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The contribution to the energy barrier of a series of tethers in transannular cycloadditions of cycloalkenes with hydrazones has been computationally studied by using DFT. The Houk's distortion model has been employed to evaluate the influence of the tether in the cycloaddition reaction. That model has been extended to determine the contribution of each tether and, more importantly, the effect exerted between them. In addition to the distortion induced by the tethers, the entropy effects caused by them has also been studied. The analysis of the evolution of the electron localization function along the reaction revealed the highly concerted character of the reaction.

In developing nations, outdated technologies and sulfur-rich heavy fossil fuel usage are major contributors to air pollution, affecting urban air quality and public health. In addition, the limited resources hinder the adoption of advanced monitoring systems crucial for informed public health policies. This study addresses this challenge by introducing an affordable internet of things (IoT) monitoring system capable of tracking atmospheric pollutants and meteorological parameters. The IoT platform combines a Bresser 5-in-1 weather station with a previously developed air quality monitoring device equipped with Alphasense gas sensors. Utilizing MQTT, Node-RED, InfluxDB, and Grafana, a Raspberry Pi collects, processes, and visualizes the data it receives from the measuring device by LoRa. To validate system performance, a 15-day field campaign was conducted in Santa Clara, Cuba, using a Libelium Smart Environment Pro as a reference. The system, with a development cost several times lower than Libelium and measuring a greater number of variables, provided reliable data to address air quality issues and support health-related decision making, overcoming resource and budget constraints. The results showed that the IoT architecture has the capacity to process measurements in tropical conditions. The meteorological data provide deeper insights into events of poorer air quality.

The aim of IEEE Time-Sensitive Networking (TSN) standards is to grant deterministic communication in traditional Ethernet networks for Industry 4.0. Insofar as the use cases in the Factory need some mobility, the extension of the TSN capabilities over the fifth-generation (5G) cellular network is the next step. Some challenges in TSN over 5G, such as TSN translators time synchronization functionality, are well defined in the standards, even if they have not yet been addressed in the market. However other challenges, such as the dynamic configuration of the entire network (or part of the it) based on quality requirements of the current TSN traffic pattern, are defined at a very high level and delegated to vendors for implementation. This paper addresses this challenge, using an Automata Learning approach to monitor and reconfigure the end-to-end 5G QoS flow to keep the quality of a TSN session within the required values. Additionally, algorithms are provided to build the automata from network data and predict potential deviations of the requirements to meet the expected quality. Moreover, this work presents a functional TSN over a 5G testbed where the algorithms have been tested, demonstrating that the proposed solution achieves an improvement of around 40% compared to the usual operation of the network.

Very low latency and high reliability are two of the main requirements for new applications exploiting 5G networks. This is the case for the remote operation of robots or vehicles, the autonomous interaction of equipment in a factory, autonomous driving and tactile internet applications. Although the TCP/IP stack has been sufficient as the end-to-end solution for most of the history of the Internet, a number of surveys have appeared recently presenting many different methods for managing the end-to-end communication to meet the requirements of various technologies such as that of 5G networks. In this paper, we present a novel classification of the literature focused on new end-to-end solutions and the creation of services towards the support of low latency (1 ms) and high reliability (10-9 error rate) in current and future 5G networks. We specifically highlight how the proposals can be classified according to enabling technologies and the specific method used to achieve success in terms of the latency and reliability. The literature related to end-to-end solutions for reliable low-latency communications are organized according to three main topics: (i) end-to-end protocols that improve communication in terms of latency and reliability, (ii) functionality or technologies implemented on the network to support the current demands, and (iii) application programming interfaces that enhance the correct utilization of those protocols and additional technologies.

The ruthenium tetroxide-mediated oxidation of cyclopentane, tetrahydrofuran, tetrahydrothiophene and N-substituted pyrrolidines has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. In agreement with experimental observations and previous DFT calculations, the rate-limiting step of the reaction takes place through a highly asynchronous (3 + 2) concerted cycloaddition through a single transition structure (one kinetic step). The ELF analysis identifies the reaction as a typical one-step-two-stages process and corroborates the existence of a transient carbocation. In the case of pyrrolidines, the carbocation is completely stabilized as an energy minimum in the form of an iminium ion and the reaction takes place in two steps.

This article presents a dataset produced to investigate how data and information quality estimations enable to detect aNomalies and malicious acts in cyber-physical systems. Data were acquired making use of a cyber-physical subsystem consisting of liquid containers for fuel or water, along with its automated control and data acquisition infrastructure. Described data consist of temporal series representing five operational scenarios – Normal, aNomalies, breakdown, sabotages, and cyber-attacks – corresponding to 15 different real situations. The dataset is publicly available in the .zip file published with the article, to investigate and compare faulty operation detection and characterization methods for cyber-physical systems.

Abstract Background Pre-evaluation of endogenous immunoglobulin levels is a potential strategy to improve the results of intravenous immunoglobulins in sepsis, but more work has to be done to identify those patients who could benefit the most from this treatment. The objective of this study was to evaluate the impact of endogenous immunoglobulins on the mortality risk in sepsis depending on disease severity. Methods This was a retrospective observational study including 278 patients admitted to the ICU with sepsis fulfilling the SEPSIS-3 criteria, coming from the Spanish GRECIA and ABISS-EDUSEPSIS cohorts. Patients were distributed into two groups depending on their Sequential Organ Failure Assessment score at ICU admission (SOFA

This paper presents the extensions carried out in the Android measurement and monitoring tool TestelDroid, in order to support remote control and large-scale experimentation. The extensions includes support for Standard Commands for Programmable Instruments (SCPI), cOntrol and Management Framework (OMF) and OMFMeasurement Library (OML). SCPI is the most widespread interface for measurement equipment control in many areas, for example, electronics or telecommunications. On the other hand, the support of technologies like OMF and OML provides powerful orchestration framework languages which reduces the time required for dening experiments.

A library of C-alkyl and C-aryl nitrones has been obtained by direct condensation of primary N-substituted hydroxylamine hydrochlorides with various aldehydes and ketones without catalysts or base. The synthetic procedure, performed under MW irradiation in the absence of solvent, does not require the presence of a base, is fast, clean, high-yielding and characterized by simple work-up.

The high heterogeneity of 5G use cases requires the extension of the traditional per-component testing procedures provided by certification organizations, in order to devise and incorporate methodologies that cover the testing requirements from vertical applications and services. In this paper, we introduce an experimentation methodology that is defined in the context of the 5GENESIS project, which aims at enabling both the testing of network components and validation of E2E KPIs. The most important contributions of this methodology are its modularity and flexibility, as well as the open-source software that was developed for its application, which enable lightweight adoption of the methodology in any 5G testbed. We also demonstrate how the methodology can be used, by executing and analyzing different experiments in a 5G Non-Standalone (NSA) deployment at the University of Malaga. The key findings of the paper are an initial 5G performance assessment and KPI analysis and the detection of under-performance issues at the application level. Those findings highlight the need for reliable testing and validation procedures towards a fair benchmarking of generic 5G services and applications.

High-energy ball milling was carried out to disperse 3 vol% TiC nanoparticles (ex situ reinforcement) in a high-pressure inert gas-atomised prealloyed micron-sized 6005A Al alloy (AA6005A), with a Si/Mg atomic ratio of 1.32 powder matrix. Nanocomposite powders were consolidated by hot extrusion in strip shape at 500 °C, followed by a T6 ageing heat treatment. The microstructural features of the consolidated and precipitation hardening nanocomposites specimens were studied using X-ray diffractometry (DRX), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron backscatter diffraction (EBSD). The consolidated nanocomposites consisted of approximately equiaxed grains of different grain sizes with a high fraction of high-angle grain boundaries with average misorientation angles of approximately 35°. The nanocomposites showed remarkably higher hardness, Young’s modulus, yield, and ultimate strengths at room temperature than the extruded profiles of unreinforced milled AA6005A powders obtained through refinement of the Al alloy grain structure and a strong particle–matrix bonding, although with a drop in their ductility. The consolidated nanocomposite showed a weak response to industrial ageing heat treatment, as demonstrated by microstructural analyses and mechanical tests.

The behavior of mobile devices is highly non deterministic and barely predictable due to the interaction of the user with its applications. In consequence, analyzing the correctness of applications running on a smartphone involves dealing with the complexity of its environment. In this paper, we propose the use of model-based testing to describe the potential behaviors of users interacting with mobile applications. These behaviors are modeled by composing specially-designed state machines. These composed state machines can be exhaustively explored using a model checking tool to automatically generate all possible user interactions. Each generated trace model checker can be interpreted as a test case to drive a runtime analysis of actual applications. We have implemented a tool that follows the proposed methodology to analyze Android devices using the model checker Spin as the exhaustive generator of test cases.

Nucleobase-containing isoxazolidines spiro-bonded to an indane core have been synthesized in very good yields by regio- and diastereoselective 1,3-dipolar cycloaddition starting from indanyl nitrones and N-vinylnucleobases by using environmentally benign microwave technology. The contemporary presence of various structural groups that are individually active scaffolds of different typology of drugs, has directed us to speculate that these compounds may act as inhibitors of MDM2−p53 interaction. Therefore, both computational calculations and antiproliferative screening against A549 human lung adenocarcinoma cells and human SH-SY5Y neuroblastoma cells were carried out to support this hypothesis.

Pre-alloyed micron-sized 6005A Al alloy (AA 6005A) powders, with a Mg/Si atomic ratio of 0.75, obtained by high pressure inert gas atomization were consolidated by uniaxial cold pressing at 200 MPa into cylindrical Al containers and hot extruded at 450, 480 and 500 °C with an extrusion rate of 7:1, followed by artificial T6 precipitation hardening. Ageing conditions were varied between 170 °C and 190 °C and times of 6, 7 and 8 h. The microstructure of the extruded profiles was analysed using X-Ray diffractometry (XRD), light optical microscopy (LOM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Differential scanning calorimetry (DSC) was used to study the possible phase transformations. After our results, the peak-aging hardness condition was achieved at 180 °C for 6 h. Mechanical properties of the powder metallurgy (P/M) aluminium alloys consolidated by hot extrusion were superior to those of the extruded profiles of wrought alloy using conventional ingot metallurgy (I/M) billets. AA 6005A wrought P/M alloy via T6 heat treatment shown yield stress of 317 MPa and elongation of 21% at the extrusion pre-heating temperature of 500 °C.

The binding properties of quercetin toward chloride anions were investigated by means of 1H-NMR, 13C-NMR, and electrospray ionization mass spectrometry (ESI-MS) measurements, as well as computational calculations. The results indicate that quercetin behaves primarily as a ditopic receptor with the binding site of the B ring that exhibits stronger chloride affinity compared to the A ring. However, these sites are stronger receptors than those of catechol and resorcinol because of their conjugation with the carbonyl group located on the C ring. The 1:1 and 1:2 complexation of this flavonoid with Cl− was also supported by ESI mass spectrometry.

An efficient, eco-compatible, and very cheap method for the construction of triazoles via eliminative azide–olefin cycloaddition (EAOC) reaction has been developed by a catalytic system, IL/FeCl3, offering a highly regioselective approach to structurally diverse 1,5-disubstituted 1,2,3-triazoles in up to 95% yield. This strategy features the reuse of a catalytic system through simple operations. Mechanistic studies indicated that an asynchronous concerted dipolar cycloaddition–elimination process might be involved.

The 2-Aza-Cope rearrangement of γ-alkenyl nitrones is a rare example of the neutral thermal 2-aza-Cope process that usually takes place with cationic species. During the rearrangement, a redistribution of bonds and electronic density occurs in one kinetic step. However, the introduction of substituents with different steric requirements and electronic features might alter the activation energies and the synchronicity of the reaction. The electron localization function (ELF) analysis and its application to Bonding Evolution Theory (BET) analysis within the context of Molecular Electron Density Theory (MEDT) is an excellent tool to monitor the electron density along the reaction coordinate and thus investigate in detail bond breaking and formation and the corresponding energy barriers. By analyzing topological ELF calculations of seventeen 2-aza-Cope nitrone rearrangements with selected substituents, the main factors influencing the synchronicity of the process were investigated. This MEDT study results revealed that the rearrangement is a non-polar process mostly influenced by steric factors rather than by electronic ones, and confirms the pseudoradical character of the process rather than any pericyclic electron-reorganization.

The ZnBr2 complex of the title compound has been studied by both structural and theoretical methods. Similar reactivities have been observed for the nitrone alone and the complex in 1,3-dipolar cycloadditions and nucleophilic additions.

The 1,3-dipolar cycloaddition reaction of N-benzyl-C-(2-furyl)nitrones with electron-rich alkenes gives preferentially trans-substituted 3,5-disubstituted isoxazolidines (endo approach). These experimental results are in good qualitative agreement with the predicted ones by semiempirical (AM1 and PM3) and ab initio (HF/3-21G) methods.

Optically active nitrones derived from both aldoses and dialdoses add metallated heterocycles in a stereocontrolled way depending on the nature of the Lewis acid used as a precomplexing agent of the nitrone. Further elaborations of the resulting hydroxylamines lead to the development of new synthetic methodologies for the preparation of polyalkoxy α-amino aldehydes and α-amino acids. These compounds can be used as key advanced intermediates in the synthesis of a wide range of natural products and derivatives including amino sugars, aza sugars, and complex nucleosides.

We introduce a real-time experimentation testbed in this paper which enables more realistic analysis of quality of service (QoS) in LTE networks. This testbed is envisioned for the improvement of QoS and quality of experience (QoE) through the experimentation with real devices, services, and radio configurations. Radio configurations suggested in the literature typically arise from simulations; the testbed provides a real and controlled testing environment where such configurations can be validated. The added value of this testbed goes a long way not only in the provision of more realistic results but also in the provision of QoS and QoE cross-layer measurements through the correlation of information collected at different layers: from service and IP levels to radio and protocol parameters. Analyzing the interlayer dependencies will allow us to identify optimal settings for the radio access network and service parameters. This information can be used to suggest new cross-layer optimizations to further improve quality of experience of mobile subscribers. As a use case, we examine VoIP service over LTE, which is currently an open issue.

Protein O-fucosylation is an essential post-translational modification, involved in the folding of target proteins and in the role of these target proteins during embryonic development and adult tissue homeostasis, among other things. Two different enzymes are responsible for this modification, Protein O-fucosyltransferase 1 and 2 (POFUT1 and POFUT2, respectively). Both proteins have been characterised biologically and enzymatically but nothing is known at the molecular or structural level. Here we describe the first crystal structure of a catalytically functional POFUT1 in an apo-form and in complex with GDP-fucose and GDP. The enzyme belongs to the GT-B family and is not dependent on manganese for activity. GDP-fucose/GDP is localised in a conserved cavity connected to a large solvent exposed pocket, which we show is the binding site of epidermal growth factor (EGF) repeats in the extracellular domain of the Notch Receptor. Through both mutational and kinetic studies we have identified which residues are involved in binding and catalysis and have determined that the Arg240 residue is a key catalytic residue. We also propose a novel S(N)1-like catalytic mechanism with formation of an intimate ion pair, in which the glycosidic bond is cleaved before the nucleophilic attack; and theoretical calculations at a DFT (B3LYP/6-31+G(d,p) support this mechanism. Thus, the crystal structure together with our mutagenesis studies explain the molecular mechanism of POFUT1 and provide a new starting point for the design of functional inhibitors to this critical enzyme in the future.