Ferro- and ferrielectricity and negative piezoelectricity in thioamide-based supramolecular organic discotics.

Amide-based discotic supramolecular organic materials are of interest for fundamental understanding of cooperative self-assembly and collective dipole switching mechanisms as well as for practically relevant ferroelectric and piezoelectric properties. Here, we show how replacing amides (dipole moment of ∼3.5 D) with thioamides (∼5.1 D) as dipolar moieties in the archetypal C3-symmetric discotic molecule BTA leads to ferroelectric materials with a higher remnant polarization and lower coercive field. The thioamide-based materials also demonstrate a rare negative piezoelectricity and a previously predicted, yet never experimentally observed, polarization reversal via asymmetric intermediate states, that is, ferrielectric switching.

Energy efficiency in wastewater treatment plants: A framework for benchmarking method selection and application.

Utilities produce and store vast amount of data related to urban wastewater management. Not yet fully exploited, proper data analysis would provide relevant process information and represents a great opportunity to improve the process performance. In the last years, several statistical tools and benchmarking methods that can extract useful information from data have been described to analyse wastewater treatment plant (WWTP) energy efficiency. Improving energy efficiency at WWTPs is however a complex task which involves several actors (both internal and external to the water utility), requires an exchange of different types of information which can be analysed by a broad selection of methods. Benchmarking method therefore must not only be selected based on whether they provide a clear identification of inefficient processes; it must also match the available data and the skills of those performing the assessment and objectives of stakeholders interpreting the results. Here, we have identified the requirements of the most common benchmarking methods in terms of data, resources, complexity of use, and information provided. To do that, inefficiency is decomposed so that the analyst, considering the objective of the study and the available data, can link each element to the appropriate method for quantification and benchmarking, and relate inefficiency components with root-causes in wastewater treatment. Finally, a framework for selecting the most suitable benchmarking method to improve energy efficiency in WWTPs is proposed to assist water sector stakeholders. By offering guidelines on how integrates and links data, methods and actors in the water sector, the outcomes of this article are expected to move WWTPs towards increasing energy efficiency.

Climate- and fire-smart landscape scenarios call for redesigning protection regimes to achieve multiple management goals.

Integrated management of biodiversity and ecosystem services (ES) in heterogeneous landscapes requires considering the potential trade-offs between conflicting objectives. The UNESCO's Biosphere Reserve zoning scheme is a suitable context to address these trade-offs by considering multiple management zones that aim to minimise conflicts between management objectives. Moreover, in Mediterranean ecosystems, management and planning also needs to consider drivers of landscape dynamics such as wildfires and traditional farming and forestry practices that have historically shaped landscapes and the biodiversity they host. In this study, we applied a conservation planning approach to prioritise the allocation of management zones under future landscape and climate scenarios. We tested different landscape management scenarios reflecting the outcomes of climate-smart and fire-smart policies. We projected the expected landscape dynamics and associated changes on the distribution of 207 vertebrate species, 4 ES and fire hazard under each scenario. We used Marxan with Zones to allocate three management zones, replicating the Biosphere Reserves zoning scheme ("Core area", "Buffer zone" and "Transition area") to address the various management objectives within the Biosphere Reserve. Our results show that to promote ES supply and biodiversity conservation, while also minimising fire hazard, the reserve will need to: i) Redefine its zoning, especially regarding Core Areas, which need a considerable expansion to help mitigate changes in biodiversity and accommodate ES supply under expected changes in climate and species distribution. ii) Revisit current management policies that will result in encroached landscapes prone to high intensity, uncontrollable wildfires with the potential to heavily damage ecosystems and compromise the supply of ES. Our results support that both climate- and fire-smart policies in the Meseta Ibérica can help develop multifunctional landscapes that help mitigate and adapt to climate change and ensure the best possible maintenance of biodiversity and ES supply under uncertain future climate conditions.

Unveiling Polymerization Mechanism in pH-regulated Supramolecular Fibers in Aqueous Media.

An amine functionalized C3 -symmetric benzotrithiophene (BTT) monomer has been designed and synthetized in order to form pH responsive one-dimensional supramolecular polymers in aqueous media. While most of the reported studies looked at the effect of pH on the size of the aggregates, herein, a detailed mechanistic study is reported, carried out upon modifying the pH to trigger the formation of positively charged ammonium groups. A dramatic and reversible change in the polymerization mechanism and size of the supramolecular fibers is observed and ascribed to the combination of Coulombic repulsive forces and higher monomer solubility. Furthermore, the induced frustrated growth of the fibers is further employed to finely control the one-dimensional supramolecular polymerisation and copolymerization processes.

Transforming data to information: A parallel hybrid model for real-time state estimation in lignocellulosic ethanol fermentation.

Operating lignocellulosic fermentation processes to produce fuels and chemicals is challenging due to the inherent complexity and variability of the fermentation media. Real-time monitoring is necessary to compensate for these challenges, but the traditional process monitoring methods fail to deliver actionable information that can be used to implement advanced control strategies. In this study, a hybrid-modeling approach is presented to monitor cellulose-to-ethanol (EtOH) fermentations in real-time. The hybrid approach uses a continuous-discrete extended Kalman filter to reconciliate the predictions of a data-driven model and a kinetic model and to estimate the concentration of glucose (Glu), xylose (Xyl), and EtOH. The data-driven model is based on partial least squares (PLS) regression and predicts in real-time the concentration of Glu, Xyl, and EtOH from spectra collected with attenuated total reflectance mid-infrared spectroscopy. The estimations made by the hybrid approach, the data-driven models and the internal model were compared in two validation experiments showing that the hybrid model significantly outperformed the PLS and improved the predictions of the internal model. Furthermore, the hybrid model delivered consistent estimates even when disturbances in the measurements occurred, demonstrating the robustness of the method. The consistency of the proposed hybrid model opens the doors towards the implementation of advanced feedback control schemes.

Resource allocation explains lactic acid production in mixed-culture anaerobic fermentations.

Lactate production in anaerobic carbohydrate fermentations with mixed cultures of microorganisms is generally observed only in very specific conditions: the reactor should be run discontinuously and peptides and B vitamins must be present in the culture medium as lactic acid bacteria (LAB) are typically auxotrophic for amino acids. State-of-the-art anaerobic fermentation models assume that microorganisms optimise the adenosine triphosphate (ATP) yield on substrate and therefore they do not predict the less ATP efficient lactate production, which limits their application for designing lactate production in mixed-culture fermentations. In this study, a metabolic model taking into account cellular resource allocation and limitation is proposed to predict and analyse under which conditions lactate production from glucose can be beneficial for microorganisms. The model uses a flux balances analysis approach incorporating additional constraints from the resource allocation theory and simulates glucose fermentation in a continuous reactor. This approach predicts lactate production is predicted at high dilution rates, provided that amino acids are in the culture medium. In minimal medium and lower dilution rates, mostly butyrate and no lactate is predicted. Auxotrophy for amino acids of LAB is identified to provide a competitive advantage in rich media because less resources need to be allocated for anabolic machinery and higher specific growth rates can be achieved. The Matlab™ codes required for performing the simulations presented in this study are available at https://doi.org/10.5281/zenodo.4031144.

Metabolic modeling for predicting VFA production from protein-rich substrates by mixed-culture fermentation.

Proteinaceous organic wastes are suitable substrates to produce high added-value products in anaerobic mixed-culture fermentations. In these processes, the stoichiometry of the biotransformation depends highly on operational conditions such as pH or feeding characteristics and there are still no tools that allow the process to be directed toward those products of interest. Indeed, the lack of product selectivity strongly limits the potential industrial development of these bioprocesses. In this work, we developed a mathematical metabolic model for the production of volatile fatty acids from protein-rich wastes. In particular, the effect of pH on the product yields is analyzed and, for the first time, the observed changes are mechanistically explained. The model reproduces experimental results at both neutral and acidic pH and it is also capable of predicting the tendencies in product yields observed with a pH drop. It also offers mechanistic insights into the interaction among the different amino acids (AAs) of a particular protein and how an AA might yield different products depending on the relative abundance of other AAs. Particular emphasis is placed on the utility of this mathematical model as a process design tool and different examples are given on how to use the model for this purpose.

Ethyl alcohol threshold test: a fast, reliable and affordable olfactory Assessment tool for COVID-19 patients.

OBJECTIVE: COVID-19 patients may present mild symptoms. The identification of paucisymptomatic patients is paramount in order to interrupt the transmission chain of the virus. Olfactory loss could be one of those early symptoms which might help in the diagnosis of COVID-19 patients. In this study, we aim to develop and validate a fast, inexpensive, reliable and easy-to-perform olfactory test for the screening of suspected COVID-19 patients. STUDY DESIGN: Phase I was a case-control study and Phase II a transversal descriptive study. SUBJECTS AND METHODS: Olfaction was assessed with the ethyl alcohol threshold test and symptoms with visual analogue scales. The study was designed in two phases: In Phase I, we compared confirmed COVID-19 patients and healthy controls. In Phase II, patients with suspected COVID-19 infection referred for testing were studied. RESULTS: 275 participants were included in Phase I, 135 in Phase II. The ROC curve showed an AUC of 0.749 in Phase I, 0.737 in Phase II. The cutoff value which offered the highest amount of correctly classified patients was ≥ 2 (10% alcohol) for all age intervals. The odds ratio was 8.19 in Phase I, 6.56 in Phase II with a 75% sensitivity. When cases report normal sense of smell (VAS < 4), it misdiagnoses 57.89% of patients detected by the alcohol threshold test. CONCLUSION: The olfactory loss assessed with the alcohol threshold test has shown high sensitivity and odds ratio in both patients with confirmed COVID-19 illness and participants with suspected SARS-CoV-2 infection.

Assessment of sun-related behaviour, knowledge and attitudes among nursing students.

BACKGROUND: As future healthcare professionals, nursing students will play an important role in social training and promoting healthy behaviours including protection against sunlight. However, few studies to date have focused on their knowledge and attitudes regarding sun-related behaviour. OBJECTIVE: To evaluate the level of knowledge, attitudes and practices about sun protection and skin cancer among nursing students. METHODS: This cross-sectional study included 200 all year nursing students from University of Vigo, located in the Vigo, Ourense and Pontevedra campus. Participants completed a validated, self-reported questionnaire with 38 questions regarding their demographic characteristics, sun-related behaviour, knowledge and attitudes. RESULTS: Approximately 87% of students reported experiencing sunburn last summer and 57% stated that they had sunbathed more than 15 days. Participants showed low level of sun protection behaviours, with the exception of using sunscreen (86%) and wearing sunglasses (72.5%). Knowledge about skin cancer and sun protection was considered high (rate of correct responses 87.7%, 6.14 out of 7). Moreover, positive tanning attitudes were high in the sample overall. Nursing students awarded a high value to tanned skin and showed misconceptions about sun exposure. CONCLUSION: Although most of the students were aware of the side effects of sun exposure, their behaviours and attitudes were unsatisfactory. A high level of knowledge may not be predictive of positive practices and adequate attitudes, even among future healthcare professionals. Further guidance and educational campaigns are utmost important, particularly in a group that will be directly involved in prevention and early diagnosis of skin cancer.

Supramolecular Copolymers: Structure and Composition Revealed by Theoretical Modeling.

Supramolecular copolymers, non-covalent analogues of synthetic copolymers, constitute a new and promising class of polymers. In contrast to their covalent counterparts, the details of their mechanism of formation, as well as the factors determining their composition and length, are still poorly understood. Here, the supramolecular copolymerization between two slightly structurally different benzene-1,3,5-tricarboxamide (BTA) monomers functionalized with either oligodimethylsiloxane (oDMSi) or alkyl side chains is unraveled by combining experimental and theoretical approaches. By applying the "sergeant-and-soldiers" approach using circular dichroism (CD) experiments, we are able to obtain detailed insights into the structure and composition of these supramolecular copolymers. Moreover, we observe an unexpected chiral induction upon mixing two independently CD-silent solutions of the achiral (soldier) and chiral (sergeant) monomers. We find that the subtle differences in the chemical structure of the two monomers impact their homopolymerization mechanism: whereas alkyl-BTAs cooperatively self-assemble, oDMSi-BTAs self-assemble in an isodesmic manner. The effect of these mechanistic differences in the supramolecular copolymerization process is investigated as a function of the composition of the two monomers and explicitly rationalized by mathematical modeling. The results show that, at low fractions of oDMSi-BTA sergeants (<10 mol%), the polymerization process is cooperative and the supramolecular helicity is biased toward the helical preference of the sergeant. However, at higher fractions of oDMSi-BTA sergeant (>25 mol%), the isodesmic assembly of the increasing amounts of sergeant becomes more dominant, and different species start to coexist in the copolymerization process. The analysis of the experimental data with a newly developed theoretical model allows us to quantify the thermodynamic parameters, the distribution of different species, and the compositions and stack lengths of the formed supramolecular copolymers existing at various feed ratios of the two monomers.

Downstream mediators of Ten-m3 signalling in the developing visual pathway.

BACKGROUND: The formation of visuotopically-aligned projections in the brain is required for the generation of functional binocular circuits. The mechanisms which underlie this process are unknown. Ten-m3 is expressed in a broad high-ventral to low-dorsal gradient across the retina and in topographically-corresponding gradients in primary visual centres. Deletion of Ten-m3 causes profound disruption of binocular visual alignment and function. Surprisingly, one of the most apparent neuroanatomical changes-dramatic mismapping of ipsilateral, but not contralateral, retinal axons along the representation of the nasotemporal retinal axis-does not correlate well with Ten-m3's expression pattern, raising questions regarding mechanism. The aim of this study was to further our understanding of the molecular interactions which enable the formation of functional binocular visual circuits. METHODS: Anterograde tracing, gene expression studies and protein pull-down experiments were performed. Statistical significance was tested using a Kolmogorov-Smirnov test, pairwise-fixed random reallocation tests and univariate ANOVAs. RESULTS: We show that the ipsilateral retinal axons in Ten-m3 knockout mice are mismapped as a consequence of early axonal guidance defects. The aberrant invasion of the ventral-most region of the dorsal lateral geniculate nucleus by ipsilateral retinal axons in Ten-m3 knockouts suggested changes in the expression of other axonal guidance molecules, particularly members of the EphA-ephrinA family. We identified a consistent down-regulation of EphA7, but none of the other EphA-ephrinA genes tested, as well as an up-regulation of ipsilateral-determinants Zic2 and EphB1 in visual structures. We also found that Zic2 binds specifically to the intracellular domain of Ten-m3 in vitro. CONCLUSION: Our findings suggest that Zic2, EphB1 and EphA7 molecules may work as effectors of Ten-m3 signalling, acting together to enable the wiring of functional binocular visual circuits.

Modeling the Effect of Optical Signal Multipath.

Here, we propose a model to determine the effect of multipath in indoor environments when the shape and characteristics of the environment are known. The main paper goal is to model the multipath signal formation to solve, as much as possible, the negative effects in light communications, as well as the indoor positioning errors due to this phenomenon when using optical signals. The methodology followed was: analyze the multipath phenomenon, establish a theoretical approach and propose different models to characterize the behavior of the channel, emitter and receiver. The channel impulse response and received signal strength are obtained from different proposed algorithms. We also propose steps for implementing a numerical procedure to calculate the effects of these multipaths using information that characterizes the environment, transmitter and receiver and their corresponding positions. In addition, the results of an empirical test in a controlled environment are compared with those obtained using the model, in order to validate the latter. The results may largely vary with respect to the cell size used to discretize the environment. We have concluded that a cell size whose side is 20-times smaller than the minimum distance between emitter and receiver (i.e., 10 cm × 10 cm for a 2-m distance) provides almost identical results between the empirical tests and the proposed model, with an affordable computational load.

Indoor Positioning System Based on a PSD Detector, Precise Positioning of Agents in Motion Using AoA Techniques.

Here, we present an indoor positioning system (IPS) for detecting mobile agents based on a single Position Sensitive Device sensor (PSD) sited in the environment and InfraRed Emitter Diode (IRED) located on mobile agents. The main goal of the work is to develop an alternative IPS to other sensing technologies, cheaper, easier to install and with a low computational load to obtain a high rate of measurements per second. The proposed IPS has the capacity to accurately determine 3D position from the angle of arrival (AoA) of the signal received at the PSD sensor. In this first approach to the method, the agents are considered to move along a plane. We propose two alternatives for determining position: in one, tones are emitted on a frequency unique to each transmitter, while in the other, sequences are emitted.The paper proposes and set up a very simple and easy to deploy system capable of performing 3D positioning with a single analog sensor, obtaining a high accurate positioning and a reduced execution time for the signal processing. The low computational load of the IPS makes it possible to obtain a very high position update rate (more than 100 times per second), yielding millimetric accuracies.

Modeling Infrared Signal Reflections to Characterize Indoor Multipath Propagation.

In this paper, we propose a model to characterize Infrared (IR) signal reflections on any kind of surface material, together with a simplified procedure to compute the model parameters. The model works within the framework of Local Positioning Systems (LPS) based on IR signals (IR-LPS) to evaluate the behavior of transmitted signal Multipaths (MP), which are the main cause of error in IR-LPS, and makes several contributions to mitigation methods. Current methods are based on physics, optics, geometry and empirical methods, but these do not meet our requirements because of the need to apply several different restrictions and employ complex tools. We propose a simplified model based on only two reflection components, together with a method for determining the model parameters based on 12 empirical measurements that are easily performed in the real environment where the IR-LPS is being applied. Our experimental results show that the model provides a comprehensive solution to the real behavior of IR MP, yielding small errors when comparing real and modeled data (the mean error ranges from 1% to 4% depending on the environment surface materials). Other state-of-the-art methods yielded mean errors ranging from 15% to 40% in test measurements.

The Role of the Axial Substituent in Subphthalocyanine Acceptors for Bulk-Heterojunction Solar Cells.

Four hexachlorosubphthalocyanines SubPcCl6 -X bearing different axial substituents (X) have been synthesized for use as novel electron acceptors in solution-processed bulk-heterojunction organic solar cells. Subphthalocyanines are aromatic chromophoric molecules with cone-shaped structure, good solution processability, intense optical absorption in the visible spectral region, appropriate electron mobilities, and tunable energy levels. Solar cells with subphthalocyanines as the electron acceptor and PTB7-Th as the electron donor exhibit a power conversion efficiency up to 4 % and an external quantum efficiency approaching 60 % due to significant contributions from both the electron donor and the electron acceptor to the photocurrent, indicating a promising prospect of non-fullerene acceptors based on subphthalocyanines and structurally related systems.

A Versatile Method for the Preparation of Ferroelectric Supramolecular Materials via Radical End-Functionalization of Vinylidene Fluoride Oligomers.

A synthetic method for the end-functionalization of vinylidene fluoride oligomers (OVDF) via a radical reaction between terminal olefins and I-OVDF is described. The method shows a wide substrate scope and excellent conversions, and permits the preparation of different disc-shaped cores such as benzene-1,3,5-tricarboxamides (BTAs), perylenes bisimide (PBI), and phthalocyanines (Pc) bearing three to eight ferroelectric oligomers at their periphery. The formation, purity, OVDF conformation, and morphology of the final adducts has been assessed by a combination of techniques, such as NMR, size exclusion chromatography, differential scanning calorimetry, polarized optical microscopy, and atomic force microscopy. Finally, PBI-OVDF and Pc-OVDF materials show ferroelectric hysteresis behavior together with high remnant polarizations, with values as high as Pr ≈ 37 mC/m(2) for Pc-OVDF. This work demonstrates the potential of preparing a new set of ferroelectric materials simply by attaching OVDF oligomers to different small molecules. The use of carefully chosen small molecules paves the way to new functional materials in which ferroelectricity and electrical conductivity or light-harvesting properties coexist in a single compound.

Making the invisible visible: improved electrospray ion formation of metalloporphyrins/-phthalocyanines by attachment of the formate anion (HCOO(-)).

A protocol is developed for the coordination of the formate anion (HCOO(-)) to neutral metalloporphyrins (Pors) and -phthalocyanines (Pcs) containing divalent metals as a means to improve their ion formation in electrospray ionization (ESI). This method is particularly useful when the oxidation of the neutral metallomacrocycle fails. While focusing on Zn(II)Pors and Zn(II)Pcs, we show that formate is also readily attached to Mn(II), Mg(II) and Co(II)Pcs. However, for the Co(II)Pc secondary reactions can be observed. Upon collision-induced dissociation (CID), Zn(II)Por/Pc·formate supramolecular complexes can undergo the loss of CO2 in combination with transfer of a hydride anion (H(-)) to the zinc metal center. Further dissociation leads to electron transfer and hydrogen atom loss, generating a route to the radical anion of the Zn(II)Por/Pc without the need for electrochemical reduction, although the Zn(II)Por/Pc may have a too low electron affinity to allow electron transfer directly from the formate anion. In addition to single Por molecules, multi Por arrays were successfully analyzed by this method. In this case, multiple addition of formate occurs, giving rise to multiply charged species. In these multi Por arrays, complexation of the formate anion occurs by two surrounding Por units (sandwich). Therefore, the maximum attainment of formate anions in these arrays corresponds to the number of such sandwich complexes rather than the number of porphyrin moieties. The same bonding motif leads to dimers of the composition [(Zn(II)Por/Pc)2·HCOO](-). In these, the formate anion can act as a structural probe, allowing the distinction of isomeric ions with the formate bridging two macrocycles or being attached to a dimer of directly connected macrocycles.

Nanopatterned superlattices in self-assembled C2 -symmetric oligodimethylsiloxane-based benzene-1,3,5-tricarboxamides.

The synthesis of C3 - and C2 -symmetric benzene-1,3,5-tricarboxamides (BTAs) containing well-defined oligodimethylsiloxane (oDMS) and/or alkyl side chains has been carried out. The influence of the bulkiness of the oDMS chains in the aggregation behavior of dilute solutions of the oDMS-BTAs in methylcyclohexane was studied by temperature-dependent UV spectroscopy. The formation of hierarchically self-assembled aggregates was observed at different BTA concentrations, the tendency of aggregation increases by shortening or removing oDMS chains. Chiral BTAs were investigated with circular dichroism (CD) spectroscopy, showing a stronger tendency to aggregate than the achiral ones. Majority rules experiments show a linear behavior consistent with the existence of a high mismatch penalty energy. The most efficient oDMS-BTAs organogelators have the ability to form stable organogels at 5 mg mL(-1) (0.75 wt %) in hexane. Solid-state characterization techniques indicate the formation of an intermolecular threefold hydrogen bonding between adjacent molecules forming thermotropic liquid crystals, exhibiting a hexagonal columnar organization from room temperature to above 150 °C. A decrease of the clearing temperatures was observed when increasing the number and length of the oligodimethylsiloxane chains. In addition to the three-fold hydrogen bonding that leads to columnar liquid crystalline phase, segregation between the oDMS and aliphatic chains takes place in the BTA functionalized with two alkyl and one oDMS chain leading to a superlattice within the hexagonal structure with potential applications in lithography.

A generic methodology for the optimisation of sewer systems using stochastic programming and self-optimizing control.

The design of sewer system control is a complex task given the large size of the sewer networks, the transient dynamics of the water flow and the stochastic nature of rainfall. This contribution presents a generic methodology for the design of a self-optimising controller in sewer systems. Such controller is aimed at keeping the system close to the optimal performance, thanks to an optimal selection of controlled variables. The definition of an optimal performance was carried out by a two-stage optimisation (stochastic and deterministic) to take into account both the overflow during the current rain event as well as the expected overflow given the probability of a future rain event. The methodology is successfully applied to design an optimising control strategy for a subcatchment area in Copenhagen. The results are promising and expected to contribute to the advance of the operation and control problem of sewer systems.

Biobased short chain fatty acid production - Exploring microbial community dynamics and metabolic networks through kinetic and microbial modeling approaches.

In recent years, there has been growing interest in harnessing anaerobic digestion technology for resource recovery from waste streams. This approach has evolved beyond its traditional role in energy generation to encompass the production of valuable carboxylic acids, especially volatile fatty acids (VFAs) like acetic acid, propionic acid, and butyric acid. VFAs hold great potential for various industries and biobased applications due to their versatile properties. Despite increasing global demand, over 90% of VFAs are currently produced synthetically from petrochemicals. Realizing the potential of large-scale biobased VFA production from waste streams offers significant eco-friendly opportunities but comes with several key challenges. These include low VFA production yields, unstable acid compositions, complex and expensive purification methods, and post-processing needs. Among these, production yield and acid composition stand out as the most critical obstacles impacting economic viability and competitiveness. This paper seeks to offer a comprehensive view of combining complementary modeling approaches, including kinetic and microbial modeling, to understand the workings of microbial communities and metabolic pathways in VFA production, enhance production efficiency, and regulate acid profiles through the integration of omics and bioreactor data.