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Depression is a multifactorial disease with unknown etiology affecting globally. It’s the second most significant reason for infirmity in 2020, affecting about 50 million people worldwide, with 80% living in developing nations. Recently, a surge in depression research has been witnessed, resulting in a multitude of emerging techniques developed for prediction, evaluation, detection, classification, localization, and treatment. The main purpose of this study is to determine the volume of depression research conducted on different aspects such as genetics, proteins, hormones, oxidative stress, inflammation, mitochondrial dysfunction, and associations with other mental disorders like anxiety and stress using traditional and medical intelligence (medical with AI). In addition, it also designs a comprehensive survey on detection, treatment planning, and genetic predisposition, along with future recommendations. This work is designed through different methods, including a systematic mapping process, literature review, and network visualization. In addition, we also used VOSviewer software and some authentic databases such as Google Scholar, Scopus, PubMed, and Web of Science for data collection, analysis, and designing comprehensive picture of the study. We analyzed 60 articles related to medical intelligence, including 47 from machine learning with 513,767 subjects (mean ± SD = 10,931.212 ± 35,624.372) and 13 from deep learning with 37,917 subjects (mean ± SD = 3159.75 ± 6285.57). Additionally, we also found that stressors impact the brain's cognitive and autonomic functioning, resulting in increased production of catecholamine, decreased cholinergic and glucocorticoid activity, with increased cortisol. These factors lead to chronic inflammation and hinder the brain's normal functioning, leading to depression, anxiety, and cardiovascular disorders. In the brain, reactive oxygen species (ROS) production is increased by IL-6 stimulation and mitochondrial cytochrome c oxida

Objectives: To elucidate the association between genetic variants and the risk of GCA via large-scale genome-wide association studies (GWAS). In addition, to assess the causal effect of a specific molecule by employing the obtained GWAS results as genetic epidemiological tools. Methods: We applied additional variant quality control to the publicly available GWAS results from the biobanks of the UK (UKBB) and Finland (FinnGen), which comprised 532 cases vs 408 565 controls and 884 cases vs 332 115 controls, respectively. We further meta-analysed these two sets of results. We performed two-sample Mendelian randomization (MR) to test the causal effect of low-density lipoprotein (LDL) cholesterol on the risk of GCA. Results: The MHC class II region showed significant associations in UKBB, FinnGen and the meta-analysis. The VLDLR region was associated with GCA risk in the meta-analysis. The T allele of rs7044155 increased the expression of VLDLR, decreased the LDL cholesterol level and decreased the disease risk. The subsequent MR results indicated that a 1 S.D. increase in LDL cholesterol was associated with an increased risk of GCA (odds ratio 1.21, 95% CI 1.01–1.45; P = 0.04). Conclusions: Our study identified associations between GCA risk and the MHC class II and VLDLR regions. Moreover, LDL cholesterol was suggested to have a causal effect on the risk of developing GCA.

Research and development (R&D) in the pharmaceutical sector traditionally operated with in closed, siloed institutional settings, driven by intellectual property rights concerns that viewed data sharing as a threat. However, the evolving scientific landscape demands a more collaborative approach involving external engagement and dynamic partnerships. To address this, a hybrid contractual framework combining smart contracts, non-fungible tokens (NFTs), and traditional licensing schemes is introduced. This framework was developed through an experimental pilot platform that adhered to FAIR data principles, allowing participants to store, find, and reuse data related to drug discovery. The platform utilizes blockchain technology to document real-world assets in an immutable digital ledger. Smart contracts and NFTs offer an open and global collaborative platform for advancing drug research assets, overcoming hurdles related to standardization, interoperability, and disclosure. This framework aims to reconcile the conflict between the demand for greater data sharing and the protection of rightsholder interests in pharmaceutical R&D. By providing mechanisms for resolving practical challenges, it facilitates further cooperation and innovation in the field.

In recent years, there has been significant progress in the field of quantum information processing and quantum sensing. Researchers have been actively exploring new quantum systems that possess high accuracy, scalability, and compatibility with other systems. The focus of this thesis is to examine various molecular systems that hold promise for quantum sensing and information processing applications.We report a ferrocene-supported ytterbium based complex ((thiolfan)YbCl(THF), thiolfan = 1,1'-bis(2,4-di-tert-butyl-6-thiomethylenephenoxy)ferrocene) that exhibits an isolated ultranarrow absorption linewidth in solution at room temperature with a full width at half maximum (FWHM) of (151 $\pm$ 1) GHz. A detailed absorption spectroscopy analysis from room temperature (RT) to 5 K and emission spectroscopy allow us to assign the narrow near infrared (NIR) transitions to atom-centered \textit{f-f} transitions. Zeeman spectroscopy and electron paramagnetic resonance measurement help us to determine the dominant quantum numbers and Land\'e g-factors of the ground and excited states. A combination of density functional theory and multireference methods match experimental transition energies and oscillator strengths, providing insights into the role of spin-orbit coupling and asymmetric ligand field in enhancing absorption and pointing toward molecular design principles that create well-protected yet observable electronic transitions in lanthanide (Ln) complexes.We demonstrate that the ultranarrow linewidth of this system allows for magnetic field imaging and magnetic field sensing down to Earth scale, which we term an "atom-like molecular sensor" (ALMS). Furthermore, by optically depleting some population, we are able to selectively address the burned spectral hole with a FHWM of 99 kHz, paving the way for optical state preparation and readout of ground state coherence in this liquid molecular system.In addition, we also describe our efforts in building surface-based molecula

© 2002 The American Physical Society. The authors would like to thank John Jefferson for helpful discussions and comments. This research was supported by the EU through the TMR program ‘‘Quantum Transport in the Frequency and Time Domains,’’ and by the DGES (Spain) through Grant No. PB96-0875., In the limit of low particle density, electrons confined to a quantum dot form strongly correlated states termed Wigner molecules, in which the Coulomb interaction causes the electrons to become highly localized in space. By using an effective model of Hubbard-type to describe these states, we investigate how an oscillatory electric field can drive the dynamics of a two-electron Wigner molecule held in a square quantum dot. We find that, for certain combinations of frequency and strength of the applied field, the tunneling between various charge configurations can be strongly quenched, and we relate this phenomenon to the presence of anticrossings in the Floquet quasi-energy spectrum. We further obtain simple analytic expressions for the location of these anti-crossings, which allows the effective parameters for a given quantum dot to be directly measured in experiment, and suggests the exciting possibility of using ac-fields to control the time evolution of entangled states in mesoscopic devices., EU through the TMR program ‘‘Quantum Transport in the Frequency and Time Domains,’’, DGES (Spain), Depto. de Física de Materiales, Fac. de Ciencias Físicas, TRUE, pub

The development of synthetic molecules able to transport ions through lipid bilayer membranes is of growing interest in the field of supramolecular chemistry. The balance of anions and cations has an important role in the biology of all living organisms. This thesis will focus on the development of copper(I) transporters, the methodologies developed to study them, and their biological applications. The first part of this thesis is focused on the development of copper(I) transmembrane transporters and the methodology required for their study. These transporters were developed for a potential therapeutic application, with the idea that synthetic copper(I) transporters could replace dysfunctional copper(I) transport proteins, which are responsible for distributing copper(I) within cells. Dysfunction of these proteins is the cause of Wilson and Menkes diseases.Calix4arene functionalised with two imidazole groups can strongly bind copper(I) through a linear coordination motif. This ability and their high lipophilicity made them good candidates to transport copper(I) through bilayer membranes. For that, a new assay was developed using liposomes as model systems for membranes, in which a phenanthroline based copper(I) sensitive dye is encapsulated. The changes in fluorescence as monitored by spectroscopy allowed for the observation of copper(I) transport. Most of these results are reported in the publication: “Transmembrane transport of copper(I) by imidazole-functionalised calix[4]arenes” N. Renier, O. Reinaud, I. Jabin, and H. Valkenier. Chem. Commun. 2020, 56, 8206-8209. The improvement and limitations of the transport assay are also described. In the second part, the development of a deliverable copper(I) transporter is described along with the biological effects of the compound on various biological systems. A new transporter was synthesised and shown to be able to reach liposomes membrane when added from an organic solution or from other liposomes, which was not th, Doctorat en Sciences de l'ingénieur et technologie, info:eu-repo/semantics/nonPublished

Sleep is vital for all mammals including humans, its distortion implies different health risks and pathologies such as depression, and cardiovascular diseases, and in the end, it can lead to death. In this sense, it is important to find the molecular bases of sleep, among them the genes and their proteins that play a key role in the homeostasis of the living being. Information was collected using the PubMed/Scopus databases in English with a 10-year history using the PICO methodology to determine the words P=Genes, I=Molecular basis, C=Not applicable, O=Sleep. Original articles were determined into two large groups, among these are the "Clock Genes" and other "Genes and Proteins" related to sleep. Among the important clock genes identified are those linked to dopamine (DRD 2) and (DAT 1) and other genes such as pdm3 that participate in the genesis of the innervation of the dopaminergic system and the ANXA3 and 17GAM genes which has shown that overexpression of these is related to sleep deprivation. Understanding the molecular bases of sleep and its gaps still to be studied are key to future studies such as identifying targets and drugs to treat sleep disorders., El sueño es vital para todos los mamíferos incluyendo al ser humano, su distorsión implica diferentes riesgos para la salud y patologías como depresión, enfermedades cardiovasculares y en el extremo puede llevar a la muerte. En ese sentido es de importancia encontrar las bases moleculares del sueño entre ellos los genes y sus proteínas que ejecutan un rol clave en la homeostasis del ser vivo. Se recopiló información utilizando las bases de datos PubMed/Scopus en ingles con 10 años de anterioridad utilizando el protocolo PICO para determinar las palabras P=Genes, I=Base molecular, C=No aplica, O= Sueño. Se determinaron artículos originales en dos grandes grupos entre estos estan los “Genes Reloj” y otros “Genes y Proteínas” relacionados al sueño. Entre los genes reloj de importancia identificados están los vinculados a la dopamina (DRD 2) y el (DAT 1) y otros genes como el pdm3 que participa en la génesis de la inervación del sistema dopaminérgico y los genes ANXA3 y 17GAM, en la que se ha demostrado que una sobreexpresión de estos se relaciona a la privación del sueño. Entender las bases moleculares del sueño y sus vacíos aun por estudiar son clave para futuros estudios como identificar dianas y drogas para tratar los trastornos del sueño.

Tidigare forskning visar att det knappt finns forskning om vilken undervisningsform som lämpar sig för implementering för yngre elever i kemi. Frågan om att hitta en undervisningsmetod som ökar elevernas prestationer i kemi är en utmaning i det moderna skolsystemet. Fortsättningsvis visar forskning att laborationer inte var en lämplig undervisningsform som introduktion för ett naturvetenskapligt lärande i de lägre åldrarna, men det saknas gedigna empiriska bevis som stödjer detta påstående. Därför, i den föreliggande studien, undersöks laboratorie- och traditionella undervisningsmetoder på ämnet vattnets aggressionsformer. Denna studie involverade 50 deltagare som är grundskoleelever i årskurs 3. Data samlades in med ett för- och eftertest. Resultatet av denna studie visade ingen uppenbar skillnad i testpoängen mellan jämförelse- och experimentgruppen. Resultaten visade även att den laborativa undervisningsmetoden gav ett bättre utfall på elevernas förståelse på mikronivå. Till skillnad från experimentgruppen kunde den traditionella undervisningen nämna vattnets fasomvandlingar mycket mer än vad laboratorieundervisningen kunde. Avslutningsvis, visade studien ingen tydlig skillnad i testpoängen mellan jämförelse- och experimentgrupp., Previous research shows that there is hardly any research on teaching methods suitable for implementation for younger students in chemistry. The issue of finding a teaching method that increases student achievement in chemistry is a challenge in modern school systems. Research shows that laboratory work was not a suitable form of teaching as an introduction to chemistry at younger ages, but there is a lack of solid empirical evidence to support this claim. Therefore, in the present study, the laboratory and traditional teaching methods are examined on the topic of water's state of matter. The research involved fifty participants that are primary school students in grade 3. Data was collected using a pre-test and post-test. The results also showed that the laboratory teaching method improved students' understanding at the micro-level. Unlike the experimental group, the traditional teaching could mention water phase transformations much more than the laboratory teaching could. The outcome of this study showed no evident difference in the test scores between the comparison and experimental groups.

The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO2 nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with N-hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO2 NPs. The covalent bond to the silica surface was confirmed by solid state NMR, whereas thermogravimetric analysis unveiled a functionalization degree much higher compared to that achieved by a conventional double-step post-grafting procedure. In light of these intriguing results, the strategy was successfully extended to naturally occurring sepiolite fibers, widely employed as fillers in technological applications. Finally, a preliminary proof of concept of the photoreversibility of the obtained SiO2@CINN-APTES system has been carried out through UV diffuse reflectance. The overall outcomes prove the consistency and the versatility of the methodological protocol adopted, which appears promising for the design of hybrid NPs to be employed as building blocks for photoresponsive materials with the ability to change their molecular structure and subsequent properties when exposed to different light stimuli.

Tidigare forskning visar att det knappt finns forskning om vilken undervisningsform som lämpar sig för implementering för yngre elever i kemi. Frågan om att hitta en undervisningsmetod som ökar elevernas prestationer i kemi är en utmaning i det moderna skolsystemet. Fortsättningsvis visar forskning att laborationer inte var en lämplig undervisningsform som introduktion för ett naturvetenskapligt lärande i de lägre åldrarna, men det saknas gedigna empiriska bevis som stödjer detta påstående. Därför, i den föreliggande studien, undersöks laboratorie- och traditionella undervisningsmetoder på ämnet vattnets aggressionsformer. Denna studie involverade 50 deltagare som är grundskoleelever i årskurs 3. Data samlades in med ett för- och eftertest. Resultatet av denna studie visade ingen uppenbar skillnad i testpoängen mellan jämförelse- och experimentgruppen. Resultaten visade även att den laborativa undervisningsmetoden gav ett bättre utfall på elevernas förståelse på mikronivå. Till skillnad från experimentgruppen kunde den traditionella undervisningen nämna vattnets fasomvandlingar mycket mer än vad laboratorieundervisningen kunde. Avslutningsvis, visade studien ingen tydlig skillnad i testpoängen mellan jämförelse- och experimentgrupp., Previous research shows that there is hardly any research on teaching methods suitable for implementation for younger students in chemistry. The issue of finding a teaching method that increases student achievement in chemistry is a challenge in modern school systems. Research shows that laboratory work was not a suitable form of teaching as an introduction to chemistry at younger ages, but there is a lack of solid empirical evidence to support this claim. Therefore, in the present study, the laboratory and traditional teaching methods are examined on the topic of water's state of matter. The research involved fifty participants that are primary school students in grade 3. Data was collected using a pre-test and post-test. The results also showed that the laboratory teaching method improved students' understanding at the micro-level. Unlike the experimental group, the traditional teaching could mention water phase transformations much more than the laboratory teaching could. The outcome of this study showed no evident difference in the test scores between the comparison and experimental groups.

В данной статье собраны вместе опубликованные ранее доказательства единой природы физических процессов и явлений в веществе с точки зрения изменения энергии молекулы вещества. Доказана единая физическая природа всех этих физических явлений, как единого многоступенчатого процесса энергетической распаковки молекул вещества, которую логично назвать молекулярно-энергетической концепцией распаковки вещества. К рассмотренным процессам относятся следующие процессы. Разрыв поверхности, характеризуемый коэффициентом поверхностного натяжения. Процесс плавления вещества, характеризуемый температурой плавления. Процесс кипения, характеризуемый температурой кипения. Процесс испарения (и конденсации), характеризуемый внутренней энергией и энтальпией, а также критической температурой. Выводы теории подтверждены известными эмпирическими зависимостями и данными из справочников физических свойств простых веществ: внутренней энергии, энтальпии, поверхностного натяжения, температур плавления, кипения и критической температуры., This article brings together previously published evidence of the unified nature of physical processes and phenomena in terms of changes in the energy of a substance molecule. The unified physical nature of all these physical phenomena has been proven, as a single multistage process of energetic unpacking of molecules of a substance, which is logical to call the molecular-energy concept of unpacking a substance. The considered processes include the following processes. Surface rupture, characterized by the surface tension coefficient. The melting process of a substance characterized by its melting point. A boiling process characterized by the boiling point. Evaporation (and condensation) process characterized by internal energy and enthalpy as well as critical point. The conclusions of the theory are confirmed by well-known empirical dependences and by reference books of the physical properties of simple substances: internal energy, enthalpy, surface tension, melting point, boiling point and critical point.

В данной статье собраны вместе опубликованные ранее доказательства единой природы физических процессов и явлений в веществе с точки зрения изменения энергии молекулы вещества. Доказана единая физическая природа всех этих физических явлений, как единого многоступенчатого процесса энергетической распаковки молекул вещества, которую логично назвать молекулярно-энергетической концепцией распаковки вещества. К рассмотренным процессам относятся следующие процессы. Разрыв поверхности, характеризуемый коэффициентом поверхностного натяжения. Процесс плавления вещества, характеризуемый температурой плавления. Процесс кипения, характеризуемый температурой кипения. Процесс испарения (и конденсации), характеризуемый внутренней энергией и энтальпией, а также критической температурой. Выводы теории подтверждены известными эмпирическими зависимостями и данными из справочников физических свойств простых веществ: внутренней энергии, энтальпии, поверхностного натяжения, температур плавления, кипения и критической температуры., This article brings together previously published evidence of the unified nature of physical processes and phenomena in terms of changes in the energy of a substance molecule. The unified physical nature of all these physical phenomena has been proven, as a single multistage process of energetic unpacking of molecules of a substance, which is logical to call the molecular-energy concept of unpacking a substance. The considered processes include the following processes. Surface rupture, characterized by the surface tension coefficient. The melting process of a substance characterized by its melting point. A boiling process characterized by the boiling point. Evaporation (and condensation) process characterized by internal energy and enthalpy as well as critical point. The conclusions of the theory are confirmed by well-known empirical dependences and by reference books of the physical properties of simple substances: internal energy, enthalpy, surface tension, melting point, boiling point and critical point.

Green phosphorus and its monolayer variant, green phosphorene (GreenP), are the recent members of two-dimensional (2D) phosphorus polymorphs. The new polymorph possesses the high stability, tunable direct bandgap, exceptional electronic transport, and directionally anisotropic properties. All these unique features could reinforce it the new contender in a variety of electronic, optical, and sensing devices. Herein, we present gas-sensing characteristics of pristine and defected GreenP towards major environmental gases (i. e., NH3, NO, NO2, CO, CO2, and H2O) using combination of the density functional theory, statistical thermodynamic modeling, and the non-equilibrium Green's function approach (NEGF). The calculated adsorption energies, density of states (DOS), charge transfer, and Crystal Orbital Hamiltonian Population (COHP) reveal that NO, NO2, CO, CO2 are adsorbed on GreenP, stronger than both NH3 and H2O, which are weakly physisorbed via van der Waals interactions. Furthermore, substitutional doping by sulfur can selectively intensify the adsorption towards crucial NO2 gas because of the enhanced charge transfer between p orbitals of the dopant and the analyte. The statistical estimation of macroscopic measurable adsorption densities manifests that the significant amount of NO2 molecules can be practically adsorbed at ambient temperature even at the ultra-low concentration of part per billion (ppb). In addition, the current-voltage (I–V) characteristics of S-doped GreenP exhibit a variation upon NO2 exposure, indicating the superior sensitivity in sensing devices. Our work sheds light on the promising application of the novel GreenP as promising chemical gas sensors., QC 20240109

Using the 1. Mall thermocouple, the relative intensity of radiation in an electric furnace with "black body" details in the temperature range of 300-750 K was measured.2. To check the Stefan-Bolsman law, a graph of the dependence of radiation intensity on absolute temperature and distance was drawn.

Using the 1.Mall thermocouple, the relative intensity of radiation in an electric furnace with "black body" details in the temperature range of 300-750 K was measured. 2. To check the Stefan-Bolsman law, a graph of the dependence of radiation intensity on absolute temperature and distance was drawn.

Using the 1. Mall thermocouple, the relative intensity of radiation in an electric furnace with "black body" details in the temperature range of 300-750 K was measured.2. To check the Stefan-Bolsman law, a graph of the dependence of radiation intensity on absolute temperature and distance was drawn.

Using the 1.Mall thermocouple, the relative intensity of radiation in an electric furnace with "black body" details in the temperature range of 300-750 K was measured. 2. To check the Stefan-Bolsman law, a graph of the dependence of radiation intensity on absolute temperature and distance was drawn.

Experimentelle Untersuchungen negativer Molekülionen, einst beschränkt auf die Bestimmung von Elektronenaffinitäten, ist in den letzten Jahren zu einem Mainstream-Schwerpunkt für physikalische und chemische Forschung. Die Verfügbarkeit von schmalen Lichtquellen, fortschrittlichen Techniken in Ionenspeicherung und Methoden der Aktionsspektroskopie haben Forschergruppen die Charakterisierung von Molekülzustände, Lebensdauer und Dynamik. Die hier vorgestellten veröffentlichten Werke Dissertation einen breiten Überblick über moderne experimentelle Untersuchungen negativer Ionen. Die Spektroskopie des zweiten Schwingungsobertons in OH^- ist ein Beispiel für die Anwendung einer hochmodernen Methode der Aktionsspektroskopie. Schwellenwert für die Lichtablösung des astrophysikalischen Anions CN^- treibt unser Verständnis der Wirkung von molekularen Rotation auf der Dipol-Elektron-Wechselwirkung. Die Beobachtung eines dipolgebundenen Zustands in der Schwellenphotoablösung von C_3N^- weist auf das Potenzial für die Bildung von C_3N^- hin Arten im interstellaren Raum. Die vorstehenden Messungen wurden alle im 22. Polionenfalle betrieben in der Arbeitsgruppe „Molekulare Systeme“ der Universität Innsbruck. Diese Studien verbunden mit der Präsentation von zwei weiteren Projekten, nämlich Quantenzustandspräparation und Detektion von H_2^+ co-gefangen mit lasergekühltem Be^+ in a Lineare Quadrupolfalle im Laboratoire Kastler-Brossel, Paris und Schwellen-Photodetachment von CH^- am DESIREE-Speicherring an der Universität Stockholm Highlight die Vielfalt in der Anwendbarkeit der Molekularspektroskopie und der Bandbreite der Technologien in modernen experimentellen Untersuchungen verwendet., Experimental investigations of negative molecular ions, once restricted to the determination of electron affinities, has, in recent years, become a mainstream focus for physical and chemical research. The availability of narrow light sources, advanced techniques in ion storage and methods of action spectroscopy have allowed research groups to characterise molecular states, lifetimes and dynamics. The published works presented in this dissertation represent a broad overview of modern experimental investigations of negative ions. Spectroscopy of the second vibrational overtone in OH^- is an example of the application of a state of the art method in action spectroscopy. Threshold photodetachment of the astrophysical anion CN^- pushes our understanding of the effects of molecular rotation on the dipole-electron interaction. The observation of a dipole bound state in threshold photodetachment of C_3N^- indicates at the potential for formation of this species in interstellar space. The foregoing measurements were all performed in the 22- pole ion trap operated in the working group “Molecular Systems” at the University of Innsbruck. These studies combined with the presentation of two further projects, namely quantum state preparation and detection of H_2^+ co-trapped with laser cooled Be^+ in a linear quadrupole trap at the Laboratoire Kastler-Brossel, Paris and threshold photodetachment of CH^- at the DESIREE storage ring at Stockholm University highlight the diversity in the applicability of molecular spectroscopy and the range of technologies used in modern experimental investigations., Malcolm James Simpson, MSc, Abweichender Titel laut Übersetzung der Verfasserin/des Verfassers, Kumulative Dissertation aus vier Artikeln, In den Artikeln sind die Zahlen tiefgestellt und -+ hochgestellt, Dissertation University of Innsbruck 2021

Experimentelle Untersuchungen negativer Molekülionen, einst beschränkt auf die Bestimmung von Elektronenaffinitäten, ist in den letzten Jahren zu einem Mainstream-Schwerpunkt für physikalische und chemische Forschung. Die Verfügbarkeit von schmalen Lichtquellen, fortschrittlichen Techniken in Ionenspeicherung und Methoden der Aktionsspektroskopie haben Forschergruppen die Charakterisierung von Molekülzustände, Lebensdauer und Dynamik. Die hier vorgestellten veröffentlichten Werke Dissertation einen breiten Überblick über moderne experimentelle Untersuchungen negativer Ionen. Die Spektroskopie des zweiten Schwingungsobertons in OH^- ist ein Beispiel für die Anwendung einer hochmodernen Methode der Aktionsspektroskopie. Schwellenwert für die Lichtablösung des astrophysikalischen Anions CN^- treibt unser Verständnis der Wirkung von molekularen Rotation auf der Dipol-Elektron-Wechselwirkung. Die Beobachtung eines dipolgebundenen Zustands in der Schwellenphotoablösung von C_3N^- weist auf das Potenzial für die Bildung von C_3N^- hin Arten im interstellaren Raum. Die vorstehenden Messungen wurden alle im 22. Polionenfalle betrieben in der Arbeitsgruppe „Molekulare Systeme“ der Universität Innsbruck. Diese Studien verbunden mit der Präsentation von zwei weiteren Projekten, nämlich Quantenzustandspräparation und Detektion von H_2^+ co-gefangen mit lasergekühltem Be^+ in a Lineare Quadrupolfalle im Laboratoire Kastler-Brossel, Paris und Schwellen-Photodetachment von CH^- am DESIREE-Speicherring an der Universität Stockholm Highlight die Vielfalt in der Anwendbarkeit der Molekularspektroskopie und der Bandbreite der Technologien in modernen experimentellen Untersuchungen verwendet., Experimental investigations of negative molecular ions, once restricted to the determination of electron affinities, has, in recent years, become a mainstream focus for physical and chemical research. The availability of narrow light sources, advanced techniques in ion storage and methods of action spectroscopy have allowed research groups to characterise molecular states, lifetimes and dynamics. The published works presented in this dissertation represent a broad overview of modern experimental investigations of negative ions. Spectroscopy of the second vibrational overtone in OH^- is an example of the application of a state of the art method in action spectroscopy. Threshold photodetachment of the astrophysical anion CN^- pushes our understanding of the effects of molecular rotation on the dipole-electron interaction. The observation of a dipole bound state in threshold photodetachment of C_3N^- indicates at the potential for formation of this species in interstellar space. The foregoing measurements were all performed in the 22- pole ion trap operated in the working group “Molecular Systems” at the University of Innsbruck. These studies combined with the presentation of two further projects, namely quantum state preparation and detection of H_2^+ co-trapped with laser cooled Be^+ in a linear quadrupole trap at the Laboratoire Kastler-Brossel, Paris and threshold photodetachment of CH^- at the DESIREE storage ring at Stockholm University highlight the diversity in the applicability of molecular spectroscopy and the range of technologies used in modern experimental investigations., Malcolm James Simpson, MSc, Abweichender Titel laut Übersetzung der Verfasserin/des Verfassers, Kumulative Dissertation aus vier Artikeln, In den Artikeln sind die Zahlen tiefgestellt und -+ hochgestellt, Dissertation University of Innsbruck 2021

©2020 American Chemical Society C.G. was funded by Spanish Ministry of Science, Innovation and Universities under the projects MAT2017-88258-R and MDM-2014-0377 (María de Maeztu Programme for Units of Excellence in R&D). C.G. acknowledge the computer resources at Cibeles and the technical support provided by 405 the Scientific Computing Center at UAM, project FI-2019- 0028. PM acknowledges support from the A.v. Humboldt Foundation, the ERC Synergy Program (grant no. ERC-2013-SYG-610256, Nanocosmos), Spanish MINECO (MAT2017-85089-C2-1-R) and the “Comunidad de Madrid” for its support to the FotoArt-CM Project S2018/NMT-4367 through the Program of R&D activities between research groups in Technologies 2013, cofinanced by European Structural Funds., The hexagonal close packed surface of gold shows a 22 x root 3 "herringbone" surface reconstruction which makes it unique among the (111) surfaces of all metals. This long-range energetically favored dislocation pattern appears in response to the strong tensile stress that would be present on the unreconstructed surface. Adsorption of molecular and atomic species can be used to tune this surface stress and lift the herringbone reconstruction. Here we show that herringbone reconstruction can be controllably lifted in ultrahigh vacuum at cryogenic temperatures by precise hot electron injection in the presence of hydrogen molecules. We use the sharp tip of a scanning tunneling microscope (STM) for charge carrier injection and characterization of the resulting chain nanostructures. By comparing STM images, rotational spectromicroscopy and ab initio calculations, we show that formation of gold atomic chains is associated with release of gold atoms from the surface, lifting of the reconstruction, dissociation of H_2 molecules, and formation of surface hydrides. Gold hydrides grow in a zipper-like mechanism forming chains along the [1 (1) over bar0] directions of the Au(111) surface and can be manipulated by further electron injection. Finally, we demonstrate that Au(111) terraces can be transformed with nearly perfect terrace selectivity over distances of hundreds of nanometers., Unión Europea. FP7, Ministerio de Economía y Competitividad (MINECO), Comunidad de Madrid, Universidad Autónoma de Madrid (UAM), Unidad de Excelencia María de Maeztu, Depto. de Física de Materiales, Fac. de Ciencias Físicas, TRUE, pub

Der Erste dieser Arbeit befasst sich mit der STM Untersuchung einer Grenzschicht in umgebender Atmosphäre, welche sich durch die Adsorption von Graphen auf einer Glimmeroberfläche ausbildet. Durch die umgebene Luftfeuchtigkeit interkalieren Wassermoleküle in diese Grenzschicht. Durch die Variation der relativen Luftfeuchtigkeit gibt diese Wasser ab bzw. nimmt auf, und es manifestieren sich sternförmig wachsende Fraktale, in denen Graphen etwa um den Durchmesser eines Wassermoleküls an Höhe absinkt. Die STM Untersuchung, welche primär sensitiv auf die Zustandsdichte von Graphen reagiert, zeigte, dass sich anders als in den SFM Untersuchungen, zusätzliche signifikante Höhenänderungen von Graphen innerhalb der Fraktale bildeten. Dieses deutet auf eine Wasserschicht hin, welche Domänen mit signifikant unterscheidbaren Polarisationsrichtungen aufweisen, welche die Zustandsdichte von Graphen verändern kann. Dies ist aber gleichbedeutend mit der Annahme, dass sich in jener Grenzschicht mindestens zwei oder mehr lagen Wasser bilden müssen. Der zweiten Teil befasst sich mit der STM Untersuchung einer funktionalisierten Oberfläche die charakterisiert ist durch eine leitende Oberfläche (Graphen und HOPG) adsorbierten funktionalisierte Dyade an einer Fest-Flüssig Grenzfläche. Diese Dyade besteht im Wesentlichen aus einem Zink-Tetraphenylporphyrin (ZnTPP) und mit diesem über einem flexiblen Arm verbundenen Spiropyranderivat. Letztere ändert seine Konformation durch die Einstrahlung mit Licht geeigneter Wellenlänge, womit sich das Dipolmoment stark ändert. Es zeigte sich, dass das Schaltverhalten auf einen Graphen mit dem Schaltverhalten einer Dyade in Lösung vergleichbar ist. Dieses lässt den Schluss zu, dass das Schalteigenschaften einer einzelnen Dyade auf das adsorbierte Kollektiv übertragen werden kann, da es keine signifikanten beeinflussenden Wechselwirkungen durch die leitende Oberfläche und der benachbarten Dyaden auswirkte., The first of this two-part work deals with the STM investigation of an interface in the surrounding natural atmosphere, which is formed by the adsorption of the conductive graphene onto the mica surface. In this interface, water molecules may intercalate by the surrounding humidity. By varying the relative humidity, the interface is rewetted, respectively, dewetted and it manifests itself in a star shape growing fractals, where the height of graphene is decreased by approximately the diameter of one water molecule. The STM investigation - which is primarily sensitive to the density of states of graphene - shows that additional significant changes in the height of graphene are formed within the fractal, unlike in the SFM investigations. This suggests that there is a water layer by which the density of graphene is differently affected by domains with significant distinguishable polarisation alignments. However, this is equivalent to the assumption that there are two or more water layers exist within the interface. The second part of this work deals with the STM investigation of a functionalized surface characterised by a functionalized dyad adsorbed onto a conductive surface (graphene and HOPG) at a solid-liquid interface. This dyad essentially comprises a zinc-tetraphenylporphyrin (ZnTPP) and is connected with a spiropyran derivative via a flexible linker. This changes its conformation through irradiation with light with a suitable wavelength, by which the dipole moment is also strongly changed. It was found that the switching behaviour of a graphene-based conductive surface is comparable with the switching behaviour of a dyad, which itself can move freely in solution. This leads to the conclusion that the switching properties of a single dyad can be transmitted to its collective because it affected no significant influence interactions by the conductive surface and the adjacent dyads.

The electronic properties of Triphenylamine (TPA) in gas phase and adsorbed on gold(111) have been simulated with Quantum Espresso using Density Functional Theory (DFT). To better understand how the presence of a gold surface affects sunlight absorption in the system, partial Density Of States (pDOS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) of the system have been calculated. To describe the electronic excitation, three different methods have been used, No Core Hole (NCH), Full Core Hole (FCH) and Half Core Hole (HCH) approximation. The excitation of the TPA molecule was made in the nitrogen (N) atom and in the four different carbon (C) atoms with different electronic environments, C-ipso, C-ortho, C-meta and C-para. When using the HCH method, the absorbing atom must be described by a pseudopotential (PP) which includes half of a hole in the 1s orbital. This PP has been generated and a detailed summary of the process is described. The TPA/gold system relaxes to a position with the central N atom of TPA above an gold (Au) atom in the second layer of the surface and at a distance of 3.66 Angstrom, to the first layer. TPA keeps its symmetry with only small differences in the length of atomic bonds when adsorbed. The most striking result of this study is how the band gap of TPA is affected by the gold layer. From the pDOS we can observe that TPA in gas phase has a clear band gap of 2.2 eV with C-ortho dominating in the valence region and the four carbons dominating in the first unoccupied states. When depositing the molecule on the surface of Au(111), the band gap is essentially gone and a number of states appear between the previous highest occupied and lowest unoccupied molecular orbital in TPA. These new states align in energy with three clusters of states of the gold suggesting an interaction between the molecule and the surface. In the generated NEXAFS of nitrogen and carbon in TPA gas phase, one can observe a small pre-peak before the first unoccupie

Der Erste dieser Arbeit befasst sich mit der STM Untersuchung einer Grenzschicht in umgebender Atmosphäre, welche sich durch die Adsorption von Graphen auf einer Glimmeroberfläche ausbildet. Durch die umgebene Luftfeuchtigkeit interkalieren Wassermoleküle in diese Grenzschicht. Durch die Variation der relativen Luftfeuchtigkeit gibt diese Wasser ab bzw. nimmt auf, und es manifestieren sich sternförmig wachsende Fraktale, in denen Graphen etwa um den Durchmesser eines Wassermoleküls an Höhe absinkt. Die STM Untersuchung, welche primär sensitiv auf die Zustandsdichte von Graphen reagiert, zeigte, dass sich anders als in den SFM Untersuchungen, zusätzliche signifikante Höhenänderungen von Graphen innerhalb der Fraktale bildeten. Dieses deutet auf eine Wasserschicht hin, welche Domänen mit signifikant unterscheidbaren Polarisationsrichtungen aufweisen, welche die Zustandsdichte von Graphen verändern kann. Dies ist aber gleichbedeutend mit der Annahme, dass sich in jener Grenzschicht mindestens zwei oder mehr lagen Wasser bilden müssen. Der zweiten Teil befasst sich mit der STM Untersuchung einer funktionalisierten Oberfläche die charakterisiert ist durch eine leitende Oberfläche (Graphen und HOPG) adsorbierten funktionalisierte Dyade an einer Fest-Flüssig Grenzfläche. Diese Dyade besteht im Wesentlichen aus einem Zink-Tetraphenylporphyrin (ZnTPP) und mit diesem über einem flexiblen Arm verbundenen Spiropyranderivat. Letztere ändert seine Konformation durch die Einstrahlung mit Licht geeigneter Wellenlänge, womit sich das Dipolmoment stark ändert. Es zeigte sich, dass das Schaltverhalten auf einen Graphen mit dem Schaltverhalten einer Dyade in Lösung vergleichbar ist. Dieses lässt den Schluss zu, dass das Schalteigenschaften einer einzelnen Dyade auf das adsorbierte Kollektiv übertragen werden kann, da es keine signifikanten beeinflussenden Wechselwirkungen durch die leitende Oberfläche und der benachbarten Dyaden auswirkte., The first of this two-part work deals with the STM investigation of an interface in the surrounding natural atmosphere, which is formed by the adsorption of the conductive graphene onto the mica surface. In this interface, water molecules may intercalate by the surrounding humidity. By varying the relative humidity, the interface is rewetted, respectively, dewetted and it manifests itself in a star shape growing fractals, where the height of graphene is decreased by approximately the diameter of one water molecule. The STM investigation - which is primarily sensitive to the density of states of graphene - shows that additional significant changes in the height of graphene are formed within the fractal, unlike in the SFM investigations. This suggests that there is a water layer by which the density of graphene is differently affected by domains with significant distinguishable polarisation alignments. However, this is equivalent to the assumption that there are two or more water layers exist within the interface. The second part of this work deals with the STM investigation of a functionalized surface characterised by a functionalized dyad adsorbed onto a conductive surface (graphene and HOPG) at a solid-liquid interface. This dyad essentially comprises a zinc-tetraphenylporphyrin (ZnTPP) and is connected with a spiropyran derivative via a flexible linker. This changes its conformation through irradiation with light with a suitable wavelength, by which the dipole moment is also strongly changed. It was found that the switching behaviour of a graphene-based conductive surface is comparable with the switching behaviour of a dyad, which itself can move freely in solution. This leads to the conclusion that the switching properties of a single dyad can be transmitted to its collective because it affected no significant influence interactions by the conductive surface and the adjacent dyads.

The electronic properties of Triphenylamine (TPA) in gas phase and adsorbed on gold(111) have been simulated with Quantum Espresso using Density Functional Theory (DFT). To better understand how the presence of a gold surface affects sunlight absorption in the system, partial Density Of States (pDOS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) of the system have been calculated. To describe the electronic excitation, three different methods have been used, No Core Hole (NCH), Full Core Hole (FCH) and Half Core Hole (HCH) approximation. The excitation of the TPA molecule was made in the nitrogen (N) atom and in the four different carbon (C) atoms with different electronic environments, C-ipso, C-ortho, C-meta and C-para. When using the HCH method, the absorbing atom must be described by a pseudopotential (PP) which includes half of a hole in the 1s orbital. This PP has been generated and a detailed summary of the process is described. The TPA/gold system relaxes to a position with the central N atom of TPA above an gold (Au) atom in the second layer of the surface and at a distance of 3.66 Angstrom, to the first layer. TPA keeps its symmetry with only small differences in the length of atomic bonds when adsorbed. The most striking result of this study is how the band gap of TPA is affected by the gold layer. From the pDOS we can observe that TPA in gas phase has a clear band gap of 2.2 eV with C-ortho dominating in the valence region and the four carbons dominating in the first unoccupied states. When depositing the molecule on the surface of Au(111), the band gap is essentially gone and a number of states appear between the previous highest occupied and lowest unoccupied molecular orbital in TPA. These new states align in energy with three clusters of states of the gold suggesting an interaction between the molecule and the surface. In the generated NEXAFS of nitrogen and carbon in TPA gas phase, one can observe a small pre-peak before the first unoccupie

The synthesis of 2-hydroxybenzoyl pyridopyrimidines (M1-M4) has been carried out with 3-formyl chrome derivatives and 6-amino-1-methyluracil to employ them as anion chemosensors. Pyridopyrimidine-based compounds were studied as colorimetric and fluorescent receptors for anion sensing. The observations with naked eye and the data obtained by UV-visible, fluorescence and H-1 NMR spectroscopy demonstrated selectivity for fluoride, acetate and cyanides among the pool of different anions. However, the spectral data involving fluoride anion showed particularly sharp and strong interactions. In sensing process, the binding of pyridopyrimidine amino (NH) and hydroxyl groups (OH) via hydrogen bonding F center dot center dot center dot center dot H-N/-O induced the colorimetric and turn off fluorescent response. The binding mode of action was further studied by H-1 NMR titrations that supported gradual deprotonation mechanism. The fluoride ion detection limit was in the range of 3.51 x 10(-8) M to 1.77 x 10(-6) M for probes M1-M4 and were lower than the maximum permissible concentration of F- ion in drinking water (5.3 x 10(-3) M) set by World Health Organization (WHO) that was found to be influenced by the nature of aromatic substituents. Theoretical study of receptor interactions with fluoride anion via O-H and N-H groups was also carried out at the quantum mechanical level. (C) 2019 Elsevier Ltd. All rights reserved.

Produced by many cell types, macrophage migration inhibitory factor (MIF) is a pleiotropic cytokine with critical and supporting roles in many disease states and conditions. Its disease associations, myriad functions, receptors, and downstream signaling have been the subject of considerable research, yet many questions remain. Moreover, the relevance of MIF's partially functionally redundant family member, D-dopachrome tautomerase (D-DT), also remains to be further characterized. Here, we discuss recent discoveries demonstrating direct roles of MIF in supporting NLR Family Pyrin Domain-Containing 3 (NRLP3) inflammasome activation, as well as acting as a molecular chaperone for intracellular proteins. These findings may offer new clues to understanding MIF's multiple functions, and assist the development of putative MIF-targeting therapeutics for a variety of pathologies.Copyright © 2019 Elsevier Ltd

Germline mutations in fundamental epigenetic regulatory molecules including DNA methyltransferase 3 alpha (DNMT3A) are commonly associated with growth disorders, whereas somatic mutations are often associated with malignancy. We profiled genome-wide DNA methylation patterns in DNMT3A c.2312G > A; p.(Arg771Gln) carriers in a large Amish sibship with Tatton-Brown-Rahman syndrome (TBRS), their mosaic father, and 15 TBRS patients with distinct pathogenic de novo DNMT3A variants. This defined widespread DNA hypomethylation at specific genomic sites enriched at locations annotated as genes involved in morphogenesis, development, differentiation, and malignancy predisposition pathways. TBRS patients also displayed highly accelerated DNA methylation aging. These findings were most marked in a carrier of the AML-associated driver mutation p.Arg882Cys. Our studies additionally defined phenotype-related accelerated and decelerated epigenetic aging in two histone methyltransferase disorders: NSD1 Sotos syndrome overgrowth disorder and KMT2D Kabuki syndrome growth impairment. Together, our findings provide fundamental new insights into aberrant epigenetic mechanisms, the role of epigenetic machinery maintenance, and determinants of biological aging in these growth disorders.Copyright © 2019 Jeffries et al. This article, published in Genome Research, is available under a Creative Commons License (Attribution 4.0 International), as described at http://creativecommons.org/licenses/by/4.0/.

Produced by many cell types, macrophage migration inhibitory factor (MIF) is a pleiotropic cytokine with critical and supporting roles in many disease states and conditions. Its disease associations, myriad functions, receptors, and downstream signaling have been the subject of considerable research, yet many questions remain. Moreover, the relevance of MIF's partially functionally redundant family member, D-dopachrome tautomerase (D-DT), also remains to be further characterized. Here, we discuss recent discoveries demonstrating direct roles of MIF in supporting NLR Family Pyrin Domain-Containing 3 (NRLP3) inflammasome activation, as well as acting as a molecular chaperone for intracellular proteins. These findings may offer new clues to understanding MIF's multiple functions, and assist the development of putative MIF-targeting therapeutics for a variety of pathologies.Copyright © 2019 Elsevier Ltd

Microalgae are generally considered an excellent source of vitamins, minerals, and bioactive molecules that make them suitable to be introduced in cosmetics, pharmaceuticals, and food industries. Aphanizomenon flos-aquae (AFA), an edible microalga, contains numerous biomolecules potentially able to prevent some pathologies including age-related disorders. With the aim to include an AFA extract (Klamin®) as a functional ingredient in baked products, we investigated if its bioactive molecules are destroyed or inactivated after standard cooking temperature. The AFA extract was exposed to heat stress (AFA-HS), and no significant decrease in pigment, polyphenol, and carotenoid content was detected by spectroscopic analysis. Thermal stability of AFA-HS extract was demonstrated by thermogravimetric analysis (TGA), and no change in the morphology of the granules of the powder was noticed by SEM microscopic observation. By Folin-Ciocalteu, ORAC, and ABTS assays, no change in the antioxidant activity and polyphenol contents was found after high-temperature exposition. When added in cell culture, solubilized AFA-HS lost neither its scavenging ability against ROS generation nor its protective role against Abeta, the main peptide involved in Alzheimer's disease. Prebiotic and antioxidant activities of AFA extract that are not lost after thermal stress were verified on E. coli bacteria. Finally, AFA-HS cookies, containing the extract as one of their ingredients, showed increased polyphenols. Here, we evaluate the possibility to use the AFA extract to produce functional food and prevent metabolic and age-related diseases.

Molecular visualization software is an upcoming and growing sector than it's tracing its path thanks to the incoming technologies. Not only allows to compute time-consuming CPU and GPU programs and renders in lesser time, but also introduces more complex and complete visualization methods that allow

Many electron transport layer materials (ETL) employed in state of the art organic light emitting diodes (OLEDs) are known to be polar. We combine for the first time simulations and electrical characterization of OLEDs based on polar ETL, in order to understand the impact of such materials on the device operation. Depending on the orientation of the dipole orientation, simulations predict either a benefit or a disadvantage of the polar ETL for the device performance. We also show that OLEDs featuring a polar material are perfectly suited for extracting mobility activation energy and Injection barrier from the anode to the ETL.

Biochemical processes are conducted by interactions of individual molecules that comprise cells. It is the transient physical shape of proteins that dictates their specific functionality. However, imaging individual instances of single molecular structures is one of the notable challenges in structural biology. Presently available protein structure reconstruction techniques, Nuclear Magnetic Resonance (NMR) spectroscopy, X-ray crystallography and cryogenic Electron microscopy (cryo-EM), cannot provide images of individual molecules. Despite their power and their complementary capabilities, said techniques produce only average molecular information. They achieve this by sampling large ensembles of molecules in nearly identical conformational states. As a result, individual instances of a generic, inhomogeneous or unstable atomic structures presently remain beyond reach. We seek to address this problem in a novel way by leveraging quantum technologies. In quantum computing, qubits are usually arranged in grids and coupled to one another in a highly organised manner. However, what if a qubit was coupled to an organic cluster of nuclear spins instead, e.g. that of a single molecule? What can be done with such a system in the context of quantum control and 3D imaging of individual molecular systems? What are its ultimate limits and possibilities? We explore those questions in stages throughout the chapters of this thesis. We begin in Chapter 2 by investigating dipole-dipole interactions present between the nuclear spins in a target molecule, on one side, and between an electron-spin based qubit and each of the nuclear target spins on the other. We consider the Nitrogen Vacancy (NV) centre in diamond as an example of a suitable qubit with an active community interest as a biocompatible nano-magnetometer. Our intention is to lay down foundations that will help us advance from magnetometry to 3D molecular imaging. Our inspiration comes from drawing parallels between the sin

Achieving rigorous control over the procedures aiming at modifying surfaces by selective and covalent anchoring of bioactive molecules is a mandatory step in view of the realistic applicability of bioengineered materials in the field of tissue engineering, biosensing, and nanomedicine. In this context, we report here a proof-of-concept study carried out on a self-assembling peptide (SAP) functionalized with cysteine (Cys), as to ideally grant molecule grafting to gold surfaces. The effectiveness of the surface functionalization in a monolayer regime and the molecular stability of SAP-Cys were probed by X-ray photoelectron spectroscopy; the highly ordered self-organization attained by the grafting molecules was assessed by means of angular-dependent near edge X-ray absorption spectroscopy studies. This study opens wide perspectives for efficient chemical modification of surfaces with biomolecules to include bioactive motifs and/or to add nanometric fibrous patterns.

Many electron transport layer materials (ETL) employed in state of the art organic light emitting diodes (OLEDs) are known to be polar. We combine for the first time simulations and electrical characterization of OLEDs based on polar ETL, in order to understand the impact of such materials on the device operation. Depending on the orientation of the dipole orientation, simulations predict either a benefit or a disadvantage of the polar ETL for the device performance. We also show that OLEDs featuring a polar material are perfectly suited for extracting mobility activation energy and Injection barrier from the anode to the ETL.

Hybrid trap experiments are set-ups that allow to study the interaction between ions and atoms in cold controlled environment. In such context, molecular anions present specific theoretical and experimental interests and challenges. In this work, we have used extensive \textit{ab initio} methods to investigate several collisional anionic systems: (1) M + OH$^{-}$ (where M are alkali or alkaline earth atoms), (2) Rb and H + OH(H$_{2}$O)$_{n}^{-}$ (with $n=0,1,2,3,4$) and (3) Rb and Li + C$_{2}^{-}$. Several molecular properties such as vertical detachment energies or electroaffinities, optimized structures, harmonic frequencies, potential energy curves or surfaces, etc have been calculated using high level quantum chemistry approaches. The results have been used to make predictions on the related reactivity in low energy regime. We emphasis on electronic detachment processes by carefully analysing the difference between the neutral and anionic potential energy surface. The Rb + OH$^{-}$ system is currently under experimental investigation. Therefore, a detailed study of its reactivity is carried out in the present work. We have analysed the different reactive channels arising from both collision involving the ground state and first electronic excited state of Rb. Using our calculated potentials and a capture model based dynamics, we have extracted cross sections and rate constants. Comparison with other alkali and earth alkaline atoms are made. Hydrated hydroxide cluster anions are planned by the experimental group as upcoming studied systems. We present here our preliminary results on the possible outcome when considering collisions with Rb and we discuss their implications for hybrid trap experiments. We make comparison with H as a colliding partner and consider our results in the context of astrochemistry. Finally we propose the C$_{2}^{-}$ molecular anion as an alternative to OH$^{-}$. Its interaction and reactivity with Rb and Li are investigated and the results, Doctorat en Sciences, info:eu-repo/semantics/nonPublished

The concept of a peptidomimetic was coined about forty years ago. Since then, an enormous effort and interest has been devoted to mimic the properties of peptides with small molecules or pseudopeptides. The present report aims to review different approaches described in the past to succeed in this goal. Basically, there are two different approaches to design peptidomimetics: a medicinal chemistry approach, where parts of the peptide are successively replaced by non-peptide moieties until getting a non-peptide molecule and a biophysical approach, where a hypothesis of the bioactive form of the peptide is sketched and peptidomimetics are designed based on hanging the appropriate chemical moieties on diverse scaffolds. Although both approaches have been used in the past, the former has been more widely used to design peptidomimetics of secretory peptides, whereas the latter is nowadays getting momentum with the recent interest in designing protein-protein interaction inhibitors. The present report summarizes the relevance of the information gathered from structure-activity studies, together with a short review on the strategies used to design new peptide analogs and surrogates. In a following section there is a short discussion on the characterization of the bioactive conformation of a peptide, to continue describing the process of designing conformationally constrained analogs producing first and second generation peptidomimetics. Finally, there is a section devoted to review the use of organic scaffolds to design peptidomimetics based on the information available on the bioactive conformation of the peptide., Postprint (author's final draft)

Spin-orbit couplings have been calculated in twenty snapshots of a molecular dynamics trajectory of [Fe(bpy)(3)](2+) to address the importance of geometrical distortions and second-order spin-orbit coupling on the intersystem crossing rate constants in the light-induced spin crossover process. It was found that the effective spin-orbit coupling between the (MLCT)-M-3 and T-5(2) state is much larger than the direct coupling in the symmetric structure, which opens the possibility of a direct (MLCT)-M-3-T-5(2) deactivation without the intervention of triplet metal-centered states. Based on the calculated deactivation times, we conclude that both the direct pathway and the one involving intermediate triplet states are active in the ultrafast population of the metastable HS state, bringing in agreement two experimental observations that advocate for either deactivation mechanism. This resolves a long-standing dispute about the deactivation mechanism of Fe((II))-polypyridyl complexes in particular, and about light-induced magnetism in transition metal complexes in general.

© 2017 Jarillo et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This work was supported by grants GR35/14-920911 (Banco Santander and Universidad Complutense de Madrid, Spain), and FIS2010-17440 and FIS2015-67765-R (MINECO, Spain) to JJ, EB, JPGV, and FJC, and by grant BFU2012-31825 and BFU2015-63714-R (MINECO, Spain) to JM and BI. Additionally, JJ and EB acknowledge financial support from FPU13/02934 and FPU13/02826 grants (Ministerio de Educación, Cultura y Deporte, Spain), respectively., Ligands binding to polymers regulate polymer functions by changing their physical and chemical properties. This ligand regulation plays a key role in many biological processes. We propose here a model to explain the mechanical, thermodynamic, and kinetic properties of the process of binding of small ligands to long biopolymers. These properties can now be measured at the single molecule level using force spectroscopy techniques. Our model performs an effective decomposition of the ligand-polymer system on its covered and uncovered regions, showing that the elastic properties of the ligand-polymer depend explicitly on the ligand coverage of the polymer (i.e., the fraction of the polymer covered by the ligand). The equilibrium coverage that minimizes the free energy of the ligand-polymer system is computed as a function of the applied force. We show how ligands tune the mechanical properties of a polymer, in particular its length and stiffness, in a force dependent manner. In addition, it is shown how ligand binding can be regulated applying mechanical tension on the polymer. Moreover, the binding kinetics study shows that, in the case where the ligand binds and organizes the polymer in different modes, the binding process can present transient shortening or lengthening of the polymer, caused by changes in the relative coverage by the different ligand modes. Our model will be useful to understand ligand-binding regulation of biological processes, such as the metabolism of nucleic acid. In particular, this model allows estimating the coverage fraction and the ligand mode characteristics from the force extension curves of a ligand-polymer system., Ministerio de Economía y Competitividad (MINECO), Universidad Complutense de Madrid/Banco Santander, Ministerio de Educación, Cultura y Deporte (MEC), Depto. de Estructura de la Materia, Física Térmica y Electrónica, Fac. de Ciencias Físicas, TRUE, pub

In this work, we utilize a method based on Wang-Landau Monte Carlo sampling for studying the temperature effects of astrophysically relavant molecules. Anharmonic effects, e.g., resonances, overtones, and combination bands, are fully incoportated in this method. The calculated infrared (IR) spectra are consistent with the experimental data measured by National Institute of Standards and Technology (NIST)., QC 20200408

A systematic study, using ion trap time-of-flight mass spectrometry, is presented for the photo-dissociation processes of Bisanthenquinone (Bq) cations, C28H12O2+, a ketone substituted Polycyclic Aromatic Hydrocarbon (PAH). The Bq cation fragments through sequential loss of the two neutral carbonyl (CO) units upon laser (626nm) irradiation, resulting in a PAH-like derivative C26H12+. Upon further irradiation, C26H12+ exhibits both stepwise dehydrogenation and C2/C2H2 loss fragmentation channels. Quantum chemistry calculations reveal a detailed picture for the first CO-loss, which involves a transition state with a barrier of ∼ 3.4 eV, which is lower than the energy required for the lowest H-loss pathway (∼ 5.0 eV). The barrier for the second CO-loss is higher (∼ 4.9 eV). The subsequent loss of this unit changes the Bq geometry from a planar to a bent one. It is concluded that the photodissociation mechanism of the substituted PAH cations studied here is site selective in the substituted subunit. This work also shows that an acetone substituted PAH cation is not photo-stable upon irradiation., QC 20181220

Плазмоннi наноструктури сильно локалiзують електричне поле на їх поверхнях за допомогою колективних коливань електронiв провiдностi при стимуляцiї падаючим свiтлом на певнiй довжинi хвилi. Молекули, адсорбованi на таких поверхнях, вiдчувають сильно посилене електричне поле через локалiзований поверхневий плазмонний резонанс (ЛППР), який пiдсилює сигнал комбiнацiйного розсiювання вiд цих молекул. Це явище називають поверхневим гiгантським комбiнацiйним розсiюванням (ГКР). Подальшi полiпшення в iнтенсивностi комбiнацiйного розсiювання були досягнутi шляхом проектування плазмонних наноструктур з контрольованим розмiром, формою, складом та розташуванням. У цiй оглядовiй статтi основна увага придiляється теорiї та аналiзу впливу захисного покриття на оксиднi матерiали на iзольованi наноструктури плазмонних металiв. Починаючи з короткого опису основних принципiв, що лежать в основi ЛППР i ГКР, ми порiвнюємо два плазмонних метала, два дiелектричних матерiала i вплив змiни окремих параметрiв наноструктури на вихiдний посилений сигнал комбiнацiйного розсiювання.

Plasmonic nanostructures strongly localize electric fields on their surfaces via the collective oscillations of conducting electrons under stimulation by incident light at certain wavelength. Molecules adsorbed onto such surfaces experiences a strongly enhanced electric field due to the localized surface plasmon resonance (LSPR), which amplifies the Raman scattering signal from these molecules. This phenomenon is referred to as surface enhanced Raman scattering (SERS). Further enhancements in the Raman intensity have been achieved by designing plasmonic nanostructures with a controlled size, shape, composition, and arrangement. This review paper focuses on the theory and analyses the influence of protective coating with oxide materials an isolated plasmonic metal nanostructures. Starting with a brief description of the basic principles underlying LSPR and SERS, we compare two plasmonic metals, two dielectric materials and the effect of changing individual parameters of the nanostructure on output enhanced Raman signal., Плазмонные наноструктуры сильно локализуют электрическое поле на их поверхностях посредством коллективных колебаний проводящих электронов при стимуляции падающим светом на определенной длине волны. Молекулы, адсорбированные на таких поверхностях, испытывают сильно усиленное электрическое поле из-за локализованного поверхностного плазмонного резонанса (ЛППР), который усиливает сигнал комбинационного рассеяния от этих молекул. Это явление называют поверхностным гигантским комбинационным рассеянием (ГКР). Дальнейшие улучшения в интенсивности комбинационного рассеяния были достигнуты путем проектирования плазмонных наноструктур с контролируемым размером, формой, составом и расположением. В этой обзорной статье основное внимание уделяется теории и анализ у влияния защитного покрытия на оксидные материалы на изолированные наноструктуры плазмонных металлов. Начиная с краткого описания основных принципов, лежащих в основе ЛППР и ГКР, мы сравниваем два плазмонных металла, два диэлектрических материала и влияние изменения отдельных параметров наноструктуры на выходной усиленный сигнал комбинационного рассеяния., Плазмоннi наноструктури сильно локалiзують електричне поле на їх поверхнях за допомогою колективних коливань електронiв провiдностi при стимуляцiї падаючим свiтлом на певнiй довжинi хвилi. Молекули, адсорбованi на таких поверхнях, вiдчувають сильно посилене електричне поле через локалiзований поверхневий плазмонний резонанс (ЛППР), який пiдсилює сигнал комбiнацiйного розсiювання вiд цих молекул. Це явище називають поверхневим гiгантським комбiнацiйним розсiюванням (ГКР). Подальшi полiпшення в iнтенсивностi комбiнацiйного розсiювання були досягнутi шляхом проектування плазмонних наноструктур з контрольованим розмiром, формою, складом та розташуванням. У цiй оглядовiй статтi основна увага придiляється теорiї та аналiзу впливу захисного покриття на оксиднi матерiали на iзольованi наноструктури плазмонних металiв. Починаючи з короткого опису основних принципiв, що лежать в основi ЛППР i ГКР, ми порiвнюємо два плазмонних метала, два дiелектричних матерiала i вплив змiни окремих параметрiв наноструктури на вихiдний посилений сигнал комбiнацiйного розсiювання.

Aims: Spleen tyrosine kinase (Syk) is a non-receptor tyrosine kinase involved in the signalling pathways of the B cell receptor, Fcgamma-receptor and some leukocyte integrins. However, Syk can also be expressed by some non-haematopoietic cell types, although whether Syk signalling in these cells contributes to the pathogenesis of kidney disease is unknown. To address this question, we examined the function of Syk in antibody-independent renal interstitial fibrosis in the unilateral ureteric obstruction (UUO) model. Main Method(s): Groups of C57BL/6J mice were treated with a selective Syk inhibitor (CC0417, 30 mg/kg/bid), vehicle, or no treatment, from the time of surgery until being killed 7 days later. Key Findings: A substantial accumulation of interstitial Syk+ cells was seen in the UUO kidney. Double staining identified Syk expression by infiltrating macrophages and by a subset of alpha-SMA+ myofibroblasts. CC0417 treatment substantially reduced the Syk+ cell population in conjunction with a reduction in both myofibroblast and macrophage accumulation. This was associated with a substantial reduction in collagen IV deposition and mRNA levels of pro-fibrotic (collagen I, collagen IV, fibronectin, alpha-SMA, TGF-beta1 and PAI-1) and pro-inflammatory molecules (MCP-1, TNF-alpha and NOS2). CC0417 treatment reduced both PDGF-B mRNA levels and Ki67+ proliferating interstitial cells in the UUO kidney. Furthermore, CC0417 inhibited PDGF-AB induced ERK activation and cell proliferation of cultured primary kidney fibroblasts. Significance: This study has identified a pathologic role for Syk in renal interstitial fibrosis. Syk inhibitors may have therapeutic potential in chronic fibrotic kidney disease.Copyright © 2016 Elsevier Inc. All rights reserved.

FRATESI, GUIDO, 4403, open, In this thesis we investigated materials of relevance to photovoltaics and organic electronics, and the studied systems involving surfaces with technological applications, such as graphene and TiO2 . We make use of the density functional theory (DFT) to calculate the structural and electronic properties of the system, and the Ab initio molecular dynamics to check the temperature dependent effects. Finally, we simulate the core excited spectroscopic measurements by the transition potential approach and use the Time-Dependent DFT to calculate the optical absorption coefficient. We first focused on covalent adsorption of aromatic radicals onto graphene.. Our results show that the adsorption of an aromatic radical generates two spin-dependent mid-gap states located around the Fermi energy which induce magnetic moments in graphene. This phenomenon can modify the band of pristine graphene and introduces a gap, but this effect is almost independent of the specific chemical functionalization by the aromatic radical. In this way it is possible to magnetize graphene just using s, p electrons without any d-metal impurities. Next we investigated the adsorption of prototypical dyes (catechol and isonicotinic acid) on the TiO2 anatase (101) and rutile (110) surfaces by DFT, Ab initio molecular dynamics and TDDFT calculations. We found that thermal fluctuation induce changes in the position of the molecular levels around the TiO2 valence band edge. For the anatase (101) surface, these fluctuations enhance significantly the low-energy tail of the absorption spectrum, and the sensitization can be improved by increasing the hybridization between the adsorbed dye and TiO2 states. But sensitization effects are less relevant for the rutile (110) surface. As an extension of this work towards more realistic materials for applications, we studied two more complex species, namely PTCDA and PTCDI adsorbed on the TiO2 rutile (110) surface. These molecules determine a more pronounced sensitiza, No, open, Lin, H, Lin, H

Aims: Spleen tyrosine kinase (Syk) is a non-receptor tyrosine kinase involved in the signalling pathways of the B cell receptor, Fcgamma-receptor and some leukocyte integrins. However, Syk can also be expressed by some non-haematopoietic cell types, although whether Syk signalling in these cells contributes to the pathogenesis of kidney disease is unknown. To address this question, we examined the function of Syk in antibody-independent renal interstitial fibrosis in the unilateral ureteric obstruction (UUO) model. Main Method(s): Groups of C57BL/6J mice were treated with a selective Syk inhibitor (CC0417, 30 mg/kg/bid), vehicle, or no treatment, from the time of surgery until being killed 7 days later. Key Findings: A substantial accumulation of interstitial Syk+ cells was seen in the UUO kidney. Double staining identified Syk expression by infiltrating macrophages and by a subset of alpha-SMA+ myofibroblasts. CC0417 treatment substantially reduced the Syk+ cell population in conjunction with a reduction in both myofibroblast and macrophage accumulation. This was associated with a substantial reduction in collagen IV deposition and mRNA levels of pro-fibrotic (collagen I, collagen IV, fibronectin, alpha-SMA, TGF-beta1 and PAI-1) and pro-inflammatory molecules (MCP-1, TNF-alpha and NOS2). CC0417 treatment reduced both PDGF-B mRNA levels and Ki67+ proliferating interstitial cells in the UUO kidney. Furthermore, CC0417 inhibited PDGF-AB induced ERK activation and cell proliferation of cultured primary kidney fibroblasts. Significance: This study has identified a pathologic role for Syk in renal interstitial fibrosis. Syk inhibitors may have therapeutic potential in chronic fibrotic kidney disease.Copyright © 2016 Elsevier Inc. All rights reserved.

In this thesis we investigated materials of relevance to photovoltaics and organic electronics, and the studied systems involving surfaces with technological applications, such as graphene and TiO2 . We make use of the density functional theory (DFT) to calculate the structural and electronic properties of the system, and the Ab initio molecular dynamics to check the temperature dependent effects. Finally, we simulate the core excited spectroscopic measurements by the transition potential approach and use the Time-Dependent DFT to calculate the optical absorption coefficient. We first focused on covalent adsorption of aromatic radicals onto graphene.. Our results show that the adsorption of an aromatic radical generates two spin-dependent mid-gap states located around the Fermi energy which induce magnetic moments in graphene. This phenomenon can modify the band of pristine graphene and introduces a gap, but this effect is almost independent of the specific chemical functionalization by the aromatic radical. In this way it is possible to magnetize graphene just using s, p electrons without any d-metal impurities. Next we investigated the adsorption of prototypical dyes (catechol and isonicotinic acid) on the TiO2 anatase (101) and rutile (110) surfaces by DFT, Ab initio molecular dynamics and TDDFT calculations. We found that thermal fluctuation induce changes in the position of the molecular levels around the TiO2 valence band edge. For the anatase (101) surface, these fluctuations enhance significantly the low-energy tail of the absorption spectrum, and the sensitization can be improved by increasing the hybridization between the adsorbed dye and TiO2 states. But sensitization effects are less relevant for the rutile (110) surface. As an extension of this work towards more realistic materials for applications, we studied two more complex species, namely PTCDA and PTCDI adsorbed on the TiO2 rutile (110) surface. These molecules determine a more pronounced sensitiza