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Bimodal medical imaging based on magnetic resonance imaging (MRI) and computed tomography (CT) is a well-known strategy to increase the diagnostic accuracy. The most recent advances in MRI and CT instrumentation are related to the use of ultra-high magnetic fields (UHF-MRI) and different working voltages (spectral CT), respectively. Such advances require the parallel development of bimodal contrast agents (CAs) that are efficient under new instrumental conditions. In this work, we have synthesized, through a precipitation reaction from a glycerol solution of the precursors, uniform barium dysprosium fluoride nanospheres with a cubic fluorite structure, whose size was found to depend on the Ba/(Ba + Dy) ratio of the starting solution. Moreover, irrespective of the starting Ba/(Ba + Dy) ratio, the experimental Ba/(Ba + Dy) values were always lower than those used in the starting solutions. This result was assigned to lower precipitation kinetics of barium fluoride compared to dysprosium fluoride, as inferred from the detailed analysis of the effect of reaction time on the chemical composition of the precipitates. A sample composed of 34 nm nanospheres with a Ba0.51Dy0.49F2.49 stoichiometry showed a transversal relaxivity (r2) value of 147.11 mM-1·s-1 at 9.4 T and gave a high negative contrast in the phantom image. Likewise, it produced high X-ray attenuation in a large range of working voltages (from 80 to 140 kVp), which can be attributed to the presence of different K-edge values and high Z elements (Ba and Dy) in the nanospheres. Finally, these nanospheres showed negligible cytotoxicity for different biocompatibility tests. Taken together, these results show that the reported nanoparticles are excellent candidates for UHF-MRI/spectral CT bimodal imaging CAs.
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Distributed acoustic sensors (DAS) perform distributed and dynamic strain or temperature change measurements by comparing a measured time-domain trace with a previous fiber reference state. Large strain or temperature fluctuations or laser frequency noise impose the need to update such a reference, making it necessary to integrate the short-term variation measurements if absolute strain or temperature variations are to be obtained. This has the drawback of introducing a 1/f noise component, as noise is integrated with each cumulative variation measurement, which is detrimental to the determination of very slow processes (i.e., in the mHz frequency range or below). This work analyzes the long-term stability of chirped-pulse phase-sensitive optical time-domain reflectometry (CP-ΦOTDR) with multi-frequency database demodulation (MFDD) to carry out "calibrated" measurements in a DAS along an unmodified SMF. It is shown that, under the conditions studied in this work, a "calibrated" chirped-pulse DAS (CP-DAS) with a completely suppressed reference update-induced 1/f noise component is achieved capable of making measurements over periods of more than 2 months with the same set of references, even when switching off the interrogator during the measurement.
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Autonomous vehicles are the near future of the automobile industry. However, until they reach Level 5, humans and cars will share this intermediate future. Therefore, studying the transition between autonomous and manual modes is a fascinating topic. Automated vehicles may still need to occasionally hand the control to drivers due to technology limitations and legal requirements. This paper presents a study of driver behaviour in the transition between autonomous and manual modes using a CARLA simulator. To our knowledge, this is the first take-over study with transitions conducted on this simulator. For this purpose, we obtain driver gaze focalization and fuse it with the road's semantic segmentation to track to where and when the user is paying attention, besides the actuators' reaction-time measurements provided in the literature. To track gaze focalization in a non-intrusive and inexpensive way, we use a method based on a camera developed in previous works. We devised it with the OpenFace 2.0 toolkit and a NARMAX calibration method. It transforms the face parameters extracted by the toolkit into the point where the user is looking on the simulator scene. The study was carried out by different users using our simulator, which is composed of three screens, a steering wheel and pedals. We distributed this proposal in two different computer systems due to the computational cost of the simulator based on the CARLA simulator. The robot operating system (ROS) framework is in charge of the communication of both systems to provide portability and flexibility to the proposal. Results of the transition analysis are provided using state-of-the-art metrics and a novel driver situation-awareness metric for 20 users in two different scenarios.
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Conducción de Automóvil , Humanos , Tiempo de Reacción , Automatización , Atención , Concienciación , Accidentes de Tránsito/prevención & controlRESUMEN
We describe a wet chemical method for the synthesis of uniform and well-dispersed dysprosium vanadate (DyVO4) and holmium vanadate (HoVO4) nanoparticles with an almost spherical shape and a mean size of â¼60 nm and their functionalization with poly(acrylic acid). The transverse magnetic relaxivity of both systems at 9.4 T is analyzed on the basis of magnetic susceptibility and magnetization measurements in order to evaluate their potential for application as high-field MRI contrast agents. In addition, the X-ray attenuation properties of these systems are also studied to determine their capabilities as computed tomography contrast agent. Finally, the colloidal stability under physiological pH conditions and the cytotoxicity of the functionalized NPs are also addressed to assess their suitability for bioimaging applications.
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Medios de Contraste/química , Disprosio/química , Holmio/química , Imagen por Resonancia Magnética , Tomografía Computarizada por Rayos X , Vanadatos/química , Resinas Acrílicas/química , Supervivencia Celular/efectos de los fármacos , Medios de Contraste/farmacología , Disprosio/farmacología , Holmio/farmacología , Humanos , Campos Magnéticos , Nanopartículas/química , Células PC-3 , Tamaño de la Partícula , Vanadatos/farmacologíaRESUMEN
Monitoring driver attention using the gaze estimation is a typical approach used on road scenes. This indicator is of great importance for safe driving, specially on Level 3 and Level 4 automation systems, where the take over request control strategy could be based on the driver's gaze estimation. Nowadays, gaze estimation techniques used in the state-of-the-art are intrusive and costly, and these two aspects are limiting the usage of these techniques on real vehicles. To test this kind of application, there are some databases focused on critical situations in simulation, but they do not show real accidents because of the complexity and the danger to record them. Within this context, this paper presents a low-cost and non-intrusive camera-based gaze mapping system integrating the open-source state-of-the-art OpenFace 2.0 Toolkit to visualize the driver focalization on a database composed of recorded real traffic scenes through a heat map using NARMAX (Nonlinear AutoRegressive Moving Average model with eXogenous inputs) to establish the correspondence between the OpenFace 2.0 parameters and the screen region the user is looking at. This proposal is an improvement of our previous work, which was based on a linear approximation using a projection matrix. The proposal has been validated using the recent and challenging public database DADA2000, which has 2000 video sequences with annotated driving scenarios based on real accidents. We compare our proposal with our previous one and with an expensive desktop-mounted eye-tracker, obtaining on par results. We proved that this method can be used to record driver attention databases.
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Conducción de Automóvil , Accidentes de Tránsito , Algoritmos , Atención , AutomatizaciónRESUMEN
The goal of this paper is to improve our previous Dynamic Obstacle Mapping (DOMap) system by means of improving the perception stage. The new system must deal with robots and people as dynamic obstacles using LIght Detection And Range (LIDAR) sensor in order to collect the surrounding information. Although robot movement can be easily tracked by an Extended Kalman Filter (EKF), people's movement is more unpredictable and it might not be correctly linearized by an EKF. Therefore, to deal with a better estimation of both types of dynamic objects in the local map it is recommended to improve our previous work. The DOMap has been extended in three key points: first the LIDAR reflectivity remission is used to make more robust the matching in the optical flow of the detection stage, secondly static and a dynamic occlusion detectors have been proposed, and finally a tracking stage based on Particle Filter (PF) has been used to deal with robots and people as dynamic obstacles. Therefore, our new improved-DOMap (iDOMap) provides maps with information about occupancy and velocities of the surrounding dynamic obstacles (robots, people, etc.) in a more robust way and they are available to improve the following planning stage.
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(1) Background: Nanomedicine has recently emerged as a promising field, particularly for cancer theranostics. In this context, nanoparticles designed for imaging and therapeutic applications are of interest. We, therefore, studied the encapsulation of upconverting nanoparticles in mesoporous organosilica nanoparticles. Indeed, mesoporous organosilica nanoparticles have been shown to be very efficient for drug delivery, and upconverting nanoparticles are interesting for near-infrared and X-ray computed tomography imaging, depending on the matrix used. (2) Methods: Two different upconverting-based nanoparticles were synthesized with Yb3+-Er3+ as the upconverting system and NaYF4 or BaLuF5 as the matrix. The encapsulation of these nanoparticles was studied through the sol-gel procedure with bis(triethoxysilyl)ethylene and bis(triethoxysilyl)ethane in the presence of CTAB. (3) Results: with bis(triethoxysilyl)ethylene, BaLuF5: Yb3+-Er3+, nanoparticles were not encapsulated, but anchored on the surface of the obtained mesoporous nanorods BaLuF5: Yb3+-Er3+@Ethylene. With bis(triethoxysilyl)ethane, BaLuF5: Yb3+-Er3+ and NaYF4: Yb3+-Er3+nanoparticles were encapsulated in the mesoporous cubic structure leading to BaLuF5: Yb3+-Er3+@Ethane and NaYF4: Yb3+-Er3+@Ethane, respectively. (4) Conclusions: upconversion nanoparticles were located on the surface of mesoporous nanorods obtained by hydrolysis polycondensation of bis(triethoxysilyl)ethylene, whereas encapsulation occurred with bis(triethoxysilyl)ethane. The later nanoparticles NaYF4: Yb3+-Er3+@Ethane or BaLuF5: Yb3+-Er3+@Ethane were promising for applications with cancer cell imaging or X-ray-computed tomography respectively.
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Nanopartículas/química , Compuestos de Organosilicio/química , Sistemas de Liberación de Medicamentos/métodos , Erbio/química , Etano/química , Fluoruros/química , Hidrólisis , Nanomedicina/métodos , Nanotubos/química , Tecnología Farmacéutica/métodos , Iterbio/química , Itrio/químicaRESUMEN
Although much research has taken place in WiFi indoor localization systems, their accuracy can still be improved. When designing this kind of system, fingerprint-based methods are a common choice. The problem with fingerprint-based methods comes with the need of site surveying the environment, which is effort consuming. In this work, we propose an approach, based on support vector regression, to estimate the received signal strength at non-site-surveyed positions of the environment. Experiments, performed in a real environment, show that the proposed method could be used to improve the resolution of fingerprint-based indoor WiFi localization systems without increasing the site survey effort.
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Bifunctional and highly uniform Ln:BaGdF5 (Ln = Eu(3+) and Nd(3+)) nanoparticles have been successfully synthesized using a solvothermal method consisting of the aging at 120 °C of a glycerol solution containing the corresponding Lanthanide acetylacetonates and butylmethylimidazolium tetrafluoroborate. The absence of any surfactant in the synthesis process rendered hydrophilic nanospheres (with tunable diameter from 45 nm 85 nm, depending on the cations concentration of the starting solution) which are suitable for bioapplications. The particles are bifunctional because they showed both optical and magnetic properties due to the presence of the optically active lanthanides (Eu(3+) in the visible and Nd(3+) in the NIR regions of the electromagnetic spectrum) and the paramagnetic gadolinium ion, respectively. The luminescence decay curves of the nanospheres doped with different amounts of Eu(3+) and Nd(3+) have been recorded in order to determine the optimum dopant concentration in each case, which turned out to be 5% Eu(3+) and 0.5% Nd(3+). Likewise, proton relaxation times were measured at 1.5 T in water suspensions of the optimum particles found in the luminescence study. The values obtained suggested that both kinds of particles could be used as positive contrast agents for MRI. Finally, it was demonstrated that both the 5% Eu(3+) and 0.5% Nd(3+)-doped BaGdF5 nanospheres showed negligible cytotoxicity for VERO cells for concentrations up to 0.25 mg mL(-1).
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Europium-doped calcium hydroxyapatite and fluoroapatite nanophosphors functionalized with poly(acrylic acid) (PAA) have been synthesized through a one-pot microwave-assisted hydrothermal method from aqueous basic solutions containing calcium nitrate, sodium phosphate monobasic, and PAA, as well as sodium fluoride in the case of the fluoroapatite particles. In both cases a spindlelike morphology was obtained, resulting from an aggregation process of smaller subunits which also gave rise to high specific surface area. The size of the nanospindles was 191 (32) × 40 (5) nm for calcium hydroxyapatite and 152 (24) × 38 (6) nm for calcium fluoroapatite. The luminescent nanoparticles showed the typical red luminescence of Eu(3+), which was more efficient for the fluoroapatite particles than for the hydroxyapatite. This is attributed to the presence of OH(-) quenchers in the latter. The nanophosphors showed negligible toxicity for Vero cells. Both PAA-functionalized nanophosphors showed a very high (up to at least 1 week) colloidal stability in 2-(N-morpholino)ethanesulfonic acid (MES) at pH 6.5, which is a commonly used buffer for physiological pH. All these features make both kinds of apatite-based nanoparticles promising tools for biomedical applications, such as luminescent biolabels and tracking devices in drug delivery systems.
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Resinas Acrílicas/química , Apatitas/química , Durapatita/química , Europio/química , Microondas , Nanopartículas/química , Compuestos Organometálicos/química , Animales , Materiales Biocompatibles/síntesis química , Materiales Biocompatibles/química , Materiales Biocompatibles/toxicidad , Tampones (Química) , Supervivencia Celular/efectos de los fármacos , Técnicas de Química Sintética , Chlorocebus aethiops , Concentración de Iones de Hidrógeno , Cinética , Sustancias Luminiscentes/química , Fenómenos Ópticos , Compuestos Organometálicos/síntesis química , Compuestos Organometálicos/toxicidad , Células VeroRESUMEN
A procedure for the synthesis of multifunctional europium(III)-doped gadolinium(III) fluoride (Eu:GdF3) nanoparticles (~85 nm) with quasispherical shape by precipitation at 120 °C from diethylene glycol solutions containing lanthanide chlorides and an ionic liquid (1-Butyl, 2-methylimidazolium tetrafluoroborate) as fluoride source has been developed. These nanoparticles were polycrystalline and crystallized into a hexagonal structure, which is unusual for GdF3. They were also mesoporous (pore size = 3.5 Å), having a rather high BET surface area (75 m(2) g(-1)). The luminescent and magnetic (relaxivity) properties of the Eu:GdF3 nanoparticles have been also evaluated in order to assess their potentiality as "in vitro" optical biolabels and contrast agent for magnetic resonance imaging. Finally, a procedure for their functionalization with aspartic-dextran polymers is also reported. The functionalized Eu:GdF3 nanoparticles presented negligible toxicity for Vero cells, which make them suitable for biotecnological applications.
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Europio/química , Gadolinio/química , Líquidos Iónicos/química , Nanopartículas del Metal/química , Propiedades de SuperficieRESUMEN
It is well-known that when an RE2Si2O7 matrix is doped with active lanthanide ions, it displays promising luminescent responses for optical applications. The crystalline structure adopted by the silicate matrix as well as the distribution of the dopants among the available RE crystallographic sites have important effects on the luminescent yields of these compounds. The present study is aimed at analyzing the structural behavior as well as the luminescent properties of Ho(3+)-substituted La2Si2O7. Several compositions across the La2Si2O7-Ho2Si2O7 system were synthesized using the sol-gel method followed by calcination at 1600 °C. The resulting powders were analyzed by means of X-ray and neutron diffraction to determine the phase stabilities across the system. The results indicated a solid solubility region of G-(La,Ho)2Si2O7 which extends to the La0.6Ho1.4Si2O7 composition. Compositions richer in Ho(3+) show a two-phase domain (G+δ), while δ-(La,Ho)2Si2O7 is the stable phase for Ho(3+) contents higher than 90% (La0.2Ho1.8Si2O7). Anomalous diffraction data interestingly indicated that the La(3+) for Ho(3+) substitution mechanism in the G-(La,Ho)2Si2O7 polymorph is not homogeneous, but a preferential occupation of Ho(3+) for the RE2 site is observed. The Ho(3+)-doped G-La2Si2O7 phosphors exhibited a strong green luminescence after excitation at 446 nm. Lifetime measurements indicated that the optimum phosphor was that with a Ho(3+) content of 10%.
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A simple and fast (7 min) procedure for synthesis of gadolinium phosphate nanocubes (edge = 75 nm) based on the microwave-assisted heating at 120 °C of gadolinium acetylacetonate and phosphoric acid solutions in buthylene glycol is reported. These nanocubes were highly crystalline and crystallized into a tetragonal structure, which has not been ever reported for pure gadolinium phosphate. Determination of such crystal structure has been carried out here for the first time in the literature by means of powder X-ray diffraction. The developed synthesis procedure was also successful for preparation of multifunctional europium(III)-doped the gadolinium phosphate nanocubes, which were nontoxic for cells and exhibited strong red luminescence under UV illumination and high transverse relaxivity (r(2)) values. These properties confer them potential applications as biolabels for in vitro optical imaging and as negative contrast agent for magnetic resonance imaging.
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Europio/química , Gadolinio/química , Nanopartículas/química , Compuestos Organometálicos/síntesis química , Animales , Supervivencia Celular/efectos de los fármacos , Células Cultivadas , Cristalografía por Rayos X , Imagen por Resonancia Magnética , Microscopía Electrónica de Transmisión , Compuestos Organometálicos/farmacología , Tamaño de la Partícula , Factores de TiempoRESUMEN
The goal of this paper is to solve the problem of dynamic obstacle avoidance for a mobile platform using the stochastic optimal control framework to compute paths that are optimal in terms of safety and energy efficiency under constraints. We propose a three-dimensional extension of the Bayesian Occupancy Filter (BOF) (Coué et al. Int. J. Rob. Res. 2006, 25, 19-30) to deal with the noise in the sensor data, improving the perception stage. We reduce the computational cost of the perception stage by estimating the velocity of each obstacle using optical flow tracking and blob filtering. While several obstacle avoidance systems have been presented in the literature addressing safety and optimality of the robot motion separately, we have applied the approximate inference framework to this problem to combine multiple goals, constraints and priors in a structured way. It is important to remark that the problem involves obstacles that can be moving, therefore classical techniques based on reactive control are not optimal from the point of view of energy consumption. Some experimental results, including comparisons against classical algorithms that highlight the advantages, are presented.
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Algoritmos , Conducción de Automóvil , Teorema de Bayes , Humanos , Movimiento (Física)RESUMEN
Uniform sodium-dysprosium double molybdate (NaDy(MoO4)2) nanoparticles having different morphologies (spheres and ellipsoids) and tunable size have been synthesized for the first time in literature. The procedure is based on a homogeneous precipitation process at moderated temperatures (≤220 °C) from solutions containing appropriated precursors dissolved in ethylene glycol-water mixtures, in the absence (spheres) or the presence (ellipsoids) of tartrate anions. The effects of the morphological characteristics (size and shape) of the nanoparticles on the magnetic relaxivity at high field (9.4 T) have been evaluated finding that the latter magnitude was higher for the spheres than for the ellipsoids, indicating their better suitability as contrast agents for high-field magnetic resonance imaging. Such nanoparticles have been successfully coated with polymers bearing carboxylate functional groups through a layer-by-layer process, which improves the colloidal stability of the nanoparticles in physiological media. It has been also found that the coating layer had no significant effects on the nanoparticles relaxivity and that such coated nanoparticles exhibited a high biocompatibility and a high chemical stability. In summary, we have developed NaDy(MoO4)2 based bioprobes which meet the required criteria for their use as contrast agents for high-field magnetic resonance imaging.
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Medios de Contraste , Nanopartículas , Tartratos , Disprosio , Imagen por Resonancia Magnética/métodos , Polímeros , Campos Magnéticos , Aniones , Agua , Glicoles de Etileno , SodioRESUMEN
Zinc germanate doped with Mn2+ (Zn2GeO4:Mn2+) is known to be a persistent luminescence green phosphor with potential applications in biosensing and bioimaging. Such applications demand nanoparticulated phosphors with a uniform shape and size, good dispersibility in aqueous media, high chemical stability, and surface-functionalization. These characteristics could be major bottlenecks and hence limit their practical applications. This work describes a one-pot, microwave-assisted hydrothermal method to synthesize highly uniform Zn2GeO4:Mn2+ nanoparticles (NPs) using polyacrylic acid (PAA) as an additive. A thorough characterization of the NPs showed that the PAA molecules were essential to realizing uniform NPs as they were responsible for the ordered aggregation of their building blocks. In addition, PAA remained attached to the NPs surface, which conferred high colloidal stability to the NPs through electrostatic and steric interactions, and provided carboxylate groups that can act as anchor sites for the eventual conjugation of biomolecules to the surface. In addition, it was demonstrated that the as-synthesized NPs were chemically stable for, at least, 1 week in phosphate buffer saline (pH range = 6.0-7.4). The luminescence properties of Zn2GeO4 NPs doped with different contents of Mn2+ (0.25-3.00 mol %) were evaluated to find the optimum doping level for the highest photoluminescence (2.50% Mn) and the longest persistent luminescence (0.50% Mn). The NPs with the best persistent luminescence properties were photostable for at least 1 week. Finally, taking advantage of such properties and the presence of surface carboxylate groups, the Zn2GeO4:0.50%Mn2+ sample was successfully used to develop a persistent luminescence-based sandwich immunoassay for the autofluorescence-free detection of interleukin-6 in undiluted human serum and undiluted human plasma samples. This study demonstrates that our persistent Mn-doped Zn2GeO4 nanophosphors are ideal candidates for biosensing applications.
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Luminiscencia , Nanopartículas , Humanos , Nanopartículas/química , Resinas Acrílicas , Zinc/químicaRESUMEN
We have developed a trimodal bioimaging probe for near-infrared luminescent imaging, high-field magnetic resonance imaging, and X-ray computed tomography using Dy3+ as the paramagnetic component and Nd3+ as the luminescent cation, both of them incorporated in a vanadate matrix. Among different essayed architectures (single phase and core-shell nanoparticles) the one showing the best luminescent properties is that consisting of uniform DyVO4 nanoparticles coated with a first uniform layer of LaVO4 and a second layer of Nd3+-doped LaVO4. The magnetic relaxivity (r2) at high field (9.4 T) of these nanoparticles was among the highest values ever reported for this kind of probes and their X-ray attenuation properties, due to the presence of lanthanide cations, were also better than those of a commercial contrast agent (iohexol) commonly used for X-ray computed tomography. In addition, they were chemically stable in a physiological medium in which they could be easily dispersed owing to their one-pot functionalization with polyacrylic acid, and, finally, they were non-toxic for human fibroblast cells. Such a probe is, therefore, an excellent multimodal contrast agent for near-infrared luminescent imaging, high-field magnetic resonance imaging, and X-ray computed tomography.
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Elementos de la Serie de los Lantanoides , Nanopartículas , Humanos , Elementos de la Serie de los Lantanoides/química , Vanadatos , Medios de Contraste/química , Tomografía Computarizada por Rayos X/métodos , Imagen por Resonancia Magnética/métodos , Nanopartículas/químicaRESUMEN
The synthesis and structure resolution of RbLaF(4) are described. RbLaF(4) is synthesized by solid-state reaction between RbF and LaF(3) at 425 °C under a nonoxidizing atmosphere. Its crystal structure has been resolved by combining neutron and synchrotron powder diffraction data refinements (Pnma,a = 6.46281(2) Å, b = 3.86498(1) Å, c = 16.17629(4) Å, Z = 4). One-dimensional (87)Rb, (139)La, and (19)F MAS NMR spectra have been recorded and are in agreement with the proposed structural model. Assignment of the (19)F resonances is performed on the basis of both (19)F-(139)La J-coupling multiplet patterns observed in a heteronuclear DQ-filtered J-resolved spectrum and (19)F-(87)Rb HMQC MAS experiments. DFT calculations of both the (19)F isotropic chemical shieldings and the (87)Rb, (139)La electric field gradient tensors using the GIPAW and PAW methods implemented in the CASTEP code are in good agreement with the experimental values and support the proposed structural model. Finally, the conductivity of RbLaF(4) and luminescence properties of Eu-doped LaRbF(4) are investigated.
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This paper presents a complete traffic sign recognition system based on vision sensor onboard a moving vehicle which detects and recognizes up to one hundred of the most important road signs, including circular and triangular signs. A restricted Hough transform is used as detection method from the information extracted in contour images, while the proposed recognition system is based on Support Vector Machines (SVM). A novel solution to the problem of discarding detected signs that do not pertain to the host road is proposed. For that purpose infrastructure-to-vehicle (I2V) communication and a stereo vision sensor are used. Furthermore, the outputs provided by the vision sensor and the data supplied by the CAN Bus and a GPS sensor are combined to obtain the global position of the detected traffic signs, which is used to identify a traffic sign in the I2V communication. This paper presents plenty of tests in real driving conditions, both day and night, in which an average detection rate over 95% and an average recognition rate around 93% were obtained with an average runtime of 35 ms that allows real-time performance.
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Inteligencia Artificial , Conducción de Automóvil , Interpretación de Imagen Asistida por Computador/instrumentación , Directorios de Señalización y Ubicación , Reconocimiento de Normas Patrones Automatizadas/métodos , Viaje , Tecnología Inalámbrica/instrumentación , Diseño de Equipo , Análisis de Falla de Equipo , Interfaz Usuario-ComputadorRESUMEN
The use of high-field magnets for magnetic resonance imaging (MRI) is expected to experience the fastest growth rate during the present decade. Although several CAs for MRI scanners using high magnetic fields have been reported, they are mostly based on fluoride matrices, which are known for their low chemical stability in aqueous suspensions. Chemically stable MRI CAs for high-field magnets are therefore needed to enable the advances in MRI technique. Herein, we synthesized uniform DyPO4 nanoparticles (NPs) with tuneable sizes between 23 and 57 nm using homogeneous precipitation in butanol. The NPs were successfully functionalized with polyacrylic acid (PAA) and showed good colloidal stability in aqueous suspensions. Chemical stability was also assessed in PBS, showing negligible solubility. The effect of particle size on the transversal relaxivity value (r2) was further explored at 9.4 T, finding a clear increase in r2 with particle size. The r2 value found for the largest NPs was 516 mM-1 s-1, which is, to the best of our knowledge, the highest r2 value ever reported at 9.4 T for any Dy-based nanometric particles in the literature. Finally, the latter NPs were submitted to biosafety studies after polyethylene glycol (PEG) functionalization. Cell morphology, induction of necrotic/late apoptotic cells, and mitochondrial activity were thoroughly analyzed. The results clearly indicated negligible toxicity effects under the assayed conditions. Short- and long-term in vivo pharmacokinetics of the intravenously injected NPs were assessed by dynamic T2-weighted MRI and quantitative T2 mapping, revealing faster liver than spleen uptake, while no accumulation was observed in the kidneys. Finally, no histopathological changes were observed in any of the studied organs, including the liver, kidney, spleen, and lung, which provide further evidence of the biocompatibility of DyPO4 NPs and, therefore, their suitability as bioimaging probes.