Interoperable software platforms for introducing artificial intelligence components in manufacturing: A meta-framework for security and privacy.

The irruption of advanced technologies and the limited knowledge of software architectures are making it difficult for many small and medium-sized manufacturing companies to keep up with what is being called the fourth industrial revolution (Industry 4.0, Industry of the Future). Container orchestration platforms provide layers of simplification for key requirements such as interoperability, security, and privacy, and provide mechanisms that allow companies and technology providers to focus on their specific functionalities and goals, instead of investing considerable time and effort in the underlying platform on which the solution will operate. This article focuses on these platforms and the issues when developing them, and proposes a risk- and goal-oriented hybrid meta-framework for security and privacy analysis. The meta-framework uses well-known security and privacy standards and frameworks as a reference and can be used to understand assets and requirements and, in particular, to select and configure countermeasures. For practical evaluation of the meta-framework, it was applied to a real case. This case shows how the needs of the KITT4SME project platform were analyzed to support, among others, four manufacturing pilot cases and to define the key security and privacy features that should be introduced when implementing a software platform for easy uptake by small and medium enterprises.

Needs, Requirements and a Concept of a Tool Condition Monitoring System for the Aerospace Industry.

In this paper, we describe the needs and specific requirements of the aerospace industry in the field of metal machining; specifically, the concept of an edge-computing-based production supervision system for the aerospace industry using a tool and cutting process condition monitoring system. The new concept was developed based on experience gained during the implementation of research projects in Poland's Aviation Valley at aerospace plants such as Pratt & Whitney and Lockheed Martin. Commercial tool condition monitoring (TCM) and production monitoring systems do not effectively meet the requirements and specificity of the aerospace industry. The main objective of the system is real-time diagnostics and sharing of data, knowledge, and system configurations among technologists, line bosses, machine tool operators, and quality control. The concept presented in this paper is a special tool condition monitoring system comprising a three-stage (natural wear, accelerated wear, and catastrophic tool failure) set of diagnostic algorithms designed for short-run machining and aimed at protecting the workpiece from damage by a damaged or worn tool.

Self-Tuning Method for Increased Obstacle Detection Reliability Based on Internet of Things LiDAR Sensor Models.

On-chip LiDAR sensors for vehicle collision avoidance are a rapidly expanding area of research and development. The assessment of reliable obstacle detection using data collected by LiDAR sensors has become a key issue that the scientific community is actively exploring. The design of a self-tuning methodology and its implementation are presented in this paper, to maximize the reliability of LiDAR sensors network for obstacle detection in the 'Internet of Things' (IoT) mobility scenarios. The Webots Automobile 3D simulation tool for emulating sensor interaction in complex driving environments is selected in order to achieve that objective. Furthermore, a model-based framework is defined that employs a point-cloud clustering technique, and an error-based prediction model library that is composed of a multilayer perceptron neural network, and k-nearest neighbors and linear regression models. Finally, a reinforcement learning technique, specifically a Q-learning method, is implemented to determine the number of LiDAR sensors that are required to increase sensor reliability for obstacle localization tasks. In addition, a IoT driving assistance user scenario, connecting a five LiDAR sensor network is designed and implemented to validate the accuracy of the computational intelligence-based framework. The results demonstrated that the self-tuning method is an appropriate strategy to increase the reliability of the sensor network while minimizing detection thresholds.

Obstacle Recognition Based on Machine Learning for On-Chip LiDAR Sensors in a Cyber-Physical System.

Collision avoidance is an important feature in advanced driver-assistance systems, aimed at providing correct, timely and reliable warnings before an imminent collision (with objects, vehicles, pedestrians, etc.). The obstacle recognition library is designed and implemented to address the design and evaluation of obstacle detection in a transportation cyber-physical system. The library is integrated into a co-simulation framework that is supported on the interaction between SCANeR software and Matlab/Simulink. From the best of the authors' knowledge, two main contributions are reported in this paper. Firstly, the modelling and simulation of virtual on-chip light detection and ranging sensors in a cyber-physical system, for traffic scenarios, is presented. The cyber-physical system is designed and implemented in SCANeR. Secondly, three specific artificial intelligence-based methods for obstacle recognition libraries are also designed and applied using a sensory information database provided by SCANeR. The computational library has three methods for obstacle detection: a multi-layer perceptron neural network, a self-organization map and a support vector machine. Finally, a comparison among these methods under different weather conditions is presented, with very promising results in terms of accuracy. The best results are achieved using the multi-layer perceptron in sunny and foggy conditions, the support vector machine in rainy conditions and the self-organized map in snowy conditions.

Chiral recognition and atropisomerism in the sevoflurane dimer.

We have examined the stereoselectivity of molecular recognition between two molecules of the anesthetic sevoflurane using broadband rotational spectroscopy. The transient axial chirality of sevoflurane is revealed upon the formation of the dimer, as two different diastereoisomers made of either homo- or heterochiral species are detected in a supersonic jet expansion. The conformational assignment was confirmed by the observation of eighteen different isotopologues in natural abundance (all possible (13)C's and two (18)O species of the homochiral form). The two clusters are formed in practically equal proportions (1.1 : 1), probably due to their similar hydrogen bonding topologies. In both clusters the complex is stabilized by a primary C-H···O hydrogen bond, assisted by weak C-HF interactions. This intermolecular binding regime is characterized by a mixture of electrostatic and dispersive interactions, midway between classical hydrogen bonds and van der Waals clusters.

Behind the reactivity of lactones: a computational and spectroscopic study of phenol·Î³-butyrolactone.

In this work, the intermolecular interaction between phenol and γ-butyrolactone (GBL) has been studied by a combination of spectroscopic and computational techniques. The electronic and vibrational transitions of phenol · GBL were measured in a supersonic jet expansion by resonant two-photon ionization (R2PI) and ion dip IR (IDIR) spectroscopy. The results obtained were compared with calculations carried out with both M06-2X and MP2 molecular orbital methods in order to characterize the intermolecular interactions. The singly detected conformer is stabilized by a relatively strong hydrogen bond in which phenol acts as a proton donor to the carbonyl group of GBL. The phenol · GBL2 cluster has also been studied, finding up to three populated conformers. Nevertheless, in the three species, the main interaction between the phenolic hydroxyl group and the GBL's carbonyl group remains similar to that of phenol · GBL. Furthermore, the C ═ O · · · H interaction is reinforced.

Conformational flexibility of mephenesin.

The mephenesin molecule (3-(2-methylphenoxy)propane-1,2-diol) serves as a test bank to explore several structural and dynamical issues, such as conformational flexibility, the orientation of the carbon linear chain relative to the benzene plane, or the effect of substituent position on the rotational barrier of a methyl group. The molecule has been studied by rotational spectroscopy in the 4-18 GHz frequency range by Fourier-transform methods in a supersonic expansion. The experiment has been backed by a previous conformational search plus optimization of the lowest energy structures by ab initio and density functional quantum calculations. The three lowest-lying conformers that can interconvert to each other by simple bond rotations have been detected in the jet. Rotational parameters for all structures have been obtained, and methyl torsional barriers have been determined for the two lowest-lying rotamers. The lowest-lying structure of mephenesin is highly planar, with all carbon atoms lying nearly in the benzene ring plane, and is stabilized by the formation of cooperative intramolecular hydrogen bonding. An estimation of the relative abundance of the detected conformers indicates that the energetically most stable conformer will have an abundance near 80% at temperatures relevant for biological activity.

Probing the C-H⋠⋠⋠π weak hydrogen bond in anesthetic binding: the sevoflurane-benzene cluster.

Cooperativity between weak hydrogen bonds can be revealed in molecular clusters isolated in the gas phase. Here we examine the structure, internal dynamics, and origin of the weak intermolecular forces between sevoflurane and a benzene molecule, using multi-isotopic broadband rotational spectra. This heterodimer is held together by a primary C-H⋅⋅⋅π hydrogen bond, assisted by multiple weak C-H⋅⋅⋅F interactions. The multiple nonbonding forces hinder the internal rotation of benzene around the isopropyl C-H bond in sevoflurane, producing detectable quantum tunneling effects in the rotational spectrum.

The distorted tropane of scopoline.

The structural isomerization of scopine into scopoline (oscine) has been observed in a supersonic jet expansion using microwave spectroscopy. The rotational spectrum evidences a single structure in the gas phase, providing a first description of the (three-ring) structurally distorted tropane in scopoline. The absence of rotational signatures of any scopine conformation suggests a practically quantitative isomerization at the vaporization temperatures of the experiment (ca. 90 °C). The determined rotational parameters of scopoline reveal the structural consequences of the intramolecular cyclation of scopine, which breaks the original epoxy group and creates a new ether bridge and a 7ß-hydroxytropane configuration. The hydroxy group further stabilizes the molecule by an O-H⋅⋅⋅N intramolecular hydrogen bond, which, in turn, forces the N-methyl group to the less stable axial form. Supporting ab initio (MP2) and DFT (B3LYP, M06-2X) calculations are included.

Rotational spectroscopy of antipyretics: conformation, structure, and internal dynamics of phenazone.

The conformational and structural preferences of phenazone (antipyrine), the prototype of non-opioid pyrazolone antipyretics, have been probed in a supersonic jet expansion using rotational spectroscopy. The conformational landscape of the two-ring assembly was first explored computationally, but only a single conformer was predicted, with the N-phenyl and N-methyl groups on opposite sides of the pyrazolone ring. Consistently, the microwave spectrum evidenced a rotational signature arising from a single molecular structure. The spectrum exhibited very complicated fine and hyperfine patterns (not resolvable with any other spectroscopic technique) originated by the simultaneous coupling of the methyl group internal rotation and the spins of the two (14)N nuclei with the overall rotation. The internal rotation tunnelling was ascribed to the C-CH3 group and the barrier height established experimentally (7.13(10) kJ mol(-1)). The internal rotation of the N-CH3 group has a lower limit of 9.4 kJ mol(-1). The structure of the molecule was determined from the rotational parameters, with the phenyl group elevated ca. 25° with respect to the average plane of the pyrazolic moiety and a phenyl torsion of ca. 52°. The origin of the conformational preferences is discussed in terms of the competition between intramolecular C-H···N and C-H···O weak hydrogen bonds.

Free fructose is conformationally locked.

Fructose has been examined under isolation conditions using a combination of UV ultrafast laser vaporization and Fourier-transform microwave (FT-MW) spectroscopy. The rotational spectra for the parent, all (six) monosubstituted (13)C species, and two single D species reveal unambiguously that the free hexoketose is conformationally locked in a single dominant ß-pyranose structure. This six-membered-chair skeleton adopts a (2)C(5) configuration (equivalent to (1)C(4) in aldoses). The free-molecule structure sharply contrasts with the furanose form observed in biochemically relevant polysaccharides, like sucrose. The structure of free fructose has been determined experimentally using substitution and effective structures. The enhanced stability of the observed conformation is primarily attributed to a cooperative network of five intramolecular O-H···O hydrogen bonds and stabilization of both endo and exo anomeric effects. Breaking a single intramolecular hydrogen bond destabilizes the free molecule by more than 10 kJ mol(-1). The structural results are compared to ribose, recently examined with rotational resolution, where six different conformations coexist with similar conformational energies. In addition, several DFT and ab initio methods and basis sets are benchmarked with the experimental data.

Ultrafast Nonradiative Relaxation Channels of Tryptophan.

The nonradiative relaxation channels of gas-phase tryptophan excited along the S1-S4 excited states (287-217 nm) have been tracked by femtosecond time-resolved ionization. In the low-energy region, λ ≥ 240 nm, the measured transient signals reflect nonadiabatic interactions between the two bright La and Lb states of ππ* character and the dark dissociative πσ* state of the indole NH. The observed dynamical behavior is interpreted in terms of the ultrafast conversion of the prepared La state, which simultaneously populates the fluorescent Lb> and the dissociative πσ* states. At higher energies, after excitation of the S4 state, the tryptophan dynamics diverges from that observed in indole, pointing to the opening of a relaxation channel that could involve states of the amino acid part. The work provides a detailed picture of the processes and electronic states involved in the relaxation of the molecule, after photoexcitation in the near part of its UV absorption spectrum.

Ultrafast evolution of imidazole after electronic excitation.

The ultrafast dynamics of the imidazole chromophore has been tracked after electronic excitation in the 250-217 nm energy region, by time delayed ionization with 800 nm laser pulses. The time-dependent signals collected at the imidazole(+) mass channel show the signature of femtosecond dynamics, originating on the πσ*- and ππ*-type states located in the explored energy region. The fitting of the transients, which due to the appearance of nonresonant coherent adiabatic excitation requires a quantum treatment based in the Bloch equations, yields two lifetimes of 18 ± 4 and 19 ± 4 fs. The first is associated with the πσ* ← ππ* internal conversion, while the second reflects the loss of ionization cross-section as the system evolves along the dissociative πσ* surface. This study provides a comprehensive picture of the photophysics of the molecule that agrees with previous experimental and theoretical findings.

A spectroscopic and computational study of propofol dimers and their hydrated clusters.

Propofol (2,6-diisopropylphenol, PPF) homodimers and their complexes with one water molecule are analyzed by means of mass-resolved excitation spectroscopy. Using two-color resonance-enhanced multiphoton ionization (REMPI) the S(1) electronic spectra of these systems are obtained, avoiding fragmentation. Due to the large size of these species, the spectra present a large abundance of lines. Using UV/UV hole-burning spectroscopy, two isomers of PPF(2) are found and the existence of at least three isomers for propofol(2)(H(2)O)(1) (PPF(2)W(1)) is demonstrated. Comparison with the structures calculated at the M06-2X/6-311++G(d,p) and M06-2X/6-31+G(d) levels of theory shows that the main driving forces in PPF(2) are several C-H···π interactions accompanied by dipole-dipole interaction between the OH moieties. On the other hand, there is evidence for the formation of cyclic hydrogen-bond structures in the heterotrimers. A comparison of the results obtained herein with those of similar systems from previously published studies follows.

Single hydration of the peptide bond: the case of the Vince lactam.

2-Azabicyclo[2.2.1]hept-5-en-3-one (ABH or Vince lactam) and its monohydrated complex (ABH···H(2)O) have been observed in a supersonic jet by Fourier transform microwave spectroscopy. ABH is broadly used in the synthesis of therapeutic drugs, whereas the ABH···H(2)O system offers a simple model to explain the conformational preferences of water linked to a constrained peptidic bond. A single predominant form of the Vince lactam and its singly hydrated complex have been detected, determining the rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling tensor. The monohydrated complex is stabilized by two hydrogen bonds (C═O···H-O and N-H···O) closing a six-membered ring. The complexation energy has been estimated to be ∼10 kJ mol(-1) from experimental results. In addition, the observed structure in the gas phase has been compared with solid-phase diffraction data. The structural parameters and binding energies of ABH···H(2)O have also been compared with similar molecules containing peptide bonds. Ab initio (MP2) and density functional (M06-2X and B3LYP) methods have supported the experimental work, describing the rotational parameters and conformational landscape of the title compound and its singly hydrated complex.

A spectroscopic approach to the solvation of anesthetics in jets: propofol(H2O)n, n = 4-6.

Propofol is a widely used nonvolatile anesthetic that exerts its action by docking to GABAA receptors. The docking process is a competition between solvation of the anesthetic by the extracellular medium and the stabilization inside the active site, and therefore a deep knowledge of the process requires of a good understanding of the solvation process. In this work we create propofol-water complexes containing up to six water molecules using supersonic expansions. We determine their structure by means of a number of mass-resolved laser-based excitation spectroscopic techniques, namely two-color REMPI, UV/UV, and IR/UV double resonance techniques, combined with computational chemistry. The results clearly show that water tends to self-aggregate, interacting with the hydrophilic side of propofol. Furthermore, a transition from planar to three-dimensional structures is observed in propofol(H2O)6. Comparison with structural data from similar systems such as phenol-water and pure water clusters follows.

A combined spectroscopic and theoretical study of propofol·(H2O)3.

Propofol (2,6-di-isopropylphenol) is probably the most widely used general anesthetic. Previous studies focused on its complexes containing 1 and 2 water molecules. In this work, propofol clusters containing three water molecules were formed using supersonic expansions and probed by means of a number of mass-resolved laser spectroscopic techniques. The 2-color REMPI spectrum of propofol[middle dot](H(2)O)(3) contains contributions from at least two conformational isomers, as demonstrated by UV/UV hole burning. Using the infrared IR/UV double resonance technique, the IR spectrum of each isomer was obtained both in ground and first excited electronic states and interpreted in the light of density functional theory (DFT) calculations at M06-2X/6-311++G(d,p) and B3LYP/6-311++G(d,p) levels. The spectral analysis reveals that in both isomers the water molecules are forming cyclic hydrogen bond networks around propofol's OH moiety. Furthermore, some evidences point to the existence of isomerization processes, due to a complicated conformational landscape and the existence of multiple paths with low energy barriers connecting the different conformers. Such processes are discussed with the aid of DFT calculations.

Femtosecond evolution of the pyrrole molecule excited in the near part of its UV spectrum.

The evolution of the isolated pyrrole molecule has been followed after excitation in the 265-217 nm range by using femtosecond time delayed ionization. The transients collected in the whole excitation range show the vanishing of the ionization signal in the femtosecond time scale, caused by the relaxation along a πσ(∗) type state (3s a(1)←π 1a(2)), which is the lowest excited electronic state of the molecule. This surface is dissociative along the NH bond, yielding a 15 ± 3 fs lifetime that reflects the loss of the ionization cross-section induced by the ultrafast wavepacket motion. Although a weak πσ(∗) absorption is detected, the state is mainly reached through internal conversion of the higher bright ππ(∗) transitions, which occurs with a 19 ± 3 fs lifetime. In addition to its resonant excitation, the intense ππ(∗) absorption extending in the 220-190 nm interval is also out-of-resonance populated at energies far to the red from its absorption onset. This coherent adiabatic excitation of the ππ(∗) transition should follow the excitation pulse (coherent population return effect), but instead the system relaxes toward the lower πσ(∗) surface through a conical intersection during the interaction time, leading to the population of πσ(∗) state at wavelengths as long as 265 nm. According to the observed behavior, the time evolution of the system in the full excitation range studied is modeled by a coherent treatment that provides key insights on the photophysical properties of the molecule.

Mass-resolved infrared spectroscopy of complexes without chromophore by nonresonant femtosecond ionization detection.

Mass-resolved excitation spectroscopic techniques are usually limited to systems with a chromophore, that is, a functional group with electronic transitions in the Vis/UV, with lifetimes from hundreds of picoseconds to some microseconds. In this paper, we expand such techniques to any system, by using a combination of nanosecond IR pulses with nonresonant ionization with 800 nm femtosecond laser pulses. Furthermore, we demonstrate that the technique can achieve conformational specificity introducing an additional nanosecond IR laser. As a proof-of-principle, we apply the technique to the study of phenol(H(2)O)(1), propofol(H(2)O)(1) γ-butyrolactone(H(2)O)(n), n = 1-3, and (H(2)O)(2) complexes. While monohydrated phenol and propofol clusters permit a direct comparison with a well-studied system including an aromatic chromophore, γ-butyrolactone is a cyclic nonaromatic molecule, whose mass-resolved spectroscopy cannot be tackled by conventional techniques. Finally, we further demonstrate the potential of the technique by obtaining the first mass-resolved IR spectrum of the neutral water dimer, a nice example of a system whose ionization-based detection had not been possible to date.