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On‐surface synthesis has become a prominent method for growing low‐dimensional carbon‐based nanomaterials on metal surfaces. However, the necessity of decoupling organic nanostructures from metal substrates to exploit their properties requires either transfer methods or new strategies to perform reactions directly on inert surfaces. The use of on‐surface light‐induced reactions directly on semiconductor/insulating surfaces represents an alternative approach to address these challenges. Here, exploring the photochemical activity of different organic molecules on a SnSe semiconductor surface under ultra‐high vacuum, we present a novel on‐surface light‐induced reaction. The selective photodissociation of the anhydride group is observed, releasing CO and CO2. Moreover, we rationalize the relationship between the photochemical activity and the π‐conjugation of the molecular core. The different experimental behaviour of two model anhydrides was elucidated by theoretical calculations, showing how the molecular structure influences the distribution of the excited states. Our findings open new pathways for on‐surface synthesis directly on technologically relevant substrates. [ABSTRACT FROM AUTHOR]

This letter introduces an unconditionally stable finite‐difference time‐domain (FDTD) method, based on the locally one‐dimensional (LOD) technique, for the solution of the two‐dimensional scalar wave equation (WE) in homogeneous media. The second spatial derivatives in the WE are discretized by using a three‐point compact (implicit) finite‐difference formula with a free parameter. This formula has second‐order accuracy and becomes fourth‐order by properly selecting the parameter value. Moreover, the resulting algorithm only involves tridiagonal matrices, as when using standard (explicit) second‐order finite differences. Additionally, a stability analysis is performed and the numerical dispersion relation of the method is derived. The proposed compact LOD‐WE‐FDTD technique has been applied to the calculation of resonant frequencies in a metallic ridge cavity. The accuracy of the results obtained has been studied as a function of the parameter value. [ABSTRACT FROM AUTHOR]

The incorporation of non‐benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon‐based electronics. However, understanding how specific non‐benzenoid structures influence their properties remains limited, and further investigations are needed to fully comprehend their implications. Here, we report an on‐surface synthetic strategy toward fabricating non‐benzenoid nanographenes containing different combinations of pentagonal and heptagonal rings. Their structure and electronic properties were investigated via scanning tunneling microscopy and spectroscopy, complemented by computational investigations. After thermal activation of the precursor P on the Au(111) surface, we detected two major nanographene products. Nanographene Aa−a embeds two azulene units formed through oxidative ring‐closure of methyl substituents, while Aa−s contains one azulene unit and one Stone‐Wales defect, formed by the combination of oxidative ring‐closure and skeletal ring‐rearrangement reactions. Aa−a exhibits an antiferromagnetic ground state with the highest magnetic exchange coupling reported up to date for a non‐benzenoid containing nanographene, coexisting with side‐products with closed shell configurations resulted from the combination of ring‐closure and ring‐rearragement reactions (Ba−a, Ba−s, Bs‐a and Bs−s). Our results provide insights into the single gold atom assisted synthesis of novel NGs containing non‐benzenoid motifs and their tailored electronic/magnetic properties. [ABSTRACT FROM AUTHOR]

(Background) Esophagectomy (EPG) presents high morbidity and mortality. Omega-3 fatty acids (ω-3FA) are a pharmaconutrient with benefits for postoperative morbidity. Studies of ω-3FA administered parenterally after esophagectomy are scarce. This study proposes to investigate the effect of combining fish oil lipid emulsions (LE) administered parenterally with enteral nutrition support. (Methods) Randomization was 1:1:1 in three groups: Group A received a LE mixture of 0.4 g/kg/day of fish oil and 0.4 g/kg/day of LCT/MCT 50:50, Group B received 0.8 g/kg/day of fish oil LE, and Group C received 0.8 g/kg/day of LCT/MCT 50:50. Variables were measured at recruitment time and day +1, +3, and +5. Inflammatory variables studied were Interlukin-6, C-reactive protein (CRP), tumoral necrosis factor-α (TNF-α), IL-10, IL-8 and CD25s. Safety, nutritional parameters and complications were analyzed. (Results) Administration of ω-3LE in the immediate postoperative period did not modulate the earlier inflammatory response. Statistically significant differences were found in IL-6 and CRP overall temporal evolution but were not found when studying the type of LE administered or in patients needing critical care. Administration of ω-3 resulted in safe and improved hypertriglyceridemia, depending on the dose. (Conclusions) ω-3FA has no impact on the early inflammatory postoperative response assessed for a short period but was safe. More studies for longer periods are needed. [ABSTRACT FROM AUTHOR]

Nanocars are carbon‐based single‐molecules with a precise design that facilitates their atomic‐scale control on a surface. The rational design of these molecules is important in atomic and molecular‐scale manipulation to advance the development of molecular machines, as well as for a better understanding of self‐assembly, diffusion and desorption processes. Here, we introduce the molecular design and construction of a collection of minimalistic nanocars. They feature an anthracene chassis and four benzene derivatives as wheels. After sublimation and adsorption on an Au(111) surface, we show controlled and fast manipulation of the nanocars along the surface using the tip of a scanning tunneling microscope (STM). The mechanism behind the successful displacement is the induced dipole created over the nanocar by the STM tip. We utilized carbon monoxide functionalized tips both to avoid decomposition and accidentally picking the nanocars up during the manipulation. This strategy allowed thousands of maneuvers to successfully win the Nanocar Race II championship. [ABSTRACT FROM AUTHOR]

This article presents a novel mathematical model to describe the spread of an infectious disease in the presence of social and health events: it uses 15 compartments, 7 convolution integrals and 4 types of infected individuals, asymptomatic, mild, moderate and severe. A unique feature of this work is that the convolutions and the compartments have been selected to maximize the number of independent input parameters, leading to a 56-parameter model where only one had to evolve over time. The results show that 1) the proposed mathematical model is flexible and robust enough to describe the complex dynamic of the pandemic during the first three waves of the COVID-19 spread in the region of Madrid (Spain) and 2) the proposed model allows us to calculate the number of asymptomatic individuals and the number of persons who presented antibodies during the first waves. The study shows that the following results are compatible with the reported data: close to 28% of the infected individuals were asymptomatic during the three waves, close to 29% of asymptomatic individuals were detected during the subsequent waves and close to 26% of the Madrid population had antibodies at the end of the third wave. This calculated number of persons with antibodies is in great agreement with four direct measurements obtained from an independent sero-epidemiological research. In addition, six calculated curves (total number of confirmed cases, asymptomatic who are confirmed as positive, hospital admissions and discharges and intensive care units admissions) show good agreement with data from an epidemiological surveillance database. [ABSTRACT FROM AUTHOR]

Atomic scale defects significantly affect the mechanical, electronic, and optical properties of π‐conjugated polymers. Here, isolated atomic‐scale defects are deliberately introduced into a prototypical anthracene‐ethynylene π‐conjugated polymer, and its local density of states is carefully examined on the atomic scale to show how individual defects modify the inherent electronic and magnetic properties of this one‐dimensional systems. Scanning tunneling and atomic force microscopy experiments, supplemented with density functional theory calculations, reveal the existence of a sharp electronic resonance at the Fermi energy around certain defects, which is associated with the formation of a local magnetic moment accompanied by substantial mitigation of the mobility of charge carriers. While defects in traditionally synthesized polymers lead to arbitrary conformations, the presented results clearly reflect the preferential formation of low dimensional defects at specific polymer sites, which may introduce the possibility of engineering macroscopic defects in surface‐synthesized conjugated polymers. [ABSTRACT FROM AUTHOR]

A unified view of direct-integration (DI) and exponential-time-differencing (ETD) methods to incorporate Drude media, such as isotropic plasma and microwave graphene, into finite-difference time-domain (FDTD) simulators is provided. To this end, the Drude constitutive relation is expressed in integral form and the DI integrators are obtained by applying quadrature rules. Analogously, the ETD integrators are obtained by starting from the variation of constants formula and applying the same quadrature rules as in the DI case. This approach allows one to directly compare the two families of methods. In addition, the accuracy of each integrator is discussed and the stability condition of the resulting FDTD schemes is derived in exact closed form by applying the von Neumann method. [ABSTRACT FROM AUTHOR]

On‐surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N‐containing pentacene‐based precursor (tetraazapentacene) is ex‐professo synthesized endowed with terminal dibromomethylene (:CBr2) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N‐containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 °C, affording a pyrrolopyrrole‐bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 °C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N‐containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms. [ABSTRACT FROM AUTHOR]

FUNDAMENTO: A pesar de los cambios producidos en las fuentes de emisión, los niveles de partículas, SO2, y CO continúan siendo importantes en el municipio de Madrid. Por otro lado, contaminantes fotoquímicos, como el NO2 y O3, están adquiriendo una importancia creciente debido al incremento del tráfico rodado y los elevados niveles de insolación que tiene esta ciudad. El objetivo de este trabajo es establecer la relación a corto plazo entre los principales contaminantes y la mortalidad diaria en el municipio de Madrid, durante el periodo de 1992 a 1995, utilizando el protocolo estandarizado del proyecto EMECAM (Estudio Multicéntrico Español de Contaminación Atmosférica y Mortalidad). MÉTODOS: Las variaciones diarias de la mortalidad por todas las causas, menos las externas, en todas las edades y en las personas de 70 años y más, así como las del aparato circulatorio y respiratorio, se asocian con las variaciones diarias de partículas (PM10), SO2, NO2, CO y O3, mediante modelos de Poisson autorregresivos. Se controlan las variables estacionalidad, tendencia, temperatura, humedad relativa, gripe, día de la semana, y días festivos e inusuales. RESULTADOS: Se observan asociaciones positivas estadísticamente significativas del SO2 con todas las series de mortalidad analizadas, del CO con la mortalidad en las personas mayores de 69 años así como con la cardiovascular y respiratoria, y de las partículas con la mortalidad cardiovascular. El NO2 también se relaciona de forma estadísticamente significativa con la mortalidad cardiovascular. Estos efectos son inmediatos, es decir, ocurren con los contaminantes del mismo día. No se observaron asociaciones positivas significativas con el O3. CONCLUSIONES: Estos resultados sugieren que, para un espectro amplio de contaminantes principales, los niveles actuales de contaminación atmosférica en el municipio de Madrid se asocian con un incremento de la mortalidad.

A numerical dispersion analysis of the alternating-direction implicit finite-difference time-domain method for transverse-electric waves in lossy materials is presented. Two different finite-difference approximations for the conduction terms are considered: the double-average and the synchronized schemes. The numerical dispersion relation is derived in a closed form and validated through numerical simulations. This study shows that, despite its popularity, the accuracy of the double-average scheme is sensitive to how well the relaxation-time constant of the material is resolved by the time step. Poor resolutions lead to unacceptably large numerical errors. On the other hand, for good conductors, the synchronized scheme allows stability factors as large as 100 to be used without deteriorating the accuracy significantly. Index Terms--Alternating-direction implicit finite-difference time-domain (FDTD) method, lossy media, numerical dispersion, stability.

The lumped-network finite-difference time-domain (LN-FDTD) technique is an extension of the conventional FDTD method that enables the incorporation of linear one-port LNs in a single FDTD cell. This paper studies the stability and the numerical dispersion of this technique. To this end, an isotropic medium that is uniformly loaded with LNs in the x-direction is considered as a working model. The stability analysis, based on the von Neumann method, is performed for general Mth-order LNs and closed-form stability conditions are derived for some particular cases. The numerical dispersion relation is obtained for plane-wave propagation in the proposed LN-loaded medium. It is shown that LNs can be interpreted in terms of an effective frequency-dependent permittivity and, as a consequence, the LN-loaded medium can be viewed as a uniaxial medium. The numerical admittance of the LNs is also obtained showing that, as a side-effect of the time discretization, the LN parameters become frequency-dependent, e.g. for the resistor case, the resistance becomes a function of the frequency. Index Terms--Finite-difference time-domain (FDTD) methods, lumped elements, numerical dispersion, stability.

The synthesis of long n‐peri‐acenes (n‐PAs) is challenging as a result of their inherent open‐shell radical character, which arises from the presence of parallel zigzag edges beyond a certain n value. They are considered as π‐electron model systems to study magnetism in graphene nanostructures; being potential candidates in the fabrication of optoelectronic and spintronic devices. Here, we report the on‐surface formation of the largest pristine member of the n‐PA family, i.e. peri‐heptacene (n=7, 7‐PA), obtained on an Au(111) substrate under ultra‐high vacuum conditions. Our high‐resolution scanning tunneling microscopy investigations, complemented by theoretical simulations, provide insight into the chemical structure of this previously elusive compound. In addition, scanning tunneling spectroscopy reveals the antiferromagnetic open‐shell singlet ground state of 7‐PA, exhibiting singlet–triplet spin‐flip inelastic excitations with an effective exchange coupling (Jeff) of 49 meV. [ABSTRACT FROM AUTHOR]

This paper introduces an extension of the original finite-difference time-domain (FDTD) method for modeling double-negative media characterized by high-order frequency-dependent permittivity and permeability. The approach basically consists of adding electric and magnetic current densities to Maxwell's curl equations and considering Ohm's law as a constitutive relationship. Current densities are discretized by using a weighted average in time and Ohm's law by applying the Mobius transformation technique. The extended FDTD formulation is validated and its numerical features are carefully examined. More specifically, analytical stability conditions are derived for several types of double-negative media and the numerical dissipation issue is discussed. In addition, the numerical dispersion equation for general high-order double-negative media is given and the order of accuracy of the scheme is studied. Finally, the definition of numerical refractive index is addressed and it is shown that, when the discretization parameters of the problem ate not properly chosen, a negative refractive index may become a positive one in the discrete world, thus changing the physics of the problem. Index Terms--Double-negative media, finite-difference time-domain (FDTD) methods, Mobius transformation, numerical dispersion, stability.

A multiresolution in time domain method is used to model the propagation of transient signals through dispersive chiral media. The modeling of these media requires the computation of convolution integrals, whose resolution level may be increased by introducing wavelets in the time dependence of the fields. Index Terms--Bi-isotropic (BI) media, chiral media, dispersive media, multiresolution, multiresolution in time domain (MRTD) methods.

In this paper, we present a novel finite-difference time-domain model of transient wave propagation in general dispersive bi-isotropic media with losses. The special properties of these materials may lead to new applications in microwave and millimeter-wave technology. While their frequency-domain properties have been well described in the literature, their time-domain behavior has only been modeled thus far for special sub-classes and monochromatic time dependence. We have validated our method by first computing time-harmonic wave propagation through a bi-isotropic medium and comparing it with analytical results. Agreement is typically better than 1%. We have then computed transient field propagation in a general lossy dispersive bi-isotropic medium. Index Terms--Chiral media, dispersive media, finite-difference time-domain (FDTD) methods, perturbation methods, transient propagation

On-surface synthesis has recently become an essential approach toward the formation of carbon-based nanostructures. Special emphasis is set on the synthesis of π-conjugated polymers taking into consideration their relevance and potential in organic electronics, optoelectronics and spintronics. Here, we report the on-surface synthesis of conjugated ladder polymers consisting of pentacene units doubly-linked via ethynylene-like bonds on the Au(111) surface under ultra-high vacuum conditions. To this aim, we have sublimed pentacene-like precursors equipped with four :CBr2 functional groups to steer the desired reaction upon annealing on the surface. The atomically precise structure of the obtained polymers has been unambiguously characterized via low-temperature scanning tunneling microscopy and non-contact atomic force microscopy. In addition, scanning tunneling spectroscopy complemented with density-functional theory calculations reveal the narrow bandgap of the polymer. Our results provide potential for the synthesis of π-conjugated polymers with prospects in functional carbon-based nanomaterials that exploit multiple connections between molecular backbones. [ABSTRACT FROM AUTHOR]

We report on the synthesis and characterization of atomically precise one‐dimensional diradical peripentacene polymers on a Au(111) surface. By means of high‐resolution scanning probe microscopy complemented by theoretical simulations, we provide evidence of their magnetic properties, which arise from the presence of two unpaired spins at their termini. Additionally, we probe a transition of their magnetic properties related to the length of the polymer. Peripentacene dimers exhibit an antiferromagnetic (S=0) singlet ground state. They are characterized by singlet–triplet spin‐flip inelastic excitations with an effective exchange coupling (Jeff) of 2.5 meV, whereas trimers and longer peripentacene polymers reveal a paramagnetic nature and feature Kondo fingerprints at each terminus due to the unpaired spin. Our work provides access to the precise fabrication of polymers featuring diradical character which are potentially useful in carbon‐based optoelectronics and spintronics. [ABSTRACT FROM AUTHOR]

The calculation of dispersion diagrams and field patterns of metallic rectangular waveguides filled with an inhomogeneous dielectric whose permittivity varies continuously along the broad size of the guide is considered. In general, this problem has no exact solution, thus numerical techniques should be used. In this article, the pseudospectral frequency‐domain (PSFD) method is proposed to address the problem. Starting from the Helmholtz equation, a matrix eigenvalue problem is obtained by applying the collocation technique with Chebyshev polynomials as basis functions. The results obtained are compared with those calculated by the conventional finite‐difference frequency‐domain method showing that the PSFD technique provides an excellent accuracy. [ABSTRACT FROM AUTHOR]

The radial basis function-generated-finite-difference (RBF-FD) method is applied to the analysis of homogenous waveguides. To this end, the Helmholtz equation and the boundary conditions are collocated on the waveguide cross section. At each collocation node, derivatives are locally approximated by the RBF-FD formulas based on the polyharmonic splines supplemented with high-degree polynomials. As a result, a sparse matrix eigenvalue problem is obtained, which allows cutoff wavenumbers and axial fields to be calculated. To illustrate the accuracy of the method, we consider a semicircular and an eccentric circular waveguide. [ABSTRACT FROM AUTHOR]

Engineering low‐band‐gap π‐conjugated polymers is a growing area in basic and applied research. The main synthetic challenge lies in the solubility of the starting materials, which precludes advancements in the field. Here, we report an on‐surface synthesis protocol to overcome such difficulties and produce poly(p‐anthracene ethynylene) molecular wires on Au(111). To this aim, a quinoid anthracene precursor with =CBr2 moieties is deposited and annealed to 400 K, resulting in anthracene‐based polymers. High‐resolution nc‐AFM measurements confirm the nature of the ethynylene‐bridge bond between the anthracene moieties. Theoretical simulations illustrate the mechanism of the chemical reaction, highlighting three major steps: dehalogenation, diffusion of surface‐stabilized carbenes, and homocoupling, which enables the formation of an ethynylene bridge. Our results introduce a novel chemical protocol to design π‐conjugated polymers based on oligoacene precursors and pave new avenues for advancing the emerging field of on‐surface synthesis. [ABSTRACT FROM AUTHOR]

A uniaxial bianisotropic, full-dielectric structure has been designed and numerically studied. The material is based on a previously published 2D-honeycomb structure. A 3D expansion leads to an effective metamaterial showing a typical chiral electromagnetic behavior, i.e., a resonant electromagnetic activity with a small circular dichroism. [ABSTRACT FROM AUTHOR]