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The indiscriminate use of pesticides makes us susceptible to the toxicity of these chemical compounds, which may be present in high quantities in our food. It is crucial to develop inexpensive and rapid methods for determining these pesticides for government control or even for the general population. In this study, we investigated the fabrication of self-assembled LbL films using multi-walled carbon nanotubes (MWCNT) and nickel tetrasulphonated phthalocyanine (NiTsPc) as an electrochemical sensor for the herbicide Diquat (DQ). The Layer-by-Layer (LbL) assembly of the (MWCNT/NiTsPc) film was examined, along with its structural and morphological characteristics. The effect of the number of layers in DQ detection was evaluated by cyclic voltammetry, followed by the detection through differential pulse voltammetry. The achieved limit of detection was 9.62 × 10-7 mol L-1. A ~ 30% decrease in sensitivity was observed in the presence of Paraquat, a banned herbicide and electrochemical interferent due to the structural similarities, which is regularly neglected in the most published studies. The sensor was tested in real samples, demonstrating a recovery of 98.5% in organic apples.

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Significance: Continuous-wave functional near-infrared spectroscopy has proved to be a valuable tool for assessing hemodynamic activity in the human brain in a non-invasively and inexpensive way. However, most of the current processing/analysis methods assume the head is a homogeneous medium, and hence do not appropriately correct for the signal coming from the scalp. This effect can be reduced by considering light propagation in a layered model of the human head, being the Monte Carlo (MC) simulations the gold standard to this end. However, this implies large computation times and demanding hardware capabilities. Aim: In this work, we study the feasibility of replacing the homogeneous model and the MC simulations by means of analytical multilayered models, combining in this way, the speed and simplicity of implementation of the former with the robustness and accuracy of the latter. Approach: Oxy- and deoxyhemoglobin (HbO and HbR, respectively) concentration changes were proposed in two different layers of a magnetic resonance imaging (MRI)-based meshed model of the human head, and then these changes were retrieved by means of (i) a typical homogeneous reconstruction and (ii) a theoretical layered reconstruction. Results: Results suggest that the use of analytical models of light propagation in layered models outperforms the results obtained using traditional homogeneous reconstruction algorithms, providing much more accurate results for both, the extra- and the cerebral tissues. We also compare the analytical layered reconstruction with MC-based reconstructions, achieving similar degrees of accuracy, especially in the gray matter layer, but much faster (between 4 and 5 orders of magnitude). Conclusions: We have successfully developed, implemented, and validated a method for retrieving chromophore concentration changes in the human brain, combining the simplicity and speed of the traditional homogeneous reconstruction algorithms with robustness and accuracy much more similar to those provided by MC simulations.

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In this communication luminescent bioconjugated human serum albumin nanostructures (HSA NPs) with tiny ultraluminescent gold core-shell silica nanoparticles (Au@SiO2-Fl) were designed with enhanced bi-coloured luminescence properties. The HSA NPs were obtained from Human Serum Albumin free (HSA free) through the desolvation method, and Au@SiO2-Fl, through modified Turkevich and Störber methods. In this manner, porous HSA Nanostructures of 150.0-200 nm and Au@SiO2-Fl 45.0 nm final diameters were obtained. Both methodologies and structures were conjugated to obtain modified Nanocomposites based on tiny gold cores of 15 nm surrounded with well spatial Nanostructured architectures of HSA (d15 Au@SiO2-Fl-HSA) that generated variable nanopatterns depending on the modified methodology of synthesis applied within colloidal dispersions. Therefore, three methodologies of non-covalent conjugation were developed. In optimal conditions, through Transmission Electronic Microscopy (TEM), well resolved multilayered nano-architectures with a size 190.0-200 nm in average with variable contrast depending of the focused nanomaterial within the nanocomposite were shown. Optimized nanoarchitecture was based on a template tiny gold core-shell surrounded by nanostructured HSA NPs (d15 Au@SiO2-Fl-HSA). In this manner, the NanoImaging generated by laser fluorescence microscopy permitted to record improved optical properties and functionalities, such as: (i) enhanced ultraluminescent d15 Au@SiO2-Fl-HSA composites in comparison to individual components based on Metal Enhanced Fluorescence (MEF); (ii) diminished photobleaching; (iii) higher dispersibility; (iv) higher resolution of single bright nano-emitters of 210.0 nm sizes; and (v) enhanced bi-coloured Bio-MEF coupling with potential non-classical light delivery towards other non-optical active biostructures for varied applications. The characterization of these nanocomposites allowed the comparison, evaluation and discussion focused on new properties generated and functionalities based on the incorporation of different types of tuneable materials. In this context, the biocompatibility, Cargo confined spaces, protein-based materials, optical transparent could be highlighted, as well as optical active materials. Thus, the potential applications of nanotechnology to both nanomedicine and nano-pharmaceutics were discussed.

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Seeking to improve personal armor equipment by providing mobility and resistance to penetration, this research aimed to explore the potential of sustainable materials in order to assess their ability in ballistic applications. Titica vine fibers (TVFs) extracted from aerial roots of Heteropsis flexuosa from the Amazon region were incorporated at 10, 20, 30, and 40 vol% into an epoxy matrix for applications in ballistic multilayered armor systems (MASs) and stand-alone tests for personal protection against high-velocity 7.62 mm ammunition. The back-face signature (BFS) depth measured for composites with 20 and 40 vol% TVFs used as an intermediate layer in MASs was 25.6 and 32.5 mm, respectively, and below the maximum limit of 44 mm set by the international standard. Fracture mechanisms found by scanning electron microscopy (SEM) attested the relevance of increasing the fiber content for applications in MASs. The results of stand-alone tests showed that the control (0 vol%) and samples with 20 vol% TVFs absorbed the highest impact energy (Eabs) (212-176 J), and consequently displayed limit velocity (VL) values (213-194 m/s), when compared with 40 vol% fiber composites. However, the macroscopic evaluation found that, referring to the control samples, the plain epoxy shattered completely. In addition, for 10 and 20 vol% TVFs, the composites were fragmented or exhibited delamination fractures, which compromised their physical integrity. On the other hand, composites with 30 and 40 vol% TVFs, whose Eabs and VL varied between 166-130 J and 189-167 m/s, respectively, showed the best physical stability. The SEM images indicated that for composites with 10 and 20 vol% TVFs, the fracture mode was predominantly brittle due to the greater participation of the epoxy resin and the discrete action of the fibers, while for composites with 30 and 40 vol% TVFs, there was activation of more complex mechanisms such as pullout, shearing, and fiber rupture. These results indicate that the TVF composite has great potential for use in bulletproof vests.

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Several clinical conditions leading to traumatic brain injury can cause hematomas or edemas inside the cerebral tissue. If these are not properly treated in time, they are prone to produce long-term neurological disabilities, or even death. Low-cost, portable and easy-to-handle devices are desired for continuous monitoring of these conditions and Near Infrared Spectroscopy (NIRS) techniques represent an appropriate choice. In this work, we use Time-Resolved (TR) Monte Carlo simulations to present a study of NIR light propagation over a digital MRI phantom. Healthy and injured (hematoma/edema) situations are considered. TR Diffuse Reflectance simulations for different lesion volumes and interoptode distances are performed in the frontal area and the left parietal area. Results show that mean partial pathlengths, photon measurement density functions and time dependent contrasts are sensitive to the presence of lesions, allowing their detection mainly for intermediate optodes separations, which proves that these metrics represent robust means of diagnose and monitoring. Conventional Continuous Wave (CW) contrasts are also presented as a particular case of the time dependent ones, but they result less sensitive to the lesions, and have higher associated uncertainties.

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The Industrial Internet of Things (IIoT) is one of the most demanding IoT applications. The insertion of industries in the context of smart cities and other smart environments, allied with new communication technologies such as 5G, brings a new horizon of possibilities and new requirements. These requirements include low latency, the support of a massive quantity of devices and data, and the need to support horizontal communications between devices at the edge level. To make this feasible, it is necessary to establish an IIoT-to-cloud continuum distributing federated brokers across the infrastructure and providing scalability and interoperability. To attend this type of application, we present the Helix Multi-layered IoT platform and its operating modes. We report and discuss its real-world deployment in the Aveiro Tech City Living Lab in Aveiro, Portugal with functional and performance tests. We tested device-to-device communication across edge and core layers and also interconnected the infrastructure with one in São Paulo, Brazil, replicating the use of a global industry. The successful deployment validates the use of a Helix Multi-layered IoT platform as a suitable backend platform for IIoT applications capable of establishing the IIoT-to-cloud continuum. It also helps for the deployment of other applications in such a domain.

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Leishmania parasites are the causal agent of leishmaniasis, an endemic disease in more than 90 countries worldwide. Over the years, traditional approaches focused on the parasite when developing treatments against leishmaniasis. Despite numerous attempts, there is not yet a universal treatment, and those available have allowed for the appearance of resistance. Here, we propose and follow a host-directed approach that aims to overcome the current lack of treatment. Our approach identifies potential therapeutic targets in the host cell and proposes known drug interactions aiming to improve the immune response and to block the host machinery necessary for the survival of the parasite. We started analyzing transcription factor regulatory networks of macrophages infected with Leishmania major. Next, based on the regulatory dynamics of the infection and available gene expression profiles, we selected potential therapeutic target proteins. The function of these proteins was then analyzed following a multilayered network scheme in which we combined information on metabolic pathways with known drugs that have a direct connection with the activity carried out by these proteins. Using our approach, we were able to identify five host protein-coding gene products that are potential therapeutic targets for treating leishmaniasis. Moreover, from the 11 drugs known to interact with the function performed by these proteins, 3 have already been tested against this parasite, verifying in this way our novel methodology. More importantly, the remaining eight drugs previously employed to treat other diseases, remain as promising yet-untested antileishmanial therapies. IMPORTANCE This work opens a new path to fight parasites by targeting host molecular functions by repurposing available and approved drugs. We created a novel approach to identify key proteins involved in any biological process by combining gene regulatory networks and expression profiles. Once proteins have been selected, our approach employs a multilayered network methodology that relates proteins to functions to drugs that alter these functions. By applying our novel approach to macrophages during the Leishmania infection process, we both validated our work and found eight drugs already approved for use in humans that to the best of our knowledge were never employed to treat leishmaniasis, rendering our work as a new tool in the box available to the scientific community fighting parasites.

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Multi-material and multilayered micro- and nanostructures are prominently featured in nature and engineering and are recognized by their remarkable properties. Unfortunately, the fabrication of micro- and nanostructured materials through conventional processes is challenging and costly. Herein, we introduce a high-throughput, continuous, and versatile strategy for the fabrication of polymer fibers with complex multilayered nanostructures. Chaotic electrospinning (ChE) is based on the coupling of continuous chaotic printing (CCP) and electrospinning, which produces fibers with an internal multi-material microstructure. When a CCP printhead is used as an electrospinning nozzle, the diameter of the fibers is further scaled down by 3 orders of magnitude while preserving their internal structure. ChE enables the use of various polymer inks for the creation of nanofibers with a customizable number of internal nanolayers. Our results showcase the versatility and tunability of ChE to fabricate multilayered structures at the nanoscale at high throughput. We apply ChE to the synthesis of unique carbon textile electrodes composed of nanofibers with striations carved into their surface at regular intervals. These striated carbon electrodes with high surface areas exhibit 3- to 4-fold increases in specific capacitance compared to regular carbon nanofibers; ChE holds great promise for the cost-effective fabrication of electrodes for supercapacitors and other applications.

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The main objective of the present work was to design a biomimetic free-standing multilayered PEM film, constructed by the layer-by-layer (LbL) assembly approach, based on natural biopolymers and intended to recreate the complex mucus-mimetic matrices in order to provide mechanistic insights into biophysical interactions between drugs and the physiological gel-forming mucin network of mucus that covers the mucosal epithelia named as(CS/ALG)/(PGM) PEM film. The obtained results indicate that mucin may delay or increase drug precipitation on the mucus layer, depending on specific drug-mucin interactions driving drug supersaturation or drug crystallization phenomena. It was found that the drug lipophilicity characteristics governed the mucin binding degree, which had an influencing role on the drug translocation across this gel-like hydrogel. Moreover, the ionization of these drugs did not have a significant role on the drug binding ability to mucin as much as the lipophilicity properties did. The (CS/ALG)/(PGM) PEM film may be a promising tool to routine testing drug-mucus interactions to evaluate biophysical interactions between this protective barrier of the organism against different drug therapeutic products or external aggressive agents, leading to the optimization of drug delivery products or drugs for particular disease states.

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Multilayered armor systems (MAS) with a front ceramic layer backed by a relatively unknown Amazonian guaruman fiber-reinforced (Ischnosiphon koem) epoxy composites, as second layer, were for the first time ballistic tested against the threat of 7.62 mm rifle ammunition. The amount of 30 vol% guaruman fibers was investigated in three distinct configurations: (i) continuous aligned, (ii) 0-90° cross-laid, and (iii) short-cut randomly dispersed. Additionally, single-target ballistic tests were also carried out in the best MAS-performed composite with cross-laid guaruman fibers against .22 caliber ammunition. The results disclosed that all composites as MAS second layer attended the US NIJ standard with corresponding penetration depth of (i) 32.9, (ii) 27.5, and (iii) 29.6 mm smaller than the lethal limit of 44 mm in a clay witness simulating a personal body. However, the continuous aligned guaruman fiber composite lost structural integrity by delamination after the 7.62 projectile impact. By contrast, the composite with cross-laid guaruman fibers kept its integrity for subsequent shootings as recommended by the standard. The single-target tests indicated a relatively higher limit velocity for .22 caliber projectile perforation, 255 m/s, and absorbed energy of 106 J for the cross-laid guaruman fibers, which are superior to corresponding results for other less known natural fiber epoxy composites.

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Piezoelectric nanogenerators can convert energy from ambient vibrations into electrical energy. In the future, these nanogenerators could substitute conventional electrochemical batteries to supply electrical energy to consumer electronics. The optimal design of nanogenerators is fundamental in order to achieve their best electromechanical behavior. We present the analytical electromechanical modeling of a vibration-based piezoelectric nanogenerator composed of a double-clamped beam with five multilayered cross-sections. This nanogenerator design has a central seismic mass (910 µm thickness) and substrate (125 µm thickness) of polyethylene terephthalate (PET) as well as a zinc oxide film (100 nm thickness) at the bottom of each end. The zinc oxide (ZnO) films have two aluminum electrodes (100 nm thickness) through which the generated electrical energy is extracted. The analytical electromechanical modeling is based on the Rayleigh method, Euler-Bernoulli beam theory and Macaulay method. In addition, finite element method (FEM) models are developed to estimate the electromechanical behavior of the nanogenerator. These FEM models consider air damping at atmospheric pressure and optimum load resistance. The analytical modeling results agree well with respect to those of FEM models. For applications under accelerations in y-direction of 2.50 m/s2 and an optimal load resistance of 32,458 Ω, the maximum output power and output power density of the nanogenerator at resonance (119.9 Hz) are 50.44 µW and 82.36 W/m3, respectively. This nanogenerator could be used to convert the ambient mechanical vibrations into electrical energy and supply low-power consumption devices.

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The Tubarão aquifer system constitutes a very complex, multilayered aquifer enclosed in the Paraná basin (central-southern part of Brazil). Despite the relatively low productivity of wells, groundwater represents an important source of water for the very populated and industrialized zones of the State of São Paulo. An extensive water sampling campaign was carried out followed by hydrochemical and isotopic (δ 2H, δ 18O, δ 13C and 14C) studies, aiming at a better understanding of the aquifer's geochemical evolution, recharge processes, and its groundwater residence times. Two main hydrochemical facies were recognized and divide the aquifer in two portions. The shallow portion - the active hydrological zone of the aquifer - is characterized by the Ca-HCO3 water type, evolving as a system open to atmospheric CO2. Mean residence times are typically lower than 5000 years. The lower portion is mostly characterized by the stagnant, Na-HCO3 water type, evolving under closed system conditions. Residence times average up to 15,000 years, but can reach 44,000 years, which indicates the exploitation of (possibly non-renewable) fossil waters. This study contributes to the establishment of proper policies regarding the sustainable groundwater exploitation of the Tubarão aquifer system.

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This work proposes a numerical procedure to simulate and optimize the thermal response of a multilayered wallboard system for building envelopes, where each layer can be possibly made of Phase Change Materials (PCM)-based composites to take advantage of their Thermal-Energy Storage (TES) capacity. The simulation step consists in solving the transient heat conduction equation across the whole wallboard using the enthalpy-based finite element method. The weather is described in detail by the Typical Meteorological Year (TMY) of the building location. Taking the TMY as well as the wall azimuth as inputs, EnergyPlusTM is used to define the convective boundary conditions at the external surface of the wall. For each layer, the material is chosen from a predefined vade mecum, including several PCM-based composites developed at the Institut für Werkstoffe im Bauwesen of TU Darmstadt together with standard insulating materials (i.e., EPS or Rockwool). Finally, the optimization step consists in using genetic algorithms to determine the stacking sequence of materials across the wallboard to minimize the undesired heat loads. The current simulation-based optimization procedure is applied to the design of envelopes for minimal undesired heat losses and gains in two locations with considerably different weather conditions, viz. Sauce Viejo in Argentina and Frankfurt in Germany. In general, for each location and all the considered orientations (north, east, south and west), optimal results consist of EPS walls containing a thin layer made of the PCM-based composite with highest TES capacity, placed near the middle of the wall and closer to the internal surface.

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BACKGROUND: Microcapsules fabricated using layer-by-layer self-assembly have unique properties, making them attractive for drug delivery applications. The technique has been improved, allowing the deposition of multiple layers of oppositely charged polyelectrolytes on spherical, colloidal templates. These templates can be decomposed by coating multiple layers, resulting in hollow shells. In this paper, we describe a novel drug delivery system for loading photosensitizer drugs into hollow multilayered microcapsules for photoprocess applications. METHODS: Manganese carbonate particles were prepared by mixing NH4HCO3 and MnSO4 and performing consecutive polyelectrolyte adsorption processes onto these templates using poly-(sodium 4-styrene sulfonate) and poly-(allylamine hydrocholoride). A photosensitizer was also incorporated into the layers. Hollow spheres were fabricated by removing the cores in the acidic solution. The hollow, multilayered microcapsules were studied by scanning electron microscopy, steady-state, and time-resolved techniques. Their biological activity was evaluated in vitro with cancer cells using a conventional MTT assay. RESULTS: The synthesized CaCO3 microparticles were uniform, non-aggregated, and highly porous spheres. The phthalocyanine derivatives loaded in the microcapsules maintained their photophysical behaviour after encapsulation. The spectroscopic results presented here showed excellent photophysical behaviour of the studied drug. We observed a desirable increase in singlet oxygen production, which is favourable for the PDT protocol. Cell viability after treatment was determined and the proposed microcapsules caused 80% cell death compared to the control. CONCLUSIONS: The results demonstrate that photosensitizer adsorption into the CaCO3 microparticle voids together with the layer-by-layer assembly of biopolymers provide a method for the fabrication of biocompatible microcapsules for use as biomaterials.

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The ballistic performance of plain woven jute fabric-reinforced polyester matrix composites was investigated as the second layer in a multilayered armor system (MAS). Volume fractions of jute fabric, up to 30 vol %, were mixed with orthophthalic polyester to fabricate laminate composites. Ballistic tests were conducted using high velocity 7.62 mm ammunition. The depth of penetration caused by the bullet in a block of clay witness, simulating a human body, was used to evaluate the MAS ballistic performance according to the international standard. The fractured materials after tests were analyzed by scanning electron microscopy (SEM). The results indicated that jute fabric composites present a performance similar to that of the much stronger Kevlar™, which is an aramid fabric laminate, as MAS second layer with the same thickness. The mechanism of this similar ballistic behavior as well as the comparative advantages of the jute fabric composites over the Kevlar™ are discussed.

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Multilayered microresonators commonly use sensitive coating or piezoelectric layers for detection of mass and gas. Most of these microresonators have a variable cross-section that complicates the prediction of their fundamental resonant frequency (generally of the bending mode) through conventional analytical models. In this paper, we present an analytical model to estimate the first resonant frequency and deflection curve of single-clamped multilayered microresonators with variable cross-section. The analytical model is obtained using the Rayleigh and Macaulay methods, as well as the Euler-Bernoulli beam theory. Our model is applied to two multilayered microresonators with piezoelectric excitation reported in the literature. Both microresonators are composed by layers of seven different materials. The results of our analytical model agree very well with those obtained from finite element models (FEMs) and experimental data. Our analytical model can be used to determine the suitable dimensions of the microresonator's layers in order to obtain a microresonator that operates at a resonant frequency necessary for a particular application.

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