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The aim of our study was to analyze circadian rhythm of the hematological profile of horses housed in a loose box and paddock during the different seasons (spring, summer, autumn, and winter). Blood samples were performed every 4 h for 48 consecutive hours. Red blood cells (RBCs), hemoglobin (HGB), hematocrit (HCT), white blood cells (WBCs), platelets (PLTs), and leukocyte subpopulations (neutrophils, basophils, eosinophils, lymphocytes, and monocytes) were analyzed, and, at the same time, environmental conditions were recorded. A statistically significant effect of housing conditions ( p < 0.0001) was observed on all hematological values except for WBC during winter and for neutrophils ( p < 0.0001) during spring and autumn. A statistically significant effect of season ( p < 0.0001) was found for RBC, HCT, and PLT and for all leukocyte cells ( p < 0.0001) except for basophils. The single Cosinor method revealed a daily rhythm of hematological parameters during spring in both groups, and a daily rhythm for lymphocytes and neutrophils was observed during spring and summer in horses kept in a loose box and during winter in horses housed in a paddock. Our results revealed that the response of the immune system is regulated by circadian physiology. Knowledge of the periodic temporal structure of mammals should be considered when evaluating animals' adaptation to temporizations imposed by the environment.

Polyester fibers are widely employed in a multitude of sectors and applications from the technical textiles to everyday life thanks to their durability, strength, and flexibility. Despite these advantages, polyester lacks in dyeability, adhesion of coating, hydrophilicity, and it is characterized by a low wettability respect to natural fibers. On this regard, beyond the harmful hydrophobic textile finishings of polyester fabrics containing fluorine-compounds, and in order to avoid pre-treatments, such as laser irradiation to improve their surface properties, research is moving towards the development of fluorine-free and safer coatings. In this work, the (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and various long alkyl-chain alkoxysilanes were employed for the fabrication in the presence of a catalyst of a water-based superhydrophobic finishing for polyester fabrics with a simple sol-gel, non-fluorinated, sustainable approach and the dip-pad-dry-cure method. The finished polyester fabrics surface properties were investigated by static and dynamic water repellency tests. Additionally, the resistance to common water-based liquids, abrasion resistance, moisture adsorption, and air permeability measurements were performed. Scanning electron microscopy was employed to examine the micro- and nano-morphology of the functionalized polyester fabrics surfaces. The obtained superhydrophobic finishings displayed high water-based stain resistance as well as good hydrophobicity after different cycles of abrasion., Competing Interests: The authors declare no conflict of interest.

Water quality and disposability are among the main challenges that governments and societies will outside during the next years due to their close relationship to population growth and urbanization and their direct influence on the environment and socio-economic development. Potable water suitable for human consumption is a key resource that, unfortunately, is strongly limited by anthropogenic pollution and climate change. In this regard, new groups of compounds, referred to as emerging contaminants, represent a risk to human health and living species; they have already been identified in water bodies as a result of increased industrialization. Pesticides, cosmetics, personal care products, pharmaceuticals, organic dyes, and other man-made chemicals indispensable for modern society are among the emerging pollutants of difficult remediation by traditional methods of wastewater treatment. However, the majority of the currently used waste management and remediation techniques require significant amounts of energy and chemicals, which can themselves be sources of secondary pollution. Therefore, this review reported newly advanced, efficient, and sustainable techniques and approaches for water purification. In particular, new advancements in sustainable membrane-based filtration technologies are discussed, together with their modification through a rational safe-by-design to modulate their hydrophilicity, porosity, surface characteristics, and adsorption performances. Thus, their preparation by the use of biopolymer-based gels is described, as well as their blending with functional cross-linkers or nanofillers or by advanced and innovative approaches, such as electrospinning.

Background and Aim: Healthy patellofemoral (PF) joint mechanics are critical to optimal knee joint function. Patella plays a vital role in distributing quadriceps load during the knee extension. Patellar tracking, not physiological tracking, causes an increase of strains in PF ligaments, peaks of localized stress of soft tissues and articular cartilage and bony parts, and knee pain; these problems lead to complications such as bone abnormalities and osteoarthritis. This research aimed to develop a Finite Element (FE) model to evaluate patellar instability due to the medial retinaculum asymmetric loading effect., Methods: A numerical model of the knee was obtained by matching nuclear magnetic resonance (MRI) for soft tissues and computerized tomography (CT) for bones, carried on a normal adult. Loading setup was chosen by using literature data. The intensity of the muscle forces was calculated by a static optimization taking into account ground reaction and knee flexion/extension during walking. The effect of patellar instability was obtained by gradually unbalancing this symmetry, one side was unloaded till 90 N, and the other loaded till 110 N., Results: Unbalanced forces of 10 N acting on the retinaculum alone can produce a real difference in displacements of about 7 mm, and an increment of about 44% on patellar contact forces., Conclusion: This research demonstrated how an unbalanced forces acting on the retinaculum can produce significant patellar instability. Patellar instability starts at 25-30° of the knee flexion angle but tends to appear at 15° when the unbalanced muscular loading conditions are acting., Competing Interests: None., (© 2022 Professor P K Surendran Memorial Education Foundation. Published by Elsevier B.V. All rights reserved.)

In the past few years, corrosion protection of metal materials has become a global challenge, due to its great economic importance. For this reason, various methods have been developed to inhibit the corrosion process, such as surface treatment approaches, by employing corrosion inhibitors through the deposition of opportunely designed functional coatings, employed to preserve from corrosion damages metallic substrates. Recently, among these techniques and in order to avoid the toxic chromate-based pre-treatment coatings, silane-based coatings and films loaded with organic and inorganic corrosion inhibitors have been widely used in corrosion mitigation water-based surface treatment. In this study, the synthetic approach was devoted to create an embedded, hosted, waterborne, and eco-friendly matrix, obtained by use of the sol-gel technique, through the reaction of functional alkoxysilane cross-linking precursors, namely (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and (3-aminopropyl)triethoxysilane (APTES), in the presence of graphene oxide (GO) intercalated with natural and non-toxic phytic acid (PA) molecules. As a matter of fact, all experimental results from FT-IR spectroscopy, UV-Vis analysis, and SEM confirmed that PA molecules were successfully decorated on GO. Furthermore, polarization measurements and a neutral salt spray test were used to evaluate the anticorrosive performance on aluminum and steel substrates, thus showing that the GO-PA nanofiller improved the barrier and corrosion protection properties of the developed functional silane-based coatings.

The textile-finishing industry, is one of the main sources of persistent organic pollutants in water; in this regard, it is necessary to develop and employ new sustainable approaches for fabric finishing and treatment. This research study shows the development of an efficient and eco-friendly procedure to form highly hydrophobic surfaces on cotton fabrics using different modified silica sols. In particular, the formation of highly hydrophobic surfaces on cotton fabrics was studied by using a two-step treatment procedure, i.e., first applying a hybrid silica sol obtained by hydrolysis and subsequent condensation of (3-Glycidyloxypropyl)trimethoxy silane with different alkyl(trialkoxy)silane under acid conditions, and then applying hydrolyzed hexadecyltrimethoxysilane on the treated fabrics to further improve the fabrics' hydrophobicity. The treated cotton fabrics showed excellent water repellency with a water contact angle above 150° under optimum treatment conditions. The cooperative action of rough surface structure due to the silica sol nanoparticles and the low surface energy caused by long-chain alkyl(trialkoxy)silane in the nanocomposite coating, combined with the expected roughness on microscale due to the fabrics and fiber structure, provided the treated cotton fabrics with excellent, almost super, hydrophobicity and water-based stain resistance in an eco-sustainable way.

In recent years thanks to the Internet of Things (IoT), the demand for the development of miniaturized and wearable sensors has skyrocketed. Among them, novel sensors for wearable medical devices are mostly needed. The aim of this review is to summarize the advancements in this field from current points of view, focusing on sensors embedded into textile fabrics. Indeed, they are portable, lightweight, and the best candidates for monitoring biometric parameters. The possibility of integrating chemical sensors into textiles has opened new markets in smart clothing. Many examples of these systems are represented by color-changing materials due to their capability of altering optical properties, including absorption, reflectance, and scattering, in response to different external stimuli (temperature, humidity, pH, or chemicals). With the goal of smart health monitoring, nanosized sol-gel precursors, bringing coupling agents into their chemical structure, were used to modify halochromic dyestuffs, both minimizing leaching from the treated surfaces and increasing photostability for the development of stimuli-responsive sensors. The literature about the sensing properties of functionalized halochromic azo dyestuffs applied to textile fabrics is reviewed to understand their potential for achieving remote monitoring of health parameters. Finally, challenges and future perspectives are discussed to envisage the developed strategies for the next generation of functionalized halochromic dyestuffs with biocompatible and real-time stimuli-responsive capabilities.

Biofouling has destructive effects on shipping and leisure vessels, thus producing severe problems for marine and naval sectors due to corrosion with consequent elevated fuel consumption and higher maintenance costs. The development of anti-fouling or fouling release coatings creates deterrent surfaces that prevent the initial settlement of microorganisms. In this regard, new silica-based materials were prepared using two alkoxysilane cross-linkers containing epoxy and amine groups (i.e., 3-Glycidyloxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane, respectively), in combination with two functional fluoro-silane (i.e., 3,3,3-trifluoropropyl-trimethoxysilane and glycidyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylether) featuring well-known hydro repellent and anti-corrosion properties. As a matter of fact, the co-condensation of alkoxysilane featuring epoxide and amine ends, also mixed with two opportune long chain and short chain perfluorosilane precursors, allows getting stable amphiphilic, non-toxic, fouling release coatings. The sol-gel mixtures on coated glass slides were fully characterized by FT-IR spectroscopy, while the morphology was studied by scanning electron microscopy (SEM), and atomic force microscopy (AFM). The fouling release properties were evaluated through tests on treated glass slides in different microbial suspensions in seawater-based mediums and in seawater natural microcosms. The developed fluorinated coatings show suitable antimicrobial activities and low adhesive properties; no biocidal effects were observed for the microorganisms (bacteria).

The need to ensure adequate antifouling protection of the hull in the naval sector led to the development of real painting cycles, which involve the spreading of three layers of polymeric material on the hull surface exposed to the marine environment, specifically defined as primer, tie coat and final topcoat. It is already well known that coatings based on suitable silanes provide an efficient and non-toxic approach for the hydrophobic and antifouling/fouling release treatment of surfaces. In the present work, functional hydrophobic hybrid silica-based coatings (topcoats) were developed by using sol-gel technology and deposited on surfaces with the "doctor blade" method. In particular, those organic silanes, featuring opportune functional groups such as long (either fluorinated) alkyl chains, have a notable influence on surface wettability as showed in this study. Furthermore, the hydrophobic behavior of this functionalized coating was improved by introducing an intermediate commercial tie-coat layer between the primer and the topcoat, in order to decrease the wettability (i.e., decreasing the surface energy with a matching increase in the contact angle, CA) and to therefore make such coatings ideal for the design and development of fouling release paints. The hereby synthesized coatings were characterized by optical microscopy, contact angle analysis and a mechanical pull-off test to measure the adhesive power of the coating against a metal substrate typically used in the nautical sector. Analysis to evaluate the bacterial adhesion and the formation of microbial biofilm were related in laboratory and simulation (microcosm) scales, and assessed by SEM analysis., Competing Interests: The authors declare no conflict of interest.

Thermoregulation is an important mechanism to ensure thermal homeostasis. In horses, different housing conditions could influence this mechanism by exposing animals to different microclimates. The circadian rhythm of body temperature is well known. For this reason, we wanted to investigate the daily rhythm of cutaneous (jugular, shoulder, inner thigh and croup) temperature in comparison to rectal temperature in athletic horses kept under two different housing conditions. Ten clinically healthy Italian Saddle horses were divided into two equal groups: the first group was housed in individual boxes, and the second group was kept in paddocks. In all horses, rectal and cutaneous temperature measurements were performed every 4 h for 48 consecutive hours during different seasons (spring, summer, autumn and winter), respectively, by means of digital and infrared thermometers. Ambient temperature, relative humidity and ventilation were recorded simultaneously. A general linear model (GLM) was applied to the recorded temperature values displaying a significant effect of season, time of day, site of recording and housing condition (p < 0.001). No statistical differences were found between the two days of monitoring (p = 0.49). A trigonometric statistical model (single cosinor method) was applied to investigate the circadian rhythm of rectal and cutaneous temperatures in the two different groups. Our results showed circadian rhythmicity of rectal temperature during all seasons and in both groups. Cutaneous temperature shows daily rhythmicity that was different in the various regions and was influenced by housing conditions and seasons. Application of GLM also showed a statistically significant effect of season and site of recording (p < 0.0001) on all circadian parameters and of management condition on amplitude and robustness (p < 0.0001). No statistical differences between the two days of monitoring were observed (p = 0.68). These findings are probably due to the animals' thermoregulatory mechanisms ensuring heat exchange between the body and the environment, and that was influenced by the microclimate. In particular, the microclimate influenced the thermodispersion disrupting the daily rhythmicity of some body regions, in horses kept in boxes. Only the temperate climatic conditions observed in summer guarantee the expression of the daily rhythmicity of all body surfaces in both management conditions. These results contribute to the knowledge of the mechanisms of homeostasis and control of body temperature in the athletic horse kept in different housing conditions, with a chronophysiological interpretation that completes the proper management of thermal well-being in horses., (© 2022. The Author(s) under exclusive licence to International Society of Biometeorology.)

In the last decades, new synthetic hybrid materials, with an inorganic and organic nature, have been developed to promote their application as protective coatings and/or structural consolidants for several substrates in the construction industry and cultural heritage field. In this context, the scientific community paid attention to geopolymers and their new hybrid functional derivatives to design and develop innovative and sustainable composites with better chemical resistance, durability and mechanical characteristics. This review offers an overview of the latest progress in geopolymer-based hybrid nanofunctional materials and their use to treat and restore cultural heritage, as well as their employment in the building and architectural engineering field. In addition, it discusses the influence of some parameters, such as the chemical and physical characteristics of the substrates, the dosage of the alkaline activator, and the curing treatment, which affect their synthesis and performance.

Relevant properties of gold nanoparticles, such as stability and biocompatibility, together with their peculiar optical and electronic behavior, make them excellent candidates for medical and biological applications. This review describes the different approaches to the synthesis, surface modification, and characterization of gold nanoparticles (AuNPs) related to increasing their stability and available features useful for employment as drug delivery systems or in hyperthermia and photothermal therapy. The synthetic methods reported span from the well-known Turkevich synthesis, reduction with NaBH 4 with or without citrate, seeding growth, ascorbic acid-based, green synthesis, and Brust-Schiffrin methods. Furthermore, the nanosized functionalization of the AuNP surface brought about the formation of self-assembled monolayers through the employment of polymer coatings as capping agents covalently bonded to the nanoparticles. The most common chemical-physical characterization techniques to determine the size, shape and surface coverage of AuNPs are described underlining the structure-activity correlation in the frame of their applications in the biomedical and biotechnology sectors.

Data here reported are connected with the research article "Benzyl Alcohol to Benzaldehyde Oxidation on MnO x Clusters: Unraveling Atomistic Features" Gueci et al. [1]. This work described and discussed structural and energetic results, calculated by Density Functional Theory (DFT). In order to get kinetic information, DFT results were refined by an original approach, which will be shortly described in the following article. The crossed analysis of experimental and computational energetic and kinetic data allowed to (i) reconstruct the complicated lattice that connects the primary and secondary mechanisms of the reaction and (ii) identify alternative process pathways capable of by-passing parasitic mechanisms, decreasing selectivity. On the other hand, the data here presented show what is the basic information necessary to obtain the modeling of a complex process of heterogeneous catalysis. Moreover, they can be used either to verify the validity of the discussion outlined in the original article Gueci et al. [1] or as a starting point to computationally explore alternative routes and the related kinetics of the same oxidation processes, in the aim to further optimize the corresponding experimental approach., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships which have, or could be perceived to have, influenced the work reported in this article., (© 2021 The Authors. Published by Elsevier Inc.)

This review presents current literature on different nanocomposite coatings and surface finishing for textiles, and in particular this study has focused on smart materials, drug-delivery systems, industrial, antifouling and nano/ultrafiltration membrane coatings. Each of these nanostructured coatings shows interesting properties for different fields of application. In this review, particular attention is paid to the synthesis and the consequent physico-chemical characteristics of each coating and, therefore, to the different parameters that influence the substrate deposition process. Several techniques used in the characterization of these surface finishing coatings were also described. In this review the sol-gel method for preparing stimuli-responsive coatings as smart sensor materials is described; polymers and nanoparticles sensitive to pH, temperature, phase, light and biomolecules are also treated; nanomaterials based on phosphorus, borates, hydroxy carbonates and silicones are used and described as flame-retardant coatings; organic/inorganic hybrid sol-gel coatings for industrial applications are illustrated; carbon nanotubes, metallic oxides and polymers are employed for nano/ultrafiltration membranes and antifouling coatings. Research institutes and industries have collaborated in the advancement of nanotechnology by optimizing conversion processes of conventional materials into coatings with new functionalities for intelligent applications.

Marine pollution due to spillage of hydrocarbons represents a well-known current environmental problem. In order to recover the otherwise wasted oils and to prevent pollution damage, polyurethane foams are considered suitable materials for their ability to separate oils from sea-water and for their reusability. In this work we studied polyurethane foams filled with carbon nanofibers, in varying amounts, aimed at enhancing the selectivity of the material towards the oils and at improving the mechanical durability of the foam. Polyurethane-based foams were experimentally characterized by morphological, surface, and mechanical analyses (optical microscopy observation, contact angle measurement, absorption test according to ASTM F726-99 standard and compression fatigue tests according to ISO 24999 standard). Results indicated an increase in hydrophobic behavior and a good oleophilic character of the composite sponges besides an improved selective absorption of the foam toward oils in mixed water/oil media. The optimal filler amount was found to be around 1 wt% for the homogeneous distribution inside the polymeric foam. Finally, the fatigue test results showed an improvement of the mechanical properties of the foam with the growing carbon filler amount.

The studied sensor consists of a microstrip interdigital capacitor covered by a gas sensing layer made of titanium dioxide (TiO 2 ). To explore the gas sensing properties of the developed sensor, oxygen detection is considered as a case study. The sensor is electrically characterized using the complex scattering parameters measured with a vector network analyzer (VNA). The experimental investigation is performed over a frequency range of 1.5 GHz to 2.9 GHz by placing the sensor inside a polytetrafluoroethylene (PTFE) test chamber with a binary gas mixture composed of oxygen and nitrogen. The frequency-dependent response of the sensor is investigated in detail and further modelled using an artificial neural network (ANN) approach. The proposed modelling procedure allows mimicking the measured sensor performance over the whole range of oxygen concentration, going from 0% to 100%, and predicting the behavior of the resonant frequencies that can be used as sensing parameters.

Cities are currently engaged through their urban policies in pushing people towards less environmentally impacting mobility modalities: therefore, cycling and walking are strongly promoted, especially by means of new and wider limited traffic and no-cars zones. In this paper, the effectiveness of the new smartphones and apps-based technologies in modifying the mobility behaviors of citizens towards more sustainable choices has been investigated. Specifically, the potential of a smartphone app, directly involving citizens by means of a game rewarding the most sustainable trips, has been tested on a university commuters' group. These latter, starting from their current mobility situation, were challenged by an enhanced scenario characterized by more restrictive and sustainable targets. Promising results have been obtained suggesting that game-based tools could be effectively used as urban policy interventions intended to obtain a more sustainable mobility., (© 2020 Published by Elsevier Ltd.)

The Internet of Things (IoT) refers to the interconnection of smart devices to collect data and make intelligent decisions. However, a lack of intrinsic security measures makes IoT vulnerable to privacy and security threats. With its "security by design," Blockchain (BC) can help in addressing major security requirements in IoT. BC capabilities like immutability, transparency, auditability, data encryption and operational resilience can help solve most architectural shortcomings of IoT. This article presents a comprehensive survey on BC and IoT integration. The objective of this paper is to analyze the current research trends on the usage of BC-related approaches and technologies in an IoT context. This paper presents the following novelties, with respect to related work: (i) it covers different application domains, organizing the available literature according to this categorization, (ii) it introduces two usage patterns, i.e., device manipulation and data management (open marketplace solution), and (iii) it reports on the development level of some of the presented solutions. We also analyze the main challenges faced by the research community in the smooth integration of BC and IoT, and point out the main open issues and future research directions. Last but not least, we also present a survey about novel uses of BC in the machine economy.

Objective: to assess the validity of the Direct Assessment of Functional Status (DAFS) performance-based functional scale for the staging of dementia severity by comparing it with established clinical, functional and cognitive scales., Patients and Methods: 93 consecutive Alzheimer's disease patients underwent DAFS. Socio-demographic variables, cognitive status (Mini-Mental State Examination; MMSE), global disease severity (Clinical Dementia Rating; CDR), disease duration, physical performance (Physical Performance Test, PPT) and functional status (as reported by the primary caregiver) were also recorded and basic (B) and instrumental (I) activities of daily living (ADL) assessed., Results: a significant correlation was found between DAFS and MMSE (Pearson's r = 0.60; P < 0.01), PPT (r = 0.54; P < 0.01) and CDR (Spearman correlation coefficient: -0.48; P < 0.01). A mild, significant correlation was found between DAFS score and daily function as reported by the primary caregiver (r = -0.30 for BADL and r = - 0.27 for IADL). On multiple regression analysis, only MMSE and PPT were independently associated with the DAFS score, explaining 56% of DAFS total variance. ADL scales did not independently contribute to DAFS variance. A multivariate regression model of the association of DAFS with CDR showed that the association was significant even after adjustment for MMSE and PET, suggesting that DAFS scores provide additional information on dementia severity., Conclusion: DAFS is a valid tool for the assessment of dementia severity, capturing cognitive and physical aspects of disability.