Migration of silver nanoparticles from plastic materials, with antimicrobial action, destined for food contact.

Five materials with antimicrobial function, by adding silver, were investigated to evaluate total silver concentration in the polymers and migration of silver nanoparticles from the materials in contact with food. The migration test was carried out by contacting plastic material with food simulant. Migration concentrations and average silver particle sizes were determined by mass spectrometry with inductively coupled plasma, performed in single particle mode (spICP-MS). Additionally, silver particles size and shape were characterized by scanning electron microscopy (SEM) with chemical identification by energy-dispersive X-ray spectroscopy (EDS). Most of samples showed detectable total silver concentrations and all samples showed migration of silver nanoparticles, with concentrations found between 0.00433 and 1.35 ng kg-1. Indeed, the migration study indicated the presence of silver nanoparticles in all food simulants, with sizes bellow 95 nm. The average particle size determined for acetic acid was greater than that observed in the other simulants. In the images obtained by SEM/EDS also confirmed the presence of spherical silver nanoparticles, between 17 and 80 nm. The findings reported herein will aid the health area concerning of human health risk assessments, aiming at regulating this type of material from a food safety point of view.

Forwarding in Energy-Constrained Wireless Information Centric Networks.

Information Centric Networks (ICNs) have been considered one of the most promising candidates to overcome the disadvantages of host-centric architectures when applied to IoT networks, having the potential to address the challenges of a smart city. One of the foundations of a smart city is its sensory capacity, which is obtained through devices associated with the IoT concept. The more sensors spread out, the greater the ability to sense the city. However, such a scale demands high energy requirements and an effective improvement in the energy management is unavoidable. To improve the energy management, we are proposing an efficient forwarding scheme in energy-constrained wireless ICNs. To achieve this goal, we consider the type of devices, their internal energy and the network context, among other parameters. The proposed forwarding strategy extends and adapts concepts of ICNs, by means of packet domain analysis, neighbourhood evaluation and node sleeping and waking strategies. The proposed solution takes advantage of the neighbourhood to be aware of the moments to listen and forward packets in order to consistently address mobility, improving the quality of content delivery. The evaluation is performed by simulation with real datasets of urban mobility, one from the lagoon of "Ria de Aveiro" and the other from a vehicular network in the city of Porto. The results show that the proposed forwarding scheme resulted in significant improvements in network content availability, in the overall energy saving and, consequently, in the network lifetime.

Impact of nanoconfinement on acetylacetone Equilibria in Ordered Mesoporous Silicates.

Nanoconfinement is one of the most intriguing nanoscale effects and affects several physical and chemical properties of molecules and materials, including viscosity, reaction kinetics, and glass transition temperature. In this work, liquid nuclear magnetic resonance (NMR) was used to analyze the behavior of 2,4-pentadienone in ordered mesoporous materials with a pore diameter of between 3 and 10 nm. The liquid NMR results showed meaningful changes in the hydrogen chemical shift and the keto-enol chemical equilibrium, which were associated with the pore diameter, allowing the authors to observe the effects of nanoconfinement. An interesting phenomenon was observed where the chemical equilibria of 2,4-pentadienone confined in a mesoporous material with a pore diameter of 3.5 nm was similar to that obtained with free (bulk) 2,4-pentadienone in larger pore materials. Another interesting result was observed for the enthalpy and entropy of the tautomeric equilibria of 2,4-pentadienone confined in mesoporous materials with a 5.5 nm pore diameter being -7.9 kJ mol-1 and -15.9 J mol-1.K. These values are similar to those obtained by dimethyl sulfoxide. This phenomenon indicates the possible use of ordered mesoporous materials as a reaction substitute in organic solvents. It was further observed that while the values of enthalpy (ΔH) and entropy (ΔS) had been modified by confinement, the Gibbs free energy (ΔG) value remained closer to that observed in free (bulk) 2,4-pentadienone. It is expected that this study will help in understanding the effects of nanoconfinement and provide a simple method to employ NMR techniques to analyze these phenomena.

An Efficient and Secure Alert System for VANETs to Improve Crosswalks' Security in Smart Cities.

A key characteristic of Smart Cities is the ability to reduce conflicts between different agents coexisting in a dynamic system, such as the interaction between vehicles and pedestrians. This paper presents a system to augment the awareness of vehicle drivers regarding the presence of pedestrians in nearby crosswalks. The proposed system interconnects Road Side Units (RSUs), which are informed about the state of the crosswalks, and vehicles, in order to spread to vehicles, the information about the presence of pedestrians in crosswalks. To prevent false information spreading, RSUs sign the alert messages they broadcast and all vehicles can validate the signatures. This poses strong security requirements, such as non-repudiation of alert messages, as well as strong real-time requirements, such as minimum message validation delays among vehicles approaching a crosswalk of interest. To manage the signed alert messages, we are proposing Nimble Asymmetric Cryptography (NAC), which authenticates implicit broadcast messages. NAC minimizes the usage of asymmetric ciphers, which are fundamental to assure non-repudiation but increase performance penalties and uses hash chaining for source authentication of implicit messages.

A Multi-Technology Communication Platform for Urban Mobile Sensing.

A common concern in smart cities is the focus on sensing procedures to provide city-wide information to city managers and citizens. To meet the growing demands of smart cities, the network must provide the ability to handle a large number of mobile sensors/devices, with high heterogeneity and unpredictable mobility, by collecting and delivering the sensed information for future treatment. This work proposes a multi-wireless technology communication platform for opportunistic data gathering and data exchange with respect to smart cities. Through the implementation of a proprietary long-range (LoRa) network and an urban sensor network, our platform addresses the heterogeneity of Internet of Things (IoT) devices while conferring communications in an opportunistic manner, increasing the interoperability of our platform. It implements and evaluates a medium access communication (MAC) protocol for LoRa networks with multiple gateways. It also implements mobile Opportunistic VEhicular (mOVE), a delay-tolerant network (DTN)-based architecture to address the mobility dimension. The platform provides vehicle-to-everything (V2X) communication with support for highly reliable and actionable information flows. Moreover, taking into account the high mobility pattern that a smart city scenario presents, we propose and evaluate two forwarding strategies for the opportunistic sensor network.

Wurtzite Gallium Phosphide via Chemical Beam Epitaxy: Impurity-Related Luminescence vs Growth Conditions.

The metastable wurtzite crystal phase in gallium phosphide (WZ GaP) is a relatively new structure with little available information about its emission properties compared to the most stable zinc-blend phase. Here, the effect of growth conditions of WZ GaP nano- and microstructures obtained via chemical beam epitaxy on the optical properties was studied using power- and temperature-dependent photoluminescence (PL). We showed that the PL spectra are dominated by two strong broad emission bands at 1.68 and 1.88 eV and two relatively narrow peaks at 2.04 and 2.09 eV. The broad emissions are associated with the presence of carbon and a small number of extended crystal defects, respectively. For the sharp emissions, two main radiative recombination channels were observed with ionization energies estimated in the range of 50-80 meV and lower than 10 meV. No variation of the low-temperature PL spectra was observed for samples grown at different P precursor flows, while increasing Ga content enhanced the dominant broad emission at around 1.68 eV, suggesting that the group III organometallic precursor is the main source of impurities. Finally, Be-doped samples were grown, and their characteristic optical emission at 2.03 eV was identified. These results contribute to the understanding of impurity-related luminescence in hexagonal GaP, being useful for further crystal growth optimization required for the fabrication of optoelectronic devices.

Structural characterization and plasmonic properties of manganese oxide-coated gold nanorods.

The preparation of metal@(dielectric or semiconductor) core@shell hybrid materials have been shown promising for both SERS and SEF applications due to improved stability in the presence of ions and the adsorbate compared to non-covered metallic nanoparticles. However, fine control over the thickness of the covering layer is essential to maximize the intrinsic trade-off between the plasmonic enhancement and the chemical stability improvement. Here, the preparation of manganese dioxide ultrathin layers covered gold nanorods (AuNR@MnO2) with varying thicknesses of the MnO2 layer is reported, and the characterization and evaluation of the resulting materials as SERS and SEF substrate. The MnO2 layer over the AuNR was prepared by reducing potassium permanganate by sodium oxalate in a basic medium. The AuNR@MnO2 hybrid material was characterized by UV-Vis spectroscopy, transmission electron microscopy, X-ray powder diffraction, and cyclic voltammetry. It was studied the SEF effect of the cyanine dye IR-820 excited at 785 nm with high performance for several thicknesses of the MnO2 ultrathin film. The enhancement factor increased for thicker oxide layers. The SERS effect of the IR-820 dye excited at 633 nm showed the most significant enhancement factor for thinner layers. The seemly opposite behavior of the two plasmonic effects may be assigned to the distance dependence of the electromagnetic field generated in the AuNR, which results in decreasing SERS performance. For SEF, the thinner layers resulted in the Au nanoparticles' emission quenching, so a more significant distance was necessary to observe enhancement.

Unraveling structural and compositional information in 3D FinFET electronic devices.

Non-planar Fin Field Effect Transistors (FinFET) are already present in modern devices. The evolution from the well-established 2D planar technology to the design of 3D nanostructures rose new fabrication processes, but a technique capable of full characterization, particularly their dopant distribution, in a representative (high statistics) way is still lacking. Here we propose a methodology based on Medium Energy Ion Scattering (MEIS) to address this query, allowing structural and compositional quantification of advanced 3D FinFET devices with nanometer spatial resolution. When ions are backscattered, their energy losses unfold the chemistry of the different 3D compounds present in the structure. The FinFET periodicity generates oscillatory features as a function of backscattered ion energy and, in fact, these features allow a complete description of the device dimensions. Additionally, each measurement is performed over more than thousand structures, being highly representative in a statistical meaning. Finally, independent measurements using electron microscopy corroborate the proposed methodology.