and their associated ectomycorrhizal (EM) communities from NH4+ and NO3- . We hypothesized that a proportional fraction of ectomycorrhizal N uptake is transferred to the host, thereby resulting in the same uptake patterns of plants and their associated mycorrhizal communities. 15 N uptake was studied under various field conditions after short-term and long-term exposure to a pulse of equimolar NH4+ and NO3- concentrations, where one compound was replaced by 15 N. In native EM assemblages, long-term and short-term 15 N uptake from NH4+ was higher than that from NO3- , regardless of season, water availability and site exposure, whereas in beech long-term 15 N uptake from NO3- was higher than that from NH4+ . The transfer rates from the EM to beech were lower for 15 N from NH4+ than from NO3- . 15 N content in EM was correlated with 15 N uptake of the host for 15 NH4+ , but not for 15 NO3- -derived N. These findings suggest stronger control of the EM assemblage on N provision to the host from NH4+ than from NO3- . Different host and EM accumulation patterns for inorganic N will result in complementary resource use, which might be advantageous in forest ecosystems with limited N availability.

[BREASTFEEDING AS A METHOD OF BREAST CANCER PREVENTION]. / La Lactancia materna. COMO MÉTODO BE PREVENCIÓN DEL CÁNCER DE MAMA.

INTRODUCTION: Breast cancer is the most common type or cancer in women with an incidence of about 720,000 cases per year and a mortality between 6 and 23 per 100,000, what it means a very important global health problem. METHOD: Sistematic review in the following databases: PubMed, SciELO, Cochrane Plus, Medline, Cuiden and Embase. The search was limited to English and Spanish languages, between 2005 and 2015 and human studies. RESULTS: All studies are observational by the characteristics of the studied pathology. It is observed that there is a decreased risk of breast cancer in women who had ever breastfed compared to those who had not. This reduced risk is most evident in postmenopausal women but also happens in premenopausal. It has also been observed that protection is increased with increasing lactation duration. The protective effect of breastfeeding happens by differentiation of breast cells, by reduction of the number of ovulatory cycles and by estrogen and carcinogens excretion through human milk. CONCLUSTONS: Breastfeeding is associated with a decreased risk of breast cancer, and health teams must therefore educate mothers about its beneficial effects to themselves and their children.

Photoresponsive arylazopyrazole surfactant/PDADMAC mixtures: reversible control of bulk and interfacial properties.

In many applications of polyelectrolyte/surfactant (P/S) mixtures, it is difficult to fine-tune them after mixing the components without changing the sample composition, e.g. pH or the ionic strength. Here we report on a new approach where we use photoswitchable surfactants to enable drastic changes in both the bulk and interfacial properties. Poly(diallyldimethylammonium chloride) (PDADMAC) mixtures with three alkyl-arylazopyrazole butyl sulfonates (CnAAP) with -H, -butyl and -octyl tails are applied and E/Z photoisomerization of the surfactants is used to cause substantially different hydrophobic interactions between the surfactants and PDADMAC. These remotely controlled changes affect significantly the P/S binding and allows for tuning both the bulk and interfacial properties of PDADMAC/CnAAP mixtures through light irradiation. For that, we have fixed the surfactant concentrations at values where they exhibit pronounced surface tension changes upon E/Z photoisomerization with 365 nm UV light (Z) and 520 nm green (E) light and have varied the PDADMAC concentration. The electrophoretic mobility can be largely tuned by photoisomerisation of CnAAP surfactants and P/S aggregates, which can even exhibit a charge reversal from negative to positive values or vice versa. In addition, low colloidal stability at equimolar concentrations of PDADMAC with CnAAP surfactants in the E configuration lead to the formation of large aggregates in the bulk which can be broken up by irradiation with UV light when the surfactant's alkyl chain is short enough (C0AAP). Vibrational sum-frequency generation (SFG) spectroscopy reveals changes at the interface similar to the bulk, where the charging state at air-water interfaces can be modified with light irradiation. Using SFG spectroscopy, we interrogated the O-H stretching modes of interfacial H2O and provide qualitative information on surface charging that is complemented by neutron reflectometry, from which we resolved the surface excesses of PDADMAC and CnAAP at the air-water interface, independently.

Targeted knockdown of Cerkl, a retinal dystrophy gene, causes mild affectation of the retinal ganglion cell layer.

In order to approach the function of the retinal dystrophy CERKL gene we generated a novel knockout mouse model by cre-mediated targeted deletion of the Cerkl first exon and proximal promoter. The excised genomic region (2.3kb) encompassed the first Cerkl exon, upstream sequences including the proximal promoter and the initial segment of the first intron. The Cerkl-/- mice were viable and fertile. The targeted Cerkl deletion resulted in a knockdown more than a knockout model, given that alternative promoters (unreported at that time) directed basal expression of Cerkl (35%). In situ hybridizations and immunohistochemistry showed that this remnant expression was moderate in the photoreceptors and weak in the ganglion and inner cell layers. Morphological characterization of the Cerkl-/- retinas did not show any gross structural changes, even at 12 months of age. However, some clear and consistent signals of gliosis and retinal stress were detected by the statistically significant increase of i) the glial fibrillary antigen protein (GFAP) expression, and ii) apoptosis, as detected by TUNEL. Remarkably, consistent non-progressive perturbation (from birth up to 12 months of age) of ganglion cells was supported by the decrease of the Brn3a marker expression as well as the reduced oscillatory potentials in the electroretinographic recordings. In conclusion, the Cerkl-/- knockdown shows a mild retinal phenotype, with increased levels of cellular stress and apoptosis indicators, and clear signs of functional alteration at the ganglion cell layer, but no detectable morphological changes.

Interspecific temporal and spatial differences in the acquisition of litter-derived nitrogen by ectomycorrhizal fungal assemblages.

The spatiotemporal dynamics of, and interspecific differences in, the acquisition of litter-derived nitrogen (N) by natural assemblages of ectomycorrhizal root tips are poorly understood. Small cylindrical mesh bags containing (15)N-labelled beech (Fagus sylvatica) leaf litter that permit hyphal but not root ingrowth were inserted vertically into the top soil layer of an old-growth beech forest. The lateral transfer of (15)N into the circumjacent soil, roots, microbes and ectomycorrhizas was measured during an 18-month exposure period. Ectomycorrhial fungi (EMF) showed large interspecific variation in the temporal pattern and extent of (15)N accumulation. Initially, when N was mainly available from the leachate, microbes were more efficient at N immobilization than the majority of EMF, but distinct fungal species also showed significant (15)N accumulation. During later phases, the enrichment of (15)N in Tomentella badia was higher than in microbes and other EMF species. Roots and soil accumulated (15)N with a large delay compared with microbes and EMF. Because approximately half of the studied fungal species had direct access to N from leaf litter and the remainder to N from leached compounds, we suggest that EMF diversity facilitates the N utilization of the host by capturing N originating from early-released solutes and late degradation products from a recalcitrant source.

Unravelling the orientation of the inositol-biphosphate ring and its dependence on phosphatidylinositol 4,5-bisphosphate cluster formation in model membranes.

HYPOTHESIS: Inositol phospholipids are well known to form clusters in the cytoplasmic leaflet of the plasma membrane that are responsible for the interaction and recruitment of proteins involved in key biological processes like endocytosis, ion channel activation and secondary messenger production. Although their phosphorylated inositol ring headgroup plays an important role in protein binding, its orientation with respect to the plane of the membrane and its lateral packing density has not been previously described experimentally. EXPERIMENTS: Here, we study phosphatidylinositol 4,5-bisphosphate (PIP2) planar model membranes in the form of Langmuir monolayers by surface pressure-area isotherms, Brewster angle microscopy and neutron reflectometry to elucidate the relation between lateral (in-plane) and perpendicular (out-of-plane) molecular organization of PIP2. FINDINGS: Different surface areas were explored through monolayer compression, allowing us to correlate the formation of transient PIP2 clusters with the change in orientation of the inositol-biphosphate headgroup, which was experimentally determined by neutron reflectometry.

Control of the structure and morphology of polypeptide/surfactant spread films by exploiting specific interactions.

We demonstrate control of the structure and morphology of polypeptide/surfactant films at the air/water interface as a function of the maximum compression ratio of the surface area, exploiting a recently developed film formation mechanism that requires minimal quantities of materials involving the dissociation of aggregates. The systems studied are poly(L-lysine) (PLL) or poly(L-arginine) (PLA) with sodium dodecyl sulfate (SDS), chosen because the surfactant (i) interacts more strongly with the latter polypeptide due to the formation of hydrogen bonds between the guanidinium group and its oxygen atoms, and (ii) induces bulk ß-sheet and α-helix conformations of the respective polypeptides. The working hypothesis is that such different interactions may be used to tune the film properties when compressed to form extended structures (ESs). Neutron reflectometry reveals that application of a high compression ratio (4.5 : 1) results in the nanoscale self-assembly of ESs containing up to two PLL-wrapped SDS bilayers. Brewster angle microscopy provides images of the PLL/SDS ESs as discrete regions on the micrometre scale while additional linear regions of PLA/SDS ESs mark macroscopic film folding. Ellipsometry demonstrates high stability of the different ESs formed. The collapse of PLL/SDS films upon compression to a very high ratio (10 : 1) is irreversible due to the formation of solid domains that remain embedded in the film upon expansion while that of PLA/SDS films is reversible. These findings demonstrate that differences in the side group of a polypeptide can have a major influence on controlling the film properties, marking a key step in the development of this new film formation mechanism for the design of biocompatible and/or biodegradable films with tailored properties for applications in tissue engineering, biosensors and antimicrobial coatings.

Engineering phosphatidylinositol-4,5-bisphosphate model membranes enriched in endocytic cargo: A neutron reflectometry, AFM and QCM-D structural study.

The combination of in vitro models of biological membranes based on solid-supported lipid bilayers (SLBs) and of surface sensitive techniques, such as neutron reflectometry (NR), atomic force microscopy (AFM) and quartz crystal microbalance with dissipation monitoring (QCM-D), is well suited to provide quantitative information about molecular level interactions and lipid spatial distributions. In this work, cellular plasma membranes have been mimicked by designing complex SLB, containing phosphatidylinositol 4,5-bisphosphate (PtdIns4,5P2) lipids as well as incorporating synthetic lipo-peptides that simulate the cytoplasmic tails of transmembrane proteins. The QCM-D results revealed that the adsorption and fusion kinetics of PtdIns4,5P2 are highly dependent of Mg2+. Additionally, it was shown that increasing concentrations of PtdIns4,5P2 leads to the formation of SLBs with higher homogeneity. The presence of PtdIns4,5P2 clusters was visualized by AFM. NR provided important insights about the structural organization of the various components within the SLB, highlighting that the leaflet symmetry of these SLBs is broken by the presence of CD4-derived cargo peptides. Finally, we foresee our study to be a starting point for more sophisticated in vitro models of biological membranes with the incorporation of inositol phospholipids and synthetic endocytic motifs.

Responsive Material and Interfacial Properties through Remote Control of Polyelectrolyte-Surfactant Mixtures.

Polyelectrolyte/surfactant (P/S) mixtures find many applications but are static in nature and cannot be reversibly reconfigured through the application of external stimuli. Using a new type of photoswitchable surfactants, we use light to trigger property changes in mixtures of an anionic polyelectrolyte with a cationic photoswitch such as electrophoretic mobilities, particle size, as well as their interfacial structure and their ability to stabilize aqueous foam. For that, we show that prevailing hydrophobic intermolecular interactions can be remotely controlled between poly(sodium styrene sulfonate) (PSS) and arylazopyrazole tetraethylammonium bromide (AAP-TB). Shifting the chemical potential for P/S binding with E/Z photoisomerization of the surfactants can reversibly disintegrate even large aggregates (>4 µm) and is accompanied by a substantial change in the net charging state of PSS/AAP-TB complexes, e.g., from negative to positive excess charges upon light irradiation. In addition to the drastic changes in the bulk solution, also at air-water interfaces, the interfacial stoichiometry and structure change drastically on the molecular level with E/Z photoisomerization, which can also drive the stability of aqueous foam on a macroscopic level.

Polyelectrolyte/surfactant films: from 2D to 3D structural control.

Reversible control of the 3D structure of polyelectrolyte/surfactant films at the air/water interface is showcased. A recently discovered mechanism is exploited to form highly efficient, stable and biocompatible films by spreading aggregates composed of poly-L-lysine and sodium dodecyl sulfate on the surface of water. Reversible control of: (1) the surface monolayer coverage, (2) the switching on or off discrete extended structures, and (3) the extended structure coverage is demonstrated for the first time. The intricacy by which the film structures can be controlled is unprecedented and opens exciting potential to optimize film properties by chemical design for novel biomedical transfer applications.