Functional group corrections to the GFN2-xTB and PM6 semiempirical methods for noncovalent interactions in alkanes and alkenes.

Analytical corrections were developed to improve the accuracy of the PM6 and GFN2-xTB semiempirical quantum mechanical methods for the evaluation of noncovalent interaction energies in alkanes and alkenes. We followed the approach of functional group corrections, wherein the atom-atom pair corrections depend on the nature of the interacting functional groups. The training set includes 21 alkane and 13 alkene complexes taken from the Donchev et al.'s database [Sci. Data 8, 55 (2021)], with interaction energies calculated at the CCSD(T)/CBS level, and our own data obtained for medium-size complexes (of 100 and 112 atoms). In general, for the systems included in the training and validation sets, the errors obtained with the PM6-FGC and xTB-FGC methods are within the chemical accuracy.

AutoMeKin2021: An open-source program for automated reaction discovery.

AutoMeKin2021 is an updated version of tsscds2018, a program for the automated discovery of reaction mechanisms (J. Comput. Chem. 2018, 39, 1922). This release features a number of new capabilities: rare-event molecular dynamics simulations to enhance reaction discovery, extension of the original search algorithm to study van der Waals complexes, use of chemical knowledge, a new search algorithm based on bond-order time series analysis, statistics of the chemical reaction networks, a web application to submit jobs, and other features. The source code, manual, installation instructions and the website link are available at: https://rxnkin.usc.es/index.php/AutoMeKin.

Correlation between ferromagnetic and isotopic tracers for sentinel lymph node detection in cutaneous melanoma: IMINEM study.

BACKGROUND: The usefulness of sentinel lymph node biopsy (SLNB) in staging cutaneous melanoma has been proven. Therefore, different tracers have been used to identify the sentinel lymph nodes (SLNs). The use of isotopic tracers together with radioactivity detectors allowed a much more precise and direct approach to the SLNs. However, not all centres have access to a Nuclear Medicine department hindering sentinel lymph node detection (SLND) and consequently, other markers such as ferromagnetic tracers have been evaluated looking for the same advantages and effectiveness as isotopic tracers. Ferromagnetic tracers have proven their usefulness in other cancer entities such as breast, prostate and thyroid cancer. The objective was to assess the detection and concordance rates between isotopic and ferromagnetic techniques for SLNB in cutaneous melanoma. METHOD: Isotopic SLNB technique and ferromagnetic tracer were compared for cutaneous melanoma in a non-inferiority multicentre prospective study carried out in six Spanish hospitals. RESULTS: A total of 60 patients were recruited and 133 lymph nodes removed. The detection rate was slightly higher with ferromagnetic tracer in head-neck and trunk melanomas, and with isotopic tracer in limbs. The patients' and nodes' concordance rates between both techniques for ex vivo samples were 95% and 86% for head-neck and trunk tumours and 97% and 93% for limbs tumours, respectively. The concordance rates for involved nodes were 100% and 88.2% for patients and nodes, respectively. CONCLUSION: The intraoperative detection and biopsy of SLN in cutaneous melanoma using a ferromagnetic was a reliable alternative method to the isotopic technique in cutaneous melanomas.

tsscds2018: A code for automated discovery of chemical reaction mechanisms and solving the kinetics.

A new software, called tsscds2018, has been developed to discover reaction mechanisms and solve the kinetics in a fully automated fashion. The program employs algorithms based on Graph Theory to find transition state (TS) geometries from accelerated semiempirical dynamics simulations carried out with MOPAC2016. Then, the TSs are connected to the corresponding minima and the reaction network is obtained. Kinetic data like populations vs time or the abundancies of each product can also be obtained with our program thanks to a Kinetic Monte Carlo routine. Highly accurate ab initio potential energy diagrams and kinetics can also be obtained using an interface with Gaussian09. The source code is available on the following site: http://forge.cesga.es/wiki/g/tsscds/HomePage © 2018 Wiley Periodicals, Inc.

Collision-induced dissociation mechanisms of [Li(uracil)]+.

The collision-induced dissociation (CID) of the [Li(uracil)](+) complex with Xe is studied by means of quasi-classical trajectory calculations. The potential energy surface is obtained "on the fly" from AM1 semiempirical calculations, supplemented with two-body analytical potentials to model the intermolecular interactions. The simulations show that Li(+) production is the primary channel, in agreement with a previous experimental study [M. T. Rodgers and P. B. Armentrout, J. Am. Chem. Soc., 2000, 122, 8548]. Collision-induced isomerization of [Li(uracil)](+) was found to be very important as well in the 2.5-10 eV collision energy range. Three minor channels are also identified: complex formation between Xe and [Li(uracil)](+), ligand exchange to form LiXe(+), and fragmentations of the uracil ring, which are strongly nonstatistical. Additional quasi-classical trajectory calculations carried out to investigate in more detail the fragmentations of the uracil ring reveal the presence of bifurcations in the potential energy surface, as trajectories starting from a transition state give rise to four different product channels. The integral cross sections for Li(+) production calculated in this work agree well with those obtained in the experiments only for the lowest collision energies, being ∼20 times greater than the experimental values for a collision energy of 10 eV. Finally, the initial translational energy is transferred preferentially to the [Li(uracil)](+) vibrational degrees of freedom, with energy transfer to rotation being modest. The amount of energy transfer to the different degrees of freedom as a function of the collision energy follows quite nicely a model recently proposed by our group.

Epigenetics, the role of DNA methylation in tree development.

During development of multicellular organisms, cells become differentiated by modulating different programs of gene expression. Cells have their own epigenetic signature which reflects genotype, developmental history, and environmental influences, and it is ultimately reflected in the phenotype of the cells and the organism. However, in normal development or disease situations, such as adaptation to climate change or during in vitro culture, some cells undergo major epigenetic reprogramming involving the removal of epigenetic marks in the nuclei followed by the establishment of a different new set of marks. Compared with animal cells, biotech-mediated achievements are reduced in plants despite the presence of cell polypotency. In forestry, any sustainable developments using biotech tools remain restricted to the lab, without progressing to the field for application. Such barriers in the translation between development and implementation need to be addressed by organizations that have the power to integrate these two fields. However, a lack of understanding of gene regulation is also to blame for this barrier. In recent years, great progress has been made in unraveling the control of gene expression. These advances are discussed in this chapter, including the possibility of applying this knowledge in forestry practice.

Basic procedures for epigenetic analysis in plant cell and tissue culture.

In vitro culture is one of the most studied techniques, and it is used to study many developmental processes, especially in forestry species, because of growth timing and easy manipulation. Epigenetics has been shown as an important influence on many research analyses such as cancer in mammals and developmental processes in plants such as flowering, but regarding in vitro culture, techniques to study DNA methylation or chromatin modifications were mainly limited to identify somaclonal variation of the micropropagated material. Because in vitro culture is not only a way to generate plant material but also a bunch of differentially induced developmental processes, an approach of techniques and some research carried out to study the different changes regarding DNA methylation and chromatin and translational modifications that take place during these processes is reviewed.

Ab initio and RRKM study of the HCN/HNC elimination channels from vinyl cyanide.

Ab initio CCSD and CCSD(T) calculations with the 6-311+G(2d,2p) and the 6-311++G(3df,3pd) basis sets were carried out to characterize the vinyl cyanide (C(3)H(3)N) dissociation channels leading to hydrogen cyanide (HCN) and its isomer hydrogen isocyanide (HNC). Our computations predict three elimination channels giving rise to HCN and another four channels leading to HNC formation. The relative HCN/HNC branching ratios as a function of internal energy of vinyl cyanide were computed using RRKM theory and the kinetic Monte Carlo method. At low internal energies (120 kcal/mol), the total HCN/HNC ratio is about 14, but at 148 kcal/mol (193 nm) this ratio becomes 1.9, in contrast with the value 124 obtained in a previous ab initio/RRKM study at 193 nm (Derecskei-Kovacs, A.; North, S. W. J. Chem. Phys.1999, 110, 2862). Moreover, our theoretical results predict a ratio of rovibrationally excited acetylene over total acetylene of 3.3, in perfect agreement with very recent experimental measurements (Wilhelm, M. J.; Nikow, M.; Letendre, L.; Dai, H.-L. J. Chem. Phys.2009, 130, 044307).

Violencia doméstica en la tercera edad / Domestic violence at the older age

La violencia doméstica es tan antigua como la humanidad. Se reconoce la violencia infantil, contra la mujer y al anciano El último grupo està conformado por una población en ascenso por las mayores expectativas de vida de los últimos años dadas, entre otros factores, por los avances médicos actuales y los estilos de vida saludables. Cuba tiene actualmente el 13 por ciento de la población con 65 años y màs y según estimados, para el 2020 existiràn por primera vez màs ancianos que niños. Por ello, en los próximos años habrà que seguir de cerca el trato a este grupo poblacional. Es de esperar que se incremente el abuso contra el anciano y el impacto de este abuso sobre la salud debe ser considerado. La gama de maltratos que puede sufrir el anciano incluye fundamentalmente, el abuso físico, emocional, financiero, sexual, por negligencia y la negación a brindarle ayuda. Garantizarles condiciones de vida que les ofrezcan independencia, protegerlos jurídicamente, crearles espacios adonde acudir para reclamar por las violaciones que pudieran sufrir y brindarles información a ellos y a la sociedad sobre las formas en que se puede manifestar el maltrato, son acciones que deben cumplirse con exactitud y que contribuirían a la prevención de la violencia

Domestic violence is as old as the origin of mankind. Infant violence and violence against the woman and the old person are well known. The older people group represents a growing population due to higher life expectancies in the last few years encouraged by the present medical advances and healthier life styles. Nowadays, 13 percent of the Cuban population is 65 years and over; but according to estimates, the elderly will outnumber the children for the first time in 2020. Therefore, one must closely watch the treatment to this population section in the forthcoming year. It is expected that elder abuse grows, so the impact of abuse on health should be taken into account. Mistreatment of the elderly mainly includes physical, emotional, financial, sexual abuse, negligence and denial of assistance. Providing them with living conditions that encourage independence, protect them from the legal viewpoint, creating adequate sites where they may claim for possible violations and giving them and the society information on the various forms of abuse are all actions that should be fully taken since they will contribute to the prevention of violence

Violencia doméstica en la tercera edad / Domestic violence at the older age

La violencia doméstica es tan antigua como la humanidad. Se reconoce la violencia infantil, contra la mujer y al anciano El último grupo està conformado por una población en ascenso por las mayores expectativas de vida de los últimos años dadas, entre otros factores, por los avances médicos actuales y los estilos de vida saludables. Cuba tiene actualmente el 13 por ciento de la población con 65 años y màs y según estimados, para el 2020 existiràn por primera vez màs ancianos que niños. Por ello, en los próximos años habrà que seguir de cerca el trato a este grupo poblacional. Es de esperar que se incremente el abuso contra el anciano y el impacto de este abuso sobre la salud debe ser considerado. La gama de maltratos que puede sufrir el anciano incluye fundamentalmente, el abuso físico, emocional, financiero, sexual, por negligencia y la negación a brindarle ayuda. Garantizarles condiciones de vida que les ofrezcan independencia, protegerlos jurídicamente, crearles espacios adonde acudir para reclamar por las violaciones que pudieran sufrir y brindarles información a ellos y a la sociedad sobre las formas en que se puede manifestar el maltrato, son acciones que deben cumplirse con exactitud y que contribuirían a la prevención de la violencia(AU)

Domestic violence is as old as the origin of mankind. Infant violence and violence against the woman and the old person are well known. The older people group represents a growing population due to higher life expectancies in the last few years encouraged by the present medical advances and healthier life styles. Nowadays, 13 percent of the Cuban population is 65 years and over; but according to estimates, the elderly will outnumber the children for the first time in 2020. Therefore, one must closely watch the treatment to this population section in the forthcoming year. It is expected that elder abuse grows, so the impact of abuse on health should be taken into account. Mistreatment of the elderly mainly includes physical, emotional, financial, sexual abuse, negligence and denial of assistance. Providing them with living conditions that encourage independence, protect them from the legal viewpoint, creating adequate sites where they may claim for possible violations and giving them and the society information on the various forms of abuse are all actions that should be fully taken since they will contribute to the prevention of violence(AU)

Victimización infantil: un problema de salud en el sistema social capitalista / Child victimization: a health problem in the capitalist social system

La victimización infantil es un fenómeno complejo de la sociedad conocido desde hace siglos. Hacia 1946, se crea la UNICEF, como primer organismo internacional para proteger la infancia, siendo esta la base para llegar a la Convención sobre los Derechos del Niño y posteriormente a la Cumbre sobre la Infancia de 1990. El incremento de la victimización infantil está estrechamente vinculado a la globalización que vive el mundo. La violencia infantil está asociada a la falta de preocupación de los estados por legislar primeramente y luego hacer cumplir las leyes que protejan a los infantes. Se tipifican algunos delitos contra los menores así como las diferentes modalidades de explotación infantil: tráfico de menores, la pornografía y prostitución infantil así como el contrabando de órganos. Se plantea que en la inmensa mayoría de los países del mundo, el trabajo no constituye una forma de capacitación y sin duda, una forma de explotación y violación de los derechos del niño. La violencia se manifiesta independientemente del sexo, raza o precedencia étnica, produciéndose de manera indistinta el abuso sexual, el físico o el emocional. La violencia contra la infancia está presente en todas las esferas de la sociedad capitalista haciéndose más crítica en los países del tercer mundo. Las acciones emprendidas por Cuba, Venezuela y otros, son ejemplos de cuanto se alcanza con mucha voluntad política y pocos recursos en la defensa de los derechos del niño.

The child victimisation is a complex phenomenon of the society known for centuries. In 1946, UNICEF was created as first international organization to protect childhood, being the basis for the Convention on the Rights of Childhood and subsequently the Summit on the Childhood in 1990. The increased child victimisation is closely linked to the globalization. The child violence is associated to lack of concern by the states regarding legislation and putting into effect laws that protect the infants. This article categorizes some crimes against children as well as different forms of child exploitation (children traffic, infant pornography and child prostitution as well as organ smuggling.) It is stated that in most of the countries, child work is not a way of training but exploitation and violation of the child's rights. Violence is present regardless of sex, race or ethnic origin leading to sexual abuse. Violence against children is present in all the spheres of the capitalist society, being more acute in the Third World countries. The actions undertaken by Cuba, Venezuela and others are examples of the achievements that can be attained in the defense of the children's rights with much political willingness and few resources.

Victimización infantil, un problema de salud en el sistema social capitalista / Child victimization, a health problem in the capitalist social system

La victimización infantil es un fenómeno complejo de la sociedad conocido desde hace siglos. Hacia 1946, se crea la UNICEF, como primer organismo internacional para proteger la infancia, siendo esta la base para llegar a la Convención sobre los Derechos del Niño y posteriormente a la Cumbre sobre la Infancia de 1990. El incremento de la victimización infantil está estrechamente vinculado a la globalización que vive el mundo. La violencia infantil está asociada a la falta de preocupación de los estados por legislar primeramente y luego hacer cumplir las leyes que protejan a los infantes. Se tipifican algunos delitos contra los menores así como las diferentes modalidades de explotación infantil: tráfico de menores, la pornografía y prostitución infantil así como el contrabando de órganos. Se plantea que en la inmensa mayoría de los países del mundo, el trabajo no constituye una forma de capacitación y sin duda, una forma de explotación y violación de los derechos del niño. La violencia se manifiesta independientemente del sexo, raza o precedencia étnica, produciéndose de manera indistinta el abuso sexual, el físico o el emocional. La violencia contra la infancia está presente en todas las esferas de la sociedad capitalista haciéndose más crítica en los países del tercer mundo. Las acciones emprendidas por Cuba, Venezuela y otros, son ejemplos de cuanto se alcanza con mucha voluntad política y pocos recursos en la defensa de los derechos del niño(AU)

The child victimisation is a complex phenomenon of the society known for centuries. In 1946, UNICEF was created as first international organization to protect childhood, being the basis for the Convention on the Rights of Childhood and subsequently the Summit on the Childhood in 1990. The increased child victimisation is closely linked to the globalization. The child violence is associated to lack of concern by the states regarding legislation and putting into effect laws that protect the infants. This article categorizes some crimes against children as well as different forms of child exploitation (children traffic, infant pornography and child prostitution as well as organ smuggling.) It is stated that in most of the countries, child work is not a way of training but exploitation and violation of the child's rights. Violence is present regardless of sex, race or ethnic origin leading to sexual abuse. Violence against children is present in all the spheres of the capitalist society, being more acute in the Third World countries. The actions undertaken by Cuba, Venezuela and others are examples of the achievements that can be attained in the defense of the children's rights with much political willingness and few resources(AU)

Reactivación de material vegetal élite de Pinus radiata D. Don. mediante microinjerto in vitro / Reactivation of elite Pinus radiata D. Don. plant tissue by in vitro micrografting

Se evaluaron dos protocolos de asepsia, tipos de púa (yemas y braquiblastos), épocas de recolección (otoño y verano) y posición de la púa (apical y basal) en el ortet, sobre el establecimiento y consolidación de microinjertos de Pinus radiata D. Don. Las púas se obtuvieron de clones adultos cultivados en vivero. Las asepsias consistieron en la inmersión en hipoclorito de sodio 2,5 por ciento v/v i.a, durante 15min (A1); o por 20min, seguido de la inmersión en una solución de benomyl+cisteína 50mg·l-1 c/u, hasta su utilización (A2). Como patrón se utilizaron hipocótilos provenientes de semillas germinadas in vitro en medio QL sin reguladores de crecimiento. Se realizaron microinjertos según la técnica apical de cuña. Estos se mantuvieron en tubos con medio QL + 0,1 mg·l-1 AIB y 1mg·l-1 BAP, a 25 ±2°C, intensidad lumínica de 80µmol·m-2·s-1 y fotoperíodo de 16h. Se utilizó un diseño completamente al azar en arreglo factorial (24), con 13 repeticiones. El establecimiento mostró diferencias significativas entre las interacciones tipo de asepsia/época del año y tipo de púa/época del año, resultando ser las yemas apicales recolectadas durante el otoño y la asepsia tipo A2, los mejores tratamientos para el establecimiento de los microinjertos de P. radiata. La consolidación estuvo influenciada por el tipo de púa y la época del año en que se realizaron los microinjertos, siendo nuevamente la yema apical (YA) el material más reactivo.