Random Access Procedures in 5G IoT via NTN: System level performances

The Internet of Things (IoT) is a critical pillar in the digital transformation because it enables interaction with the physical world through remote sensing and actuation. Owing to the advancements in wireless technology, we now have the opportunity of using their features to the best of our abilities and improve over the current situation. Indeed, the Internet of Things market is expanding at an exponential rate, with devices such as alarms and detectors, smart metres, trackers, and wearables being used on a global scale for automotive and agriculture, environment monitoring, infrastructure surveillance and management, healthcare, energy and utilities, logistics, good tracking, and so on. The Third Generation Partnership Project (3GPP) acknowledged the importance of IoT by introducing new features to support it. In particular, in Rel.13, the 3GPP introduced the so-called IoT to support Low Power Wide Area Networks (LPWAN).As these devices will be distributed in areas where terrestrial networks are not feasible or commercially viable, satellite networks will play a complementary role due to their ability to provide global connectivity via their large footprint size and short service deployment time. In this context, the goal of this thesis is to investigate the viability of integrating IoT technology with satellite communication (SatCom) systems, with a focus on the Random Access(RA) Procedure. Indeed, the RA is the most critical procedure because it allows the UE to achieve uplink synchronisation, obtain the permanent ID, and obtain uplink transmission resources. The goal of this thesis is to evaluate preamble detection in the SatCom environment.

Towards a Smart Campus Digital Twin: Promoting Awareness and Sustainability Through Wayfinding and Real-Time Environmental Data

The newly inaugurated Navile District of the University of Bologna is a complex created along the Navile canal, that now houses various teaching and research activities for the disciplines of Chemistry, Industrial Chemistry, Pharmacy, Biotechnology and Astronomy. A Building Information Modeling system (BIM) gives staff of the Navile campus several ways to monitor buildings in the complex throughout their life cycle, one of which is the ability to access real-time environmental data such as room temperature, humidity, air composition, and more, thereby simplifying operations like finding faults and optimizing environmental resource usage. But smart features at Navile are not only available to the staff: AlmaMap Navile is a web application, whose development is documented in this thesis, that powers the public touch kiosks available throughout the campus, offering maps of the district and indications on how to reach buildings and spaces. Even if these two systems, BIM and AlmaMap, don't seem to have many similarities, they share the common intent of promoting awareness for informed decision making in the campus, and they do it while relying on web standards for communication. This opens up interesting possibilities, and is the idea behind AlmaMap Navile 2.0, an app that interfaces with the BIM system and combines real-time sensor data with a comfort calculation algorithm, giving users the ability not just to ask for directions to a space, but also to see its comfort level in advance and, should they want to, check environmental measurements coming from each sensor in a granular manner. The end result is a first step towards building a smart campus Digital Twin, that can support all the people who are part of the campus life in their daily activities, improving their efficiency and satisfaction, giving them the ability to make informed decisions, and promoting awareness and sustainability.

Asynchronous Massive Machine-Type Access with Massive MIMO

In this thesis asynchronous contention resolution diversity slotted ALOHA (ACRDA) is studied and implemented on computer to simulate a typical massive IoT scenario. Chapter 1 gives a general overview of existing multiple access schemes, reporting their fundamental concepts focusing more on Coded Random Access schemes and their characteristics. In Chapter 2 the asynchronous protocol ACRDA is explained in depth analyzing all parts of the scheme. In the third Chapter the results obtained following various simulations of the asynchronous scheme are reported and their performance are analyzed.

Realizzazione di un sistema di automazione domotica con tecnologia open-hardware

Il termine Domotica deriva dall’unione dei termini domus e robotics e spazia oltre alle competenze in ambito informatico ed elettronico, avvalendosi dell’architettura e di determinati campi dell’ingegneria come: energetica, edile, dell’ automazione, elettrotecnica, delle telecomunicazioni. La Domotica agevola gli aspetti della quotidianità all’interno dell’ambiente casalingo o, più in generale, di ambienti antropizzati. Questa tesi ha l’intento di spiegare come può essere realizzato un sistema domotizzato casalingo utilizzando dispositivi open-hardware. Inizialmente verranno messi in chiaro i concetti chiave generici di un sistema domotico e verranno discussi i prodotti attualmente in commercio e verrà fatta una piccola introduzione sul concetto di open-hardware. Successivamente verrà discusso il sistema realizzato dandone una panoramica, si esaminerà la strutturazione sia software che hardware e le tecnologie ed i dispositivi utilizzati, per poi enucleare casi d’uso. A seguire le conclusioni.

Chinese Internet language: A sociolinguistic analysis of adaptations of the Chinese writing system

This paper examines the adaptations of the writing system in Internet language in mainland China from a sociolinguistic perspective. A comparison is also made of the adaptations in mainland China with those that Su (2003) found in Taiwan. In Computer-Mediated Communication (CMC), writing systems are often adapted to compensate for their inherent inadequacies (such as difficulty in input). Su (2003) investigates the creative uses of the writing system on the electronic bulletin boards (BBS) of two college student organizations in Taipei, Taiwan, and identifies four popular and creative uses of the Chinese writing system: stylized English, stylized Taiwanese-accented Mandarin, stylized Taiwanese, and the recycling of a transliteration alphabet used in elementary education. According to Coupland (2001; cited in Su 2003), stylization is “the knowing deployment of culturally familiar styles and identities that are marked as deviating from those predictably associated with the current speaking context”. Within this framework and drawing on the data in previous publications on Internet language and online sources, this study identifies five types of adaptations in mainland China’s Internet language: stylized Mandarin (e.g., 漂漂 piāopiāo for 漂亮 ‘beautiful’), stylized dialect-accented Mandarin (e.g., 灰常 huīcháng for 非常 ‘very much’), stylized English (e.g., 伊妹儿 yīmèier for ‘email’), stylized initials (e.g., bt 变态 biàntài for ‘abnormal’; pk, short form for ‘player kill’), and stylized numbers (e.g., 9494 jiùshi jiùshi 就是就是 ‘that is it’). The Internet community is composed of highly mobile individuals and thus forms a weak-tie social network. According to Milroy and Milroy (1992), a social network with weak ties is often where language innovation takes place. Adaptations of the Chinese writing system in Internet language provide interesting evidence for the innovations within a weak-tie social network. Our comparison of adaptations in mainland China and Taiwan shows that, in maximizing the effectiveness and functionality of their communication, participants of Internet communication are confronted with different language resources and situations, including differences in Romanization systems, English proficiency level, and attitudes towards English usage. As argued by Milroy and Milroy (1992), a weak-tie social network model can bridge the social class and social network. In the Internet community, the degree of diversity of the stylized linguistic varieties indexes the virtual and/or social status of its participants: the more diversified one’s Internet language is, the higher is his/her virtual and/or social status.

Detailed study of the K(L)->pi(0)pi(0)pi(0) Dalitz plot

Using a sample of 68.3x10(6) K(L)->pi(0)pi(0)pi(0) decays collected in 1996-1999 by the KTeV (E832) experiment at Fermilab, we present a detailed study of the K(L)->pi(0)pi(0)pi(0) Dalitz plot density. We report the first observation of interference from K(L)->pi(+)pi(-)pi(0) decays in which pi(+)pi(-) rescatters to pi(0)pi(0) in a final-state interaction. This rescattering effect is described by the Cabibbo-Isidori model, and it depends on the difference in pion scattering lengths between the isospin I=0 and I=2 states, a(0)-a(2). Using the Cabibbo-Isidori model, and fixing (a(0)-a(2))m(pi)(+)=0.268 +/- 0.017 as measured by the CERN-NA48 collaboration, we present the first measurement of the K(L)->pi(0)pi(0)pi(0) quadratic slope parameter that accounts for the rescattering effect: h(000)=(+0.59 +/- 0.20(stat)+/- 0.48(syst)+/- 1.06(ext))x10(-3), where the uncertainties are from data statistics, KTeV systematic errors, and external systematic errors. Fitting for both h(000) and a(0)-a(2), we find h(000)=(-2.09 +/- 0.62(stat)+/- 0.72(syst)+/- 0.28(ext))x10(-3), and m(pi)(+)(a(0)-a(2))=0.215 +/- 0.014(stat)+/- 0.025(syst)+/- 0.006(ext); our value for a(0)-a(2) is consistent with that from NA48.

Blockade of vascular smooth muscle cell proliferation and intimal thickening after balloon injury by the sulfated oligosaccharide PI-88: Phosphomannopentaose sulfate directly binds FGF-2, blocks cellular signaling, and inhibits proliferation

Percutaneous transluminal coronary angioplasty is a frequently used interventional technique to reopen arteries that have narrowed because of atherosclerosis. Restenosis, or renarrowing of the artery shortly after angioplasty, is a major limitation to the success of the procedure and is due mainly to smooth muscle cell accumulation in the artery wall at the site of balloon injury. In the present study, we demonstrate that the antiangiogenic sulfated oligosaccharide, PI-88, inhibits primary vascular smooth muscle cell proliferation and reduces intimal thickening 14 days after balloon angioplasty of rat and rabbit arteries. PI-88 reduced heparan sulfate content in the injured artery wall and prevented change in smooth muscle phenotype. However, the mechanism of PI-88 inhibition was not merely confined to the antiheparanase activity of this compound. PI-88 blocked extracellular signal-regulated kinase-1/2 (ERK1/2) activity within minutes of smooth muscle cell injury. It facilitated FGF-2 release from uninjured smooth muscle cells in vitro, and super-released FGF-2 after injury while inhibiting ERK1/2 activation. PI-88 inhibited the decrease in levels of FGF-2 protein in the rat artery wall within 8 minutes of injury. PI-88 also blocked injury-inducible ERK phosphorylation, without altering the clotting time in these animals. Optical biosensor studies revealed that PI-88 potently inhibited (K-i 10.3 nmol/L) the interaction of FGF-2 with heparan sulfate. These findings show for the first time the capacity of this sulfated oligosaccharide to directly bind FGF-2, block cellular signaling and proliferation in vitro, and inhibit injury-induced smooth muscle cell hyperplasia in two animal models. As such, this study demonstrates a new role for PI-88 as an inhibitor of intimal thickening after balloon angioplasty. The full text of this article is available online at http://www.circresaha.org.

Deteção e acompanhamento de movimento através de uma câmara de vídeo

A deteção e seguimento de pessoas tem uma grande variedade de aplicações em visão computacional. Embora tenha sido alvo de anos de investigação, continua a ser um tópico em aberto, e ainda hoje, um grande desafio a obtenção de uma abordagem que inclua simultaneamente exibilidade e precisão. O trabalho apresentado nesta dissertação desenvolve um caso de estudo sobre deteção e seguimento automático de faces humanas, em ambiente de sala de reuniões, concretizado num sistema flexível de baixo custo. O sistema proposto é baseado no sistema operativo GNU's Not Unix (GNU) linux, e é dividido em quatro etapas, a aquisição de vídeo, a deteção da face, o tracking e reorientação da posição da câmara. A aquisição consiste na captura de frames de vídeo das três câmaras Internet Protocol (IP) Sony SNC-RZ25P, instaladas na sala, através de uma rede Local Area Network (LAN) também ele já existente. Esta etapa fornece os frames de vídeo para processamento à detecção e tracking. A deteção usa o algoritmo proposto por Viola e Jones, para a identificação de objetos, baseando-se nas suas principais características, que permite efetuar a deteção de qualquer tipo de objeto (neste caso faces humanas) de uma forma genérica e em tempo real. As saídas da deteção, quando é identificado com sucesso uma face, são as coordenadas do posicionamento da face, no frame de vídeo. As coordenadas da face detetada são usadas pelo algoritmo de tracking, para a partir desse ponto seguir a face pelos frames de vídeo subsequentes. A etapa de tracking implementa o algoritmo Continuously Adaptive Mean-SHIFT (Camshift) que baseia o seu funcionamento na pesquisa num mapa de densidade de probabilidade, do seu valor máximo, através de iterações sucessivas. O retorno do algoritmo são as coordenadas da posição e orientação da face. Estas coordenadas permitem orientar o posicionamento da câmara de forma que a face esteja sempre o mais próximo possível do centro do campo de visão da câmara. Os resultados obtidos mostraram que o sistema de tracking proposto é capaz de reconhecer e seguir faces em movimento em sequências de frames de vídeo, mostrando adequabilidade para aplicação de monotorização em tempo real.

Proposta de solução de videovigilância para locais remotos

Desde tempos remotos que homens faziam a vigilância de bens e mercadorias e mais recentemente também de pessoas com o intuito de dissuadir roubos, atos de vandalismo e de violência. Nos últimos anos, com a evolução das novas tecnologias verificou-se a sua adoção para auxílio da vigilância. Os atos de terrorismo que têm acontecido um pouco por todo o mundo trouxeram um clima de insegurança à população mundial. Este fenómeno, juntamente com o elevado número de roubos e atos de violência levou à expansão de utilização dos meios de videovigilância de forma a dissuadir estes tipos de crime podendo mesmo, nalguns casos servir como prova para punir os autores dos mesmos. Em Portugal tem-se verificado uma escalada de crimes nas zonas mais rurais não só de bens como as alfaias agrícolas mas também de frutos e mesmo de animais. Estes crimes predominam em locais rurais, relativamente distantes das povoações e em locais onde não existem (ou são praticamente inexistentes) infraestruturas necessárias para implementar meios de videovigilância como a falta de rede elétrica e internet o que torna quase inviável a existência de sistemas de videovigilância nesses locais. Dotar esses locais das infra estruturas necessárias poderia tornar-se demasiado dispendioso e os vigilantes humanos poderiam correr riscos no meio dos montes ou noutros locais remotos para além dos seus elevados custos. Para além do problema dos roubos, existe um outro flagelo relacionado com os incêndios na floresta portuguesa, que todos os anos é dizimada pelo fogo devido a incêndios que surgem na sua maioria causados pelo homem sendo uma parte significativa os de origem criminosa. Para dar resposta a estes problemas e no sentido de vigiar e dissuadir estes tipos de crimes, iniciamos um estudo que pretende propor um protótipo de um sistema de videovigilância para locais remotos (SVR - Sistema de Videovigilância Remota) de baixo custo de forma a diminuir o número de crimes e assim minimizar os prejuízos económico e sociais causados pelos mesmos. Pretendemos estudar o problema e analisar tecnologias com potencial para propor uma solução que possa auxiliar a vigilância nesse tipo de locais com o pressuposto de poder vir a contribuir para a diminuição deste tipo de crimes devido ao seu efeito dissuasor pelo facto de se poder divulgar que estes locais já têm uma solução de vigilância oculta. A solução proposta contempla um sistema de videovigilância com uma camara construída com base num Raspberry Pi onde o vídeo é transmitido em streaming via Web através de comunicações móveis. A alimentação do sistema nestes espaços sem energia elétrica é feita através de um painel fotovoltaico. É proporcionado ao utilizador uma interface para visualizar o vídeo transmitido e um mecanismo de notificações por email. É ainda possível a visualização de imagens gravadas num cartão de memória relativas a ocorrências de deteção de movimentos. Foram realizados inúmeros testes ao protótipo SVR sendo os resultados obtidos aqui descritos.

Long-Lasting Protection of Activity of Nucleoside Reverse Transcriptase Inhibitors and Protease Inhibitors (PIs) by Boosted PI Containing Regimens.

BACKGROUND: The accumulation of mutations after long-lasting exposure to a failing combination antiretroviral therapy (cART) is problematic and severely reduces the options for further successful treatments. METHODS: We studied patients from the Swiss HIV Cohort Study who failed cART with nucleoside reverse transcriptase inhibitors (NRTIs) and either a ritonavir-boosted PI (PI/r) or a non-nucleoside reverse transcriptase inhibitor (NNRTI). The loss of genotypic activity <3, 3-6, >6 months after virological failure was analyzed with Stanford algorithm. Risk factors associated with early emergence of drug resistance mutations (<6 months after failure) were identified with multivariable logistic regression. RESULTS: Ninety-nine genotypic resistance tests from PI/r-treated and 129 from NNRTI-treated patients were analyzed. The risk of losing the activity of ≥1 NRTIs was lower among PI/r- compared to NNRTI-treated individuals <3, 3-6, and >6 months after failure: 8.8% vs. 38.2% (p = 0.009), 7.1% vs. 46.9% (p<0.001) and 18.9% vs. 60.9% (p<0.001). The percentages of patients who have lost PI/r activity were 2.9%, 3.6% and 5.4% <3, 3-6, >6 months after failure compared to 41.2%, 49.0% and 63.0% of those who have lost NNRTI activity (all p<0.001). The risk to accumulate an early NRTI mutation was strongly associated with NNRTI-containing cART (adjusted odds ratio: 13.3 (95% CI: 4.1-42.8), p<0.001). CONCLUSIONS: The loss of activity of PIs and NRTIs was low among patients treated with PI/r, even after long-lasting exposure to a failing cART. Thus, more options remain for second-line therapy. This finding is potentially of high relevance, in particular for settings with poor or lacking virological monitoring.

Control de dispositivos con Android

Este proyecto de final de carrera de la titulación de Ingeniería en Informática de Gestión consiste en el diseño y desarrollo de un sistema de control de dispositivos conectados a Raspberry Pi y gestionados desde un dispositivo Android. Se podrán llevar a cabo diferentes acciones como encender, apagar, programar la calefacción y consultar la temperatura actual remotamente desde un dispostivo conectado a la red wifi doméstica o desde de cualquier red que esté conectada a internet.

Database Rights in Safe European Home: The Path to More Rigorous Protection of Information

1. Introduction "The one that has compiled ... a database, the collection, securing the validity or presentation of which has required an essential investment, has the sole right to control the content over the whole work or over either a qualitatively or quantitatively substantial part of the work both by means of reproduction and by making them available to the public", Finnish Copyright Act, section 49.1 These are the laconic words that implemented the much-awaited and hotly debated European Community Directive on the legal protection of databases,2 the EDD, into Finnish Copyright legislation in 1998. Now in the year 2005, after more than half a decade of the domestic implementation it is yet uncertain as to the proper meaning and construction of the convoluted qualitative criteria the current legislation employs as a prerequisite for the database protection both in Finland and within the European Union. Further, this opaque Pan-European instrument has the potential of bringing about a number of far-reaching economic and cultural ramifications, which have remained largely uncharted or unobserved. Thus the task of understanding this particular and currently peculiarly European new intellectual property regime is twofold: first, to understand the mechanics and functioning of the EDD and second, to realise the potential and risks inherent in the new legislation in economic, cultural and societal dimensions. 2. Subject-matter of the study: basic issues The first part of the task mentioned above is straightforward: questions such as what is meant by the key concepts triggering the functioning of the EDD such as presentation of independent information, what constitutes an essential investment in acquiring data and when the reproduction of a given database reaches either qualitatively or quantitatively the threshold of substantiality before the right-holder of a database can avail himself of the remedies provided by the statutory framework remain unclear and call for a careful analysis. As for second task, it is already obvious that the practical importance of the legal protection providedby the database right is in the rapid increase. The accelerating transformationof information into digital form is an existing fact, not merely a reflection of a shape of things to come in the future. To take a simple example, the digitisation of a map, traditionally in paper format and protected by copyright, can provide the consumer a markedly easier and faster access to the wanted material and the price can be, depending on the current state of the marketplace, cheaper than that of the traditional form or even free by means of public lending libraries providing access to the information online. This also renders it possible for authors and publishers to make available and sell their products to markedly larger, international markets while the production and distribution costs can be kept at minimum due to the new electronic production, marketing and distributionmechanisms to mention a few. The troublesome side is for authors and publishers the vastly enhanced potential for illegal copying by electronic means, producing numerous virtually identical copies at speed. The fear of illegal copying canlead to stark technical protection that in turn can dampen down the demand for information goods and services and furthermore, efficiently hamper the right of access to the materials available lawfully in electronic form and thus weaken the possibility of access to information, education and the cultural heritage of anation or nations, a condition precedent for a functioning democracy. 3. Particular issues in Digital Economy and Information Networks All what is said above applies a fortiori to the databases. As a result of the ubiquity of the Internet and the pending breakthrough of Mobile Internet, peer-to-peer Networks, Localand Wide Local Area Networks, a rapidly increasing amount of information not protected by traditional copyright, such as various lists, catalogues and tables,3previously protected partially by the old section 49 of the Finnish Copyright act are available free or for consideration in the Internet, and by the same token importantly, numerous databases are collected in order to enable the marketing, tendering and selling products and services in above mentioned networks. Databases and the information embedded therein constitutes a pivotal element in virtually any commercial operation including product and service development, scientific research and education. A poignant but not instantaneously an obvious example of this is a database consisting of physical coordinates of a certain selected group of customers for marketing purposes through cellular phones, laptops and several handheld or vehicle-based devices connected online. These practical needs call for answer to a plethora of questions already outlined above: Has thecollection and securing the validity of this information required an essential input? What qualifies as a quantitatively or qualitatively significant investment? According to the Directive, the database comprises works, information and other independent materials, which are arranged in systematic or methodical way andare individually accessible by electronic or other means. Under what circumstances then, are the materials regarded as arranged in systematic or methodical way? Only when the protected elements of a database are established, the question concerning the scope of protection becomes acute. In digital context, the traditional notions of reproduction and making available to the public of digital materials seem to fit ill or lead into interpretations that are at variance with analogous domain as regards the lawful and illegal uses of information. This may well interfere with or rework the way in which the commercial and other operators have to establish themselves and function in the existing value networks of information products and services. 4. International sphere After the expiry of the implementation period for the European Community Directive on legal protection of databases, the goals of the Directive must have been consolidated into the domestic legislations of the current twenty-five Member States within the European Union. On one hand, these fundamental questions readily imply that the problemsrelated to correct construction of the Directive underlying the domestic legislation transpire the national boundaries. On the other hand, the disputes arisingon account of the implementation and interpretation of the Directive on the European level attract significance domestically. Consequently, the guidelines on correct interpretation of the Directive importing the practical, business-oriented solutions may well have application on European level. This underlines the exigency for a thorough analysis on the implications of the meaning and potential scope of Database protection in Finland and the European Union. This position hasto be contrasted with the larger, international sphere, which in early 2005 does differ markedly from European Union stance, directly having a negative effect on international trade particularly in digital content. A particular case in point is the USA, a database producer primus inter pares, not at least yet having aSui Generis database regime or its kin, while both the political and academic discourse on the matter abounds. 5. The objectives of the study The above mentioned background with its several open issues calls for the detailed study of thefollowing questions: -What is a database-at-law and when is a database protected by intellectual property rights, particularly by the European database regime?What is the international situation? -How is a database protected and what is its relation with other intellectual property regimes, particularly in the Digital context? -The opportunities and threats provided by current protection to creators, users and the society as a whole, including the commercial and cultural implications? -The difficult question on relation of the Database protection and protection of factual information as such. 6. Dsiposition The Study, in purporting to analyse and cast light on the questions above, is divided into three mainparts. The first part has the purpose of introducing the political and rationalbackground and subsequent legislative evolution path of the European database protection, reflected against the international backdrop on the issue. An introduction to databases, originally a vehicle of modern computing and information andcommunication technology, is also incorporated. The second part sets out the chosen and existing two-tier model of the database protection, reviewing both itscopyright and Sui Generis right facets in detail together with the emergent application of the machinery in real-life societal and particularly commercial context. Furthermore, a general outline of copyright, relevant in context of copyright databases is provided. For purposes of further comparison, a chapter on the precursor of Sui Generi, database right, the Nordic catalogue rule also ensues. The third and final part analyses the positive and negative impact of the database protection system and attempts to scrutinize the implications further in the future with some caveats and tentative recommendations, in particular as regards the convoluted issue concerning the IPR protection of information per se, a new tenet in the domain of copyright and related rights.

Telerobotics: Methodology for the Development of a Through-the-Internet Robotic Teleoperated System

This work presents a methodology for the development of Teleoperated Robotic Systems through the Internet. Initially, it is presented a bibliographical review of the Telerobotic systems that uses Internet as way of control. The methodology is implemented and tested through the development of two systems. The first is a manipulator with two degrees of freedom commanded remotely through the Internet denominated RobWebCam (http://www.graco.unb.br/robwebcam). The second is a system which teleoperates an ABB (Asea Brown Boveri) Industrial Robot of six degrees of freedom denominated RobWebLink (http://webrobot.graco.unb.br). RobWebCam is composed of a manipulator with two degrees of freedom, a video camera, Internet, computers and communication driver between the manipulator and the Unix system; and RobWebLink composed of the same components plus the Industrial Robot. With the use of this technology, it is possible to move far distant positioning objects minimizing transport costs, materials and people; acting in real time in the process that is wanted to be controller. This work demonstrates that the teleoperating via Internet of robotic systems and other equipments is viable, in spite of using rate transmission data with low bandwidth. Possible applications include remote surveillance, control and remote diagnosis and maintenance of machines and equipments.

Solvatochromic Shift of the pi -> pi* Transition in All-Trans, Cis-13, Cis-11, Cis-9, and Cis-7 Retinal Isomers Induced by Water and Methanol

The solvatochromic shift of the lowest singlet it pi -> pi* electronic transition in the all-trans, cis-13, cis-11, cis-9, and cis-7 retinal isomers were computed under the influence of water, methanol, and benzene solvents. Excitation energies were calculated in gas phase and in solution. The calculations in solution were performed considering the sequential Monte Carlo (MC) /Quantum Mechanical approach. The MC simulations were performed considering the full retinal isomer molecules and 900 water molecules, 900 methanol, or 400 benzene ones. The OPLS/AA parametrization was chosen for retinal, methanol, and benzene molecules and the SPC model was used for water one. From the MC calculations 100 independent configurations were selected, with 100 solvent molecules in thermodynamical equilibrium at T = 298.15 K. Average point-charges were obtained from those independent configurations for water, methanol, and benzene solvent. TDDFT and CASSCF//CASPT2 methodologies were used to compute the vertical excitation energy of the retinal isomers in different environment. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110: 2076-2087, 2010