A grande maioria da população mundial está crescentemente exposta à radiação eletromagnética proveniente de fontes que muitas vezes estão localizadas nas proximidades do corpo. A radiação eletromagnética é considerada um agente possivelmente cancerígeno para as pessoas, classificação 2B indicada pela Organização Mundial da Saúde-OMS (WHO/IARC, 2011). Devido às preocupações em relação aos riscos associados a esta exposição existem normas que recomendam os valores máximos de exposição permitidos (ICNIRP, 1998; FCC, 2001). A correta avaliação das doses de radiação é, portanto, relevante. Este trabalho tem a finalidade de avaliar o impacto dos resultados do cálculo da dose da Taxa de Absorção Específica (SAR) em usuários expostos a radiação por tablets operando na faixa de radiocomunicações Wi-fi. Os três modelos existentes de cabeça humana utilizados serão um manequim homogêneo SAM phantom e dois modelos de cabeça realistas heterogêneos: um adulto masculino e uma criança masculina. Será também utilizado nas simulações um modelo masculino de criança que foi desenvolvido através de imagens de tomografia computadorizada (TC) pelo processo de segmentação feito no software AMIRA. Será utilizado um modelo genérico de tablet. Os parâmetros dosimétricos usados para simulação da SAR serão computados pelo software SEMCAD X que é baseado no Método das Diferenças Finitas no Domínio do Tempo (FDTD). Será criado também um código do Método FDTD através do software MATLAB que servirá para a escolha dos parâmetros do SEMCAD X. A distância entre o tablet e os modelos de cabeças varia de 50 mm a 300 mm. Os resultados da SAR serão comparados com os limites de exposição recomendados pelas normas internacionais. Também serão simuladas diferentes posições da antena no tablet. Da análise dos resultados foi constatado que os valores de SAR são muito baixos e todos os resultados ficaram dentro dos limites do psSAR recomendados pela FCC de 1,6 W/kg em cada 1 g de tecido e de 2 W/kg em cada 10 g de tecido estabelecidos pela ICNIRP. Comparando os valores de SAR do modelo SAM com o modelo DUKE, o modelo SAM se mostra conservador, porém quando a comparação é feita com as crianças o SAM deixa de ser conservador. / The vast majority of the world population is increasingly exposed to electromagnetic radiation from sources which are often located near to the body. Electromagnetic radiation is considered a possible carcinogen for people, classification 2B indicated by the World Health Organization-WHO (WHO/IARC, 2011). Due to concerns regarding the risks associated with this exposition there are regulations suggesting maximum allowed exposure values (ICNIRP, 1998; FCC, 2001). The correct evaluation of radiation doses is therefore relevant. This work aims to assess the impact of the results of the calculation of Specific Absorption Rate dose (SAR) in users exposed to radiation from tablets operating in the Wi-fi band. The three existing models of human head used are a homogeneous dummy SAM phantom and two heterogeneous realistic head models: a male adult and a male child. It will also be used in the simulations a male child model which was developed from computed tomography (CT) imaging using the AMIRA software for the segmentation process. A generic model of tablet is used. Dosimetric parameters used for simulation of the SAR are computed using the SEMCAD X software which is based on the Finite Difference Method in Time Domain (FDTD). A FDTD code was developed using the MATLAB software in order to help to choose the input SEMCAD X parameters. The distances between the tablet and the head of the models varies from 50 mm to 300 mm. SAR results are compared with the exposure limits recommended by international standards. Different antenna positions on the tablet are simulated too. Examining the results it was found that the SAR values are very low and all results are within the psSAR limits recommended by FCC (1,6 W/kg averaged over 1 g of tissue) and by ICNIRP (2 W/kg in 10 g of tissue). Comparing the SAR in the SAM model with the SAR in the DUKE model, the SAM model shows to be conservative. However, when compared with the children, the SAM is not conservative.

P. aeruginosa PA14 é uma linhagem isolada de queimadura que apresenta vários fatores de patogenicidade comuns no quadro de infecção de hospedeiros filogeneticamente distintos (plantas, mamíferos ou invertebrados). O gene kerV foi revelado numa busca por mutantes atenuados em virulência em uma biblioteca de mutantes por transposons da linhagem PA14 (Rahme et al., 1997). A caracterização da linhagem D12, mutante em kerV, confirmou sua virulência atenuada (Apidianakis et al., 2005 e An et al., 2009) e resultados do transcriptoma mostraram alteração na expressão de mais de 500 genes, sendo alguns relacionados com o sistema de \"quorum sensing\" (Rahme et al, dados não publicados). O gene kerV está próximo à montante ao gene gloB, envolvido em detoxificação de metilglioxal, e à jusante aos genes rnhA e dnaQ, que codificam proteínas envolvidas na replicação e reparo do DNA. Este trabalho teve como objetivo estudar a função molecular do produto de kerV e a expressão dos genes do lócus kerV-rnhA-dnaQ. Análises de bioinformática indicam que a proteína KerV é uma metiltransferase dependente de S-adenosil-metionina (SAM), apresentando um domínio conservado de ligação a SAM e uma arquitetura de domínio compatível com a organização em fitas-beta e hélices-alfa alternadas descritas para a família das metiltransferases dependentes de SAM. Ela não apresenta outros domínios conservados que indiquem seu substrato de metilação. A expressão heteróloga desta proteína em E. coli, mostrou que ela é expressa de maneira parcialmente solúvel quando co-expressa com as chaperoninas GroEL/GroES em baixas temperaturas ou quando fusionada a MBP ou GST. A purificação desta proteína mostra que ela é co-eluída com a chaperonina GroEL sugerindo que para atingir sua conformação nativa ela necessita dessas proteínas acessórias. MBP-KerV purificado foi usado para ensaios \"in vitro\" de atividade de metiltransferase e ligação a SAM, que não foram conclusivos, pois não há certeza do seu correto estado de enovelamento. Ensaios de duplo-híbrido mostraram que KerV não interage com os produtos de rnhA e dnaQ, sugerindo que KerV não está diretamente relacionado com suas funções. A freqüência de mutação na linhagem D12 está levemente aumentada (aproximadamente quatro vezes), o que sugere que KerV não está diretamente envolvida no reparo de DNA do tipo ´mismatch repair`. Os ensaios usados para detectar metilação do DNA, proteínas e rRNAs não revelaram que KerV estaria envolvido com a metilação destes substratos. Os inícios de transcrição dos genes kerV, rnhA e dnaQ foram determinados. A deleção de kerV causa um efeito polar na transcrição do gene rnhA, que não se reflete nos níveis da proteína. A deleção também afeta a expressão de dnaQ, sugerindo que KerV seja importante para sua regulação. Os ensaios de complementação da virulência em modelos invertebrados e de células epiteliais de pulmão mostram que apenas a presença dos três genes e seus produtos em níveis normais são capazes de reverter a maioria dos fenótipos atenuados. KerV se mostrou essencial para a inibição da translocação de NF-kB para o núcleo das células, comprovando que esta proteína é relevante para a virulência de PA14, contribuindo com o silenciamento da resposta imune do hospedeiro. O conjunto dos resultados indicam uma complexa inter-relação entre a expressão dos genes kerV, rnhA e dnaQ e seu papel na biologia de P. aeruginosa. / P. aeruginosa PA14 is a burn isolate multi-host pathogen strain. The screening for virulence attenuated mutants in a PA14 transposon mutant library revealed the kerV gene (Rahme et al., 1997). The characterization of D12 strain, a kerV mutant, confirmed the attenuated virulence phenotype (Apidianakis et al., 2005 and An et al., 2009) and transcriptome analysis showed the expression of more than 500 genes are affected in D12, some of these genes are related with quorum sensing (Rahme et al, unpublished data). kerV is upstream of the gloB gene, related with methylglioxal detoxification and downstream of the rnhA and dnaQ genes, both related with DNA replication and repair. The purpose of this work was to study the molecular function of KerV product and the expression of kerV-rnhA-dnaQ locus. Bioinformatics analysis indicated that KerV is a SAM dependent methyltransferase that have a conserved SAM binding domain with architecture compatible with classic alternating β-stranded and α-helical regions. KerV does not show any other conserved motif that could indicate its methylation substrate. Heterologous expression in E. coli showed that KerV is partially soluble only when co-expressed with GroeL/GroES chaperones at low temperatures or when KerV is in fusion with MBP or GST tag. During the purification process KerV was copurified with GroEL chaperone suggesting that this association may be required for the correct folding of KerV. Methyltransferase activity and SAM binding assays were done with purified MBPKerV and the results were not conclusive since the proper conformation of MBP-KerV cannot be verified. Yeast two-hybrid assays indicated that RNaseH and DnaQ are not interaction partners of KerV, suggesting that their functions are not directly related. The mutation frequency of D12 strain increased only about four times in relation to PA14, suggesting that KerV is not directly involved with DNA mismatch repair. The assays to detect methylation in DNA, RNAs and proteins do not show that KerV is involved with methylation of these substrates. The transcription start sites of kerV, rnhA and dnaQ genes were mapped through 5\'-RACE- and primer extension experiments. The kerV deletion causes a polar effect on the transcription of rnhA gene, which is not reflected on RNaseH protein levels. The kerV deletion also affects dnaQ expression, suggesting that KerV is important for its regulation.The virulence complementation assays in flies and lung epithelial cells showed that the fully rescue of the wild type phenotype was achieved only when the entire locus is present. KerV was essential to inhibit the NF-kB nucleus translocation, demonstrating that KerV is relevant to PA14 virulence, contributing for the silencing of host immune system. Altogether, these data showed a complex inter-relation among kerV, rnhA and dnaQ genes and its role in P. aeruginosa biology

Death from hunger and starvation can be avoided with appropriate diagnosis and treatment if the necessary knowledge and resources are available. The current definitions of acute malnutrition are based either upon a weight-for-height Z-score (WHZ) below -2 standard deviations of the international reference population (World Health Organization 2006 Growth Standards) or a mid-upper arm circumference (MUAC) lower than 125 mm. These indicators are used independently to define the sum of moderate and severe acute malnutrition, commonly referred to as global acute malnutrition (GAM). Severe acute malnutrition (SAM) is defined as the children with WHZ < -3 SD or MUAC <115 mm. These cut-off points are used both to estimate the prevalence of malnutrition and also to identify those children who should be admitted for individual treatment of their acute malnutrition.However, the ramifications of the new WHO standards and the introduction of the absolute MUAC as an additional criterion have not been sufficiently explored. There appears to have been little detailed analysis of the variation of MUAC in children using these new standards. Thus, there is insufficient information available for predicting changes in patient load due to the addition of an absolute MUAC cut-off, the degree of overlap between the criteria and the factors that affect the selection of malnourished children using the two criteria, WHZ and MUACNevertheless, because of the ease of use of MUAC and strong advocacy based mainly the relative sensitivity and specificity of WHZ and MUAC in predicting long-term all-cause mortality in the community, many organizations and some governments are now moving from using MUAC to screen children in the community and elsewhere to MUAC-only programs with abandonment of using WHZ altogether.A better understanding of the relationship between these measures is important as differences can have significant implications on the decision to intervene in a nutritional crises, assessment of potential program size, resource requirements and outcome, selection of children admitted for treatment and the strategy which will have the greatest influence upon mortality and the other poor outcomes of being malnourished. To this end my thesis included the following studies which explored the variation of MUAC and WHZ in children for the assessment of malnutrition.In my first study, I examined the direction and degree of discrepancy between MUAC and WHZ of children aged 6-59 months in 1,832 anthropometric surveys from 47 countries, mainly in Africa. The results show that using MUAC or WHZ, 16.3% of children were identified with GAM and 3.5% with SAM. The proportion of overlap between the two indicators was 28.2% for GAM (15-38.5%) and 16.5 % for SAM (6.1-29.8%). Overlap for individual countries was especially low for SAM. The numbers of children diagnosed by either criterion varied dramatically by country: the difference between the relative case-load using WHZ and MUAC for GAM varied from minus 57% to plus 72%. For SAM, in four of the 38 countries, less than 25% of severely malnourished children would be identified and admitted for treatment if a MUAC-only admission policy were being used. For all countries examined, the discrepancies were not adequately explained by any single hypothesis. My second study was in three parts. Each part examined the veracity of the assertion that MUAC is a better indicator of mortality than WHZ. 1) I analysed individual data from 76,887 children admitted to a range of treatment programmes to determine the mortality rates associated with SAM. 2) I conducted an exhaustive search of the literature to identify reports of children diagnosed by WHZ or MUAC with their respective mortality rates.3) I analysed the effect of case load using the prevalence data published in the first study with Case Fatality Rates (CFRs) derived from the empirical data, the literature data and theoretical simulations. We found that mathematical coupling caused a reversal of significance generating Simpson’s paradox so that the interpretation of the relative mortality rates of WHZ and MUAC is unsafe when children with both criteria are included in each group being compared. The analysis suggests that children with SAM identified by WHZ <-3 and admitted for treatment are at as least as high a risk of death as children in treatment with MUAC<115cm and probably at higher risk. Review of 21 datasets that compared WHZ and MUAC mortality rates show problems with interpretation of the reported CFRs in each of the studies; inconsistencies greatly limit analysis, comparability and interpretation. Caseload is a more important determinant of the number of SAM related child deaths than the relative CFR to give the number of SAM attributable deaths. Where most of the children are identified as SAM using WHZ, rather than MUAC, it is estimated that fewer than half of all SAM related deaths will be identified using a MUAC-only programme.In my third study, I have conducted a Monte Carlo simulation of anthropometric surveys and imposed random errors of measurement on the data in order to examine the effect of measurement error. The results show that there is an increase in the standard deviation with each of the errors, that the spread becomes exponentially greater with the magnitude of the sort of error that occur in real life situations and that the effect of an increase in standard deviation (SD) that appears to be fairly trivial has a major effect upon the reported prevalence of the condition. I show that even within quite a narrow range of SDs (from 0.8 to 1.2) the proportion of children <-2 WHZ can increase from 6% to 15% - which would move the population from one of “acceptable” prevalence to an acute emergency situation. The corresponding SAM would increase from about 1% to nearly 5%. If one was to use such a survey to estimate the current case-load of SAM children the difference would be five-fold. However, this range of SDs is generally thought to represent a “good survey”. When larger and more complex surveys are considered, for example those included in the WHO database or the DHS surveys, the SD is frequently greater than 1.2 leading to give a higher reported prevalence of malnutrition than may be the actual prevalence. In my fourth study, I performed a secondary analysis of the surveys collected in my first study in order to examine the change in reliability of such surveys over time. I analysed the statistical distributions of the derived anthropometric parameters from 1,843 surveys conducted by 19 agencies between 1986 and 2015. The results show that with the introduction of standardised guidelines and software by 2003 and their more general application from 2007 the mean standard deviation, kurtosis and skewness of the parameters used to assess nutritional status have each moved to now approximate the distribution of the WHO standards when the exclusion of outliers from analysis is based upon the SMART flagging procedure. Where WHO flags, that only exclude data incompatible with life, are used the quality of anthropometric surveys has improved and the results now approach those seen with SMART flags and the WHO standards distribution. Agencies vary in their uptake and adherence to standard guidelines. Those agencies that fully implement the guidelines achieve the most consistently reliable results.In conclusion, well-defined and internationally accepted criteria to assess anthropometric survey quality should be universally applied and reported if the surveys are to be reliable, credible and form the basis for appropriate intervention. Using WHZ-only or MUAC-only estimates of prevalence will underestimate the burden of acute malnutrition. Such a program policy would result in between 300,000 and 600,000 SAM deaths occurring in children each year who have no possibility of being treated. WHZ and MUAC are complementary indicators, it is only by using both criteria to identify SAM and admit children for treatment that we will move towards reducing avoidable SAM- related mortality in most countries. This will only be realised when we can conveniently identify children with a low WHZ in community screening programs. / Doctorat en Sciences de la santé Publique / info:eu-repo/semantics/nonPublished

Chez les spores de bactéries, le photoproduit le plus abondant formé dans l'ADN irradié par les UV est un dimère de thymines appelé Photoproduit des spores (SP, 5-(a-thyminyl)-5,6-dihydrothymine). Au début de la germination, ce photoproduit est spécifiquement réparé par une enzyme, la Spore Photoproduct Lyase (SPL), régénérant les deux résidus thymine originaux. Cette enzyme est une protéine Fe-S qui appartient à la famille des « Radical-SAM ». Les protéines de cette famille d'enzymes possèdent un centre [4Fe-4S], coordiné par 3 cystéines conservées organisées selon le motif CxxxCxxC, et utilisent la SAdénosylméthionine comme cofacteur. Elles fonctionnent toutes selon un mécanisme <br />radicalaire, initié par la formation du radical 5'-désoxyadénosyle issu de la coupure homolytique de la S-Adénosylméthionine par le centre [4Fe-4S] réduit. Dans ce travail, nous avons effectué une caractérisation biochimique et spectroscopique des SPL de Clostridium acetobutylicum et Bacillus subtilis. Par ailleurs, nous avons synthétisé un substrat minimum sous la forme d'un dinucléoside monophosphate appelé SPTpT, pour lequel une caractérisation structurale par RMN a été réalisée. Le SPTpT est reconnu et efficacement réparé par l'enzyme, ce qui nous a permis d'obtenir de nouvelles informations sur le mécanisme enzymatique de réparation. Enfin, la séquence primaire des SPL contient une 4e cystéine conservée, essentielle à la réparation, mais qui n'est pas impliquée dans la coordination du centre [Fe-S]. Nous nous sommes intéressés au rôle de cette cystéine dans le mécanisme de réparation grâce à l'étude biochimique et enzymatique du mutant SPLC141A.

<p>Denna uppsats syftar till att ge en bild av förbundet Humanisternas debatt och porträttering av islam och muslimer. Detta med hjälp av utländska ateister som även förekommit i förbundets egen tidskrift <em>Humanisten</em>. Mina frågeställningar är: Hur framställs islam och muslimer av media och av förbundet Humanisterna? Vilken kritik har framförts av Humanisterna angående islam och muslimer? Bidrar förbundet till en ökad schablonisering av islam och muslimer? För att nämna kortfattat vad jag kommit fram till kan det sägas att Humanisterna, när de skriver om islam eller muslimer, delvis är intoleranta i sin retorik. Den kritik som framförts mot förbundet är bland annat att de vill tvinga på en sekulär livsåskådning och att de tror dig ha ett slags monopol på sanningen. Eftersom den mediebild som redan existerar av islam och muslimer är negativt laddad, så hjälper Humanisterna till att öka den bild av islam som finns som den ”onda, mörka” religionen i vår tid, det vill säga, man bidrar till redan existerande schablonisering av muslimer.</p>

SiGe nanostructures on crystalline Si substrates with (001) orientation are among the most studied system in condensed matter physics and nanoscience. This interest has been mainly driven by the important potential applications in opto and nano-electronic devices thanks to the improvement of the optical and electronic properties compared to bulk systems. These features come essentially from the possibility of engineering the strain field within the nanostructures using the lattice mismatch of ~ 4 % between Ge and Si and from the spatial confinement, capable of modifying the electronic band structure leading to an increase of the charge carrier mobility. It is obvious that these applications largely depend on the control of surface processes during the growth of the nanostructures, and their performance are strongly dependent on strain relaxation and dislocation injection. Besides the technological interest, the SiGe/Si(001) system has received much attention since it is also a model for understanding the fundamental processes occurring during 3D island formation and self-organization phenomena. In fact, the lattice mismatch between Ge and Si introduces a stress field which has dramatic effects on the growth process and is responsible for a number of structural and electronic phenomena. In particular, the stored elastic energy can be partially relieved by spontaneous formation of 3D objects of nanometric size on top of a pseudomorphic SiGe wetting layer. This growth mode, called Stranski-Krastanov (SK), is a way of easily forming self-assembled nanostructures, which can be used to obtain quantum confinement of charge carriers in nanoelectronics device applications. In recent years, considerable efforts have been devoted to the growth of hetero-epitaxial SiGe nanostructures with well controlled size, shape and positioning, and with defined stoichiometry and strain state. However, some aspects still need to be addressed for a complete understanding of this system, including: (i) the competition between kinetic and thermodynamic factors for island formation, (ii) the mechanisms governing the relative growth of individual nanostructures, (iii) the interplay between SiGe intermixing and strain relaxation mechanisms. In the present work, we carry out an experimental investigation of the relationship between morphology, elemental composition, strain state and electronic structure of self-assembled and lithographically defined SiGe nanostructures by means of several spectro-microscopy techniques. The Si and Ge diffusion dynamics and the self-organization phenomena during the growth of SiGe islands have been studied by Scanning Auger Microscopy (SAM) and Atomic Force Microscopy (AFM). Micro-Raman, SAM and Scanning Transmission Electron Microscopy coupled with Electron Energy Loss Spectroscopy (STEM-EELS) techniques have been used for the investigation of the interplay between strain relaxation mechanisms and SiGe intermixing in self-assembled islands. The effects of strain and composition on the electronic band structure in lithographically defined SiGe nanostructures, in layout very close to those used in prototype devices, have been characterized with nanoscale spatial resolution joining information from Tip Enhanced Raman Spectroscopy (TERS), nanofocused X-Ray Diffraction (XRD) and Energy-Filtered PhotoElectron Emission Microscopy (PEEM). The thesis is conceptually divided in two main parts: the first, to which belong Chapters 1, 2 and 3, deals with the experimental investigation of the Ge surface diffusion and of the self-organization phenomena of SiGe islands grown in a bottom-up approach; the second, including Chapters 4 and 5, is based on the experimental characterization of the strain state and of the strain-induced effects on the electronic band structure of lithographically defined SiGe nanostructures obtained in a top-down approach Chapter 1 presents an overview on the basic processes occurring during hetero-epitaxial growth of thin solid films. In the Chapter 2 the surface diffusion of Ge on a clean and C covered Si(001) surface promoted by annealing at high temperatures in UHV of pure Ge stripes is experimentally investigated by means of in-situ Scanning Auger Microscopy. The influence of a controlled carbon coverage on the Ge surface diffusion is quantitatively studied, showing that the diffusion coefficient presents a strong dependence on carbon coverage (see Fig. 1(a)). Chapter 3 deals with the experimental investigation of the growth process of self-assembled SiGe islands on Si(001) (see Fig. 1(b)). From the size and density evolution exhibited by the nucleated islands, we propose a scenario where the island growth is essentially driven by kinetic factors within a diffusion limited regime. Finally, we investigated the interplay among SiGe intermixing and plastic relaxation, showing that the surface thermal diffusion growth method leads to the formation of coherent islands (dislocation-free), as shown in Fig. 1(c), larger than those attainable by MBE and CVD. Chapter 4 presents the mapping with nanoscale resolution of strain, composition, local work function and valence band structure of lithographically defined SiGe embedded nano-stripes using TERS and Energy-Filtered PEEM (see Fig. 1(d) showing the Ge concentration mapping of the nano-stripes as obtained by PEEM analysis). In Chapter 5 are presented the first results of a direct characterization of the strain state of lithographically defined SiGe nano-ridges using the recently developed nanofocused XRD technique. The work presented in this thesis is the outcome of an experimental PhD research project developed at the Politecnico di Milano (Milano, Italy) in co-tutorship with the École Polytechnique (Paris, France) and the French Atomic Energy Commission (CEA-Saclay, France). SAM and AFM have been performed at Department of Physics of the Politecnico di Milano. Micro-Raman Spectroscopy has been carried out at the Materials Science Department of the Università Milano-Bicocca. PEEM measurements have been realized at CEA and during two standard experimental runs at the TEMPO beamline of SOLEIL Synchrotron (France). TERS and preliminary TEM analysis have been performed at the École Polytechnique, while more extensive TEM and STEM-EELS measurements have been developed at IMM-CNR in Catania. The nano-XRD experiment has been carried out during a standard experimental run at ID13 beamline of the European Synchrotron Radiation Facility (ESRF). The close collaboration with the laboratory L-NESS in Como made available the set of the lithographically-defined investigated samples. The experimental results have been exploited in close collaboration with a theory group at the Materials Science Department of the Università Milano-Bicocca for a deeper insight into the atomic level mechanisms during island growth process.

Nanofabrication techniques were used to manufacture nanometer scale protein templates. The fabrication approach employs electron beam lithography (EBL) patterning on poly(ethylene glycol) (PEG) thiol (CH3O(CH2CH2O)17NHCO(CH2)2SH) self-assembled monolayers (SAM) on Au. The PEG SAM prevented protein surface adhesion and binding sites for protein were created in the SAM by EBL. Subsequent to EBL, the patterns in the PEG SAM were backfilled with 40-nm NeutrAvidin-coated fluorescent spheres (FluoSpheres). The spontaneous and directed immobilization of the spheres from a solution to the patterns resulted in high resolution protein patterns. The FluoSpheres could be arranged in any arbitrary pattern with ultimately only one or a few FluoSpheres at each binding site. Growth dynamics and SAM morphology of PEG on Au were studied by atomic force microscopy (AFM). PEG SAMs on three types of Au with different microstructure were examined: thermally evaporated granular Au and two types of Au films produced by hydrogen flame annealing of granular Au, Au(111) and "terraced" Au (crystal orientation unknown). The different Au surfaces' substructure affected the morphology and mechanical properties of the PEG SAM. On Au(111), AFM imaging revealed monolayer formation through three distinct steps: island nucleation, island growth, and coalescence. The fine-structure of the SAM revealed dendritic island formation - an observation which can be explained by attractive intermolecular interactions and diffusion-limited aggregation. Island growth was not observed on the "terraced" Au. AFM studies of EBL patterned PEG SAMs on Au(111) revealed two different patterning mechanisms. At low doses, the pattern formation occurs by SAM ablation in a self-developing process where the feature depth is directly dose dependent. At higher doses electron beam induced deposition of material, so-called contamination writing, is seen in the ablated areas of the SAM. The balance between these two mechanisms is shown to depend on the geometry of the pattern. In addition to PEG SAMs, fibronectin monolayers on SiO2 surfaces were patterned by EBL. The areas exposed with EBL lose their functionality and do not bind anti-fibronectin. With this approach we constructed fibronectin templates and used them for cell studies demonstrating pattern dependent cell geometries and cell adhesion. / QC 20101008

A novel cyclopentadienylruthenium(II) thiolato Schiff base, [Ru(SC6H4NC(H)C6H4OCH2CH2SMe)(&eta / 5-C2H5]2 was synthesized and deposited as a selfassembled monolayer (SAM) on a gold electrode. Effective electronic communication between the Ru(II) centers and the gold electrode was established by electrostatically cycling the Shiff base-doped gold electrode in 0.1 M NaOH from -200 mV to +600 mV. The SAMmodified gold electrode (Au/SAM) exhibited quasi-reversible electrochemistry. The integrity of this electro-catalytic SAM, with respect to its ability to block and electro-catalyze certain Faradaic processes, was interrogated using Cyclic and Osteryoung Square Wave voltammetric experiments. The formal potential, E0', varied with pH to give a slope of about - 34 mV pH-1. The surface concentration, &Gamma / , of the ruthenium redox centers was found to be 1.591 x 10-11 mol cm-2. By electrostatically doping the Au/SAM/Horseradish peroxidase at an applied potential of +700 mV vs Ag/AgCl, a biosensor was produced for the amperometric analysis of hydrogen peroxide, cumene hydroperoxide and tert-butylhydroperoxide. The electrocatalytic-type biosensors displayed typical Michaelis-Menten kinetics with their limits of detection of 6.45 &mu / M, 6.92 &mu / M and 7.01 &mu / M for hydrogen peroxide, cumene hydroperoxide and tert-butylhydroperoxide respectively.

This thesis deals with the synthesis of electroactiveorganic compounds. The synthesis of ethylenedioxy-benzodioxinstri-dioxin and tetra-dioxin are described. These molecules wereprepared with the aim of creating donor molecules for cationicradical salts. The symmetric analogs of tri-dioxin,methylenedioxy-derivative and ethylenedioxy-naphthalene werealso synthesized. Three different cation radical salts with 2:1stoichiometries were obtained from tri-dioxin, whiletetra-dioxin merely provided polycrystalline materials.Tri-dioxin and tetra-dioxin were also successful as operationalmatrixes in PALDI-TOF. Tetrathiafulvalenes with the2-dialkyl-amino-1,3-dithiolium-4-thiolate mesoion asbuilding-block was also synthesized. A series of doublyalkylthiol-substituted TTFs were prepared with the aim offorming self-assembly monolayers on gold surfaces in theapplication of organic thin film field-effect transistors.Film-formation for two TTFs were studied and they providedrelatively dense packed monolayers with a discrete distance ofthe TTF moiety from the gold surface. The mesoionic compound was also for the first time used inanumpolungreaction. The electrophile obtained in situ bytreatment of mesoion with sulfuryl chloride was reacted with avariety of electron-rich aromatic compounds. From the receivedproducts three new arylthio-substituted TTFs weresynthesized. <b>Keywords:</b>Synthesis, Benzodioxin, Tetrathiafulvalene,Mesoion, Organic Conductor, Cation Radical Salt, CyclicVoltammetry, Electrocrystallization, Self-Assembly Monolayer,SAM, Organic Field-Effect Transistor, OFET

Building Integrated Photo Voltaics (BIPVs) are devices which are manufactured to replace building components exposed to sufficient sunlight to generate energy. Photo Voltaic Roof tiles are Building Integrated components which can be used instead of traditional roofing materials. The following thesis is focused on comparing traditional, cheaper asphalt roof tiles with Photo Voltaic (PV) roofing tiles in terms of energy cost savings during their respective Net Present Values. The method used for achieving this is computer simulation made possible by software named "Solar Advisory Model" (SAM), developed by National Renewable Energy Laboratories (NREL), to simulate energy output and resultant energy costs saved. The simulations have been run on a prototype example of a model of a dwelling unit's roof area. The simulations have been repeated for 35 cities all over the U.S.A. for 5 different climatic zones on the same prototype example of the dwelling unit. Similarly, the roof area being laid with an array of PV roof tiles has been estimated for coverage by traditional asphalt roof shingles by using data from the RS Means construction costs data. The estimated costs associated with the asphalt roof area have been adjusted to a different set of 35 locations from the 5 climatic zones by using the location factor from RS Means. A statistical analysis was done to analyze the data, net present value of roofing materials being the dependent variable versus climatic zones and roofing material as the independent variables. The statistical model also included CDD (Cooling Degree Days) and HDD (Heating Degree Days) as co-variates. The results indicate that NPV (Net Present Value) of BIPV roof is significantly different from that of asphalt roof. Another statistical analysis was done to determine the effect of climatic zones on energy savings due to the use of BIPV roofing. Energy savings (in US$) was used as a dependent variable, and climatic zone as the independent variable. HDD AND CDD were also included in this model as co-variates. The results of this test indicate that both climatic zone and HDD have an effect on total energy savings.