Electron impact excitation of Kr XXXII

Collision strengths (Ω) have been calculated for all 7750 transitions among the lowest 125 levels belonging to the View the MathML source, and 2p23ℓ configurations of boron-like krypton, Kr XXXII, for which the Dirac Atomic R -matrix Code has been adopted. All partial waves with angular momentum J⩽40 have been included, sufficient for the convergence of Ω for forbidden transitions. For allowed transitions, a top-up has been included in order to obtain converged values of Ω up to an energy of 500 Ryd. Resonances in the thresholds region have been resolved in a narrow energy mesh, and results for effective collision strengths (ϒ) have been obtained after averaging the values of Ω over a Maxwellian distribution of electron velocities. Values of ϒ are reported over a wide temperature range below View the MathML source, and the accuracy of the results is assessed. Values of ϒ are also listed in the temperature range View the MathML source, obtained from the nonresonant collision strengths from the Flexible Atomic Code.

Non-thiazolidinedione antihyperglycemic agents. Part 5: asymmetric aldol synthesis of (S)-(-)-2-oxy-3-arylpropanoic acids.

Haigh, David; Birrell, Helen C.; Cantello, Barrie C. C.; Eggleston, Drake S.; Haltiwanger, R. Curtis; Hindley, Richard M.; Ramaswamy, Anantha; Stevens, Nicola C. Department of Medicinal Chemistry, SmithKline Beecham Pharmaceuticals, Essex, UK. Tetrahedron: Asymmetry (1999), 10(7), 1353-1367. Publisher: Elsevier Science Ltd., CODEN: TASYE3 ISSN: 0957-4166. Journal written in English. CAN 131:144537 AN 1999:369514 CAPLUS (Copyright (C) 2009 ACS on SciFinder (R)) Abstract Boron-mediated asym. aldol reactions of 4-[2-(2-benzoxazolylmethylamino)ethoxy]benzaldehyde with 2-oxyethanoyloxazolidinones contg. electron withdrawing, chelating, and bulky alkoxy and aryloxy groups, gave variable yields of syn-aldol adducts in high diastereoisomeric excess. These adducts were dehydroxylated in a sequence which complements the traditional Evans asym. alkylation strategy. Cleavage of the auxiliary from these intermediates afforded antihyperglycemic (S)-(-)-2-oxy-3-arylpropanoic acids in excellent enantiomeric excess. The target compds. were ?-alkoxy-4-[2-[(benzoxazolyl)amino]ethoxy]benzenepropanoic acid derivs. The biol. activity of the compds. thus prepd. was not reported here.

Observation of K-Shell Soft X Ray Emission of Nitrogen Irradiated by XUV-Free Electron Laser FLASH at Intensities Greater than 10(16) W/cm(2)

In the past few years, the development of light sources of the 4(th) generation, namely XUV/X-ray Free Electron Lasers provides to the scientific community outstanding tools to investigate matter under extreme conditions never obtained in laboratories so far. As theory is at its infancy, the analysis of matter via the self-emission of the target is of central importance. The characterization of such dense matter is possible if photons can escape the medium. As the absorption of K-shell X-ray transitions is minimal, it plays a key role in this study. We report here the first successful observation of K-shell emission of Nitrogen at 430 eV using an XUV-Free Electron Laser to irradiate solid Boron Nitride targets under exceptional conditions: photon energy of 92 eV, pulse duration of similar to 20 fs, micro focusing leading to intensities larger than 10(16) W/cm(2). Using a Bragg crystal of THM coupled to a CCD, we resolved K-shell line emission from different charge states. We demonstrate that the spectroscopic data allow characterization of electron heating processes when X-ray radiation is interacting with solid matter. As energy transport is non-trivial because the light source is monochromatic, these results have an important impact on the theory. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Design, Manufacture and Performance of Germanium Bipolar Transistors

Germanium NPN bipolar transistors have been manufactured using phosphorus and boron ion implantation processes. Implantation and subsequent activation processes have been investigated for both dopants. Full activation of phosphorus implants has been achieved with RTA schedules at 535?C without significant junction diffusion. However, boron implant activation was limited and diffusion from a polysilicon source was not practical for base contact formation. Transistors with good output characteristics were achieved with an Early voltage of 55V and common emitter current gain of 30. Both Silvaco process and device simulation tools have been successfully adapted to model the Ge BJT(bipolar junction transistor) performance.

Synthesis of molybdenum borides and molybdenum silicides in molten salts and their oxidation behavior in an air-water mixture

The formation of various coatings in molybdenum-boron and molybdenum-silicon systems was investigated. Boronizing and siliciding treatments were conducted in molten salts under inert gas atmosphere in the 850-1050 degrees C temperature range for 7 h. The presence of boride (e.g. Mo2B, MoB, Mo2B5) and silicide (MoSi2, Mo5Si3) phases, formed on the surface of Mo plates, was confirmed by X-ray diffraction analysis. The distribution of elements was determined by means of wavelength dispersive spectroscopy (WDS) spectra of the surface and line-scan analyses from surface to interior. Depending on the process type (diffusional or electrochemical) and temperature, the thickness of the protective layers formed on the substrate ranged from 6 to 40 gm. The oxidation resistance of obtained phases was investigated in an air-water mixture in the temperature range of 500-700 degrees C for a period up to 400 h. An improved oxidation behavior of coated plates in comparison with that of pure molybdenum was observed. (c) 2004 Elsevier B.V. All rights reserved.

Discovery of a Potent Boronic Acid Derived Inhibitor of the HCV RNA-Dependent RNA Polymerase

A boronic acid moiety was found to be a critical pharmacophore for enhanced in vitro potency against wild type hepatitis C replicons and known clinical polymorphic and resistant HCV mutant replicons. The synthesis, optimization, and structure-activity relationships associated with inhibition of HCV replication in a sub-genomic replication system for a series of non-nucleoside boron-containing HCV RNA-Dependent RNA Polymerase (NS5B) inhibitors are described. A summary of the discovery of GSK5852 (3), a molecule which entered clinical trials in subjects infected with HCV in 2011, is included.

Profiling the ionome of rice and its use in discriminating geographical origins at the regional scale, China

Element profile was investigated for their use to trace the geographical origin of rice (Oryza sativa L.) samples. The concentrations of 13 elements (calcium (Ca), potassium (K), magnesium (Mg), phosphorus (P), boron (B), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), arsenic (As), selenium (Se), molybdenum (Mo), and cadmium (Cd)) were determined in the rice samples by inductively coupled plasma optical emission and mass spectrometry. Most of the essential elements for human health in rice were within normal ranges except for Mo and Se. Mo concentrations were twice as high as those in rice from Vietnam and Spain. Meanwhile, Se concentrations were three times lower in the whole province compared to the Chinese average level of 0.088 mg/kg. About 12% of the rice samples failed the Chinese national food safety standard of 0.2 mg/kg for Cd. Combined with the multi-elemental profile in rice, the principal component analysis (PCA), discriminant function analysis (DFA) and Fibonacci index analysis (FIA) were applied to discriminate geographical origins of the samples. Results indicated that the FIA method could achieve a more effective geographical origin classification compared with PCA and DFA, due to its efficiency in making the grouping even when the elemental variability was so high that PCA and DFA showed little discriminatory power. Furthermore, some elements were identified as the most powerful indicators of geographical origin: Ca, Ni, Fe and Cd. This suggests that the newly established methodology of FIA based on the ionome profile can be applied to determine the geographical origin of rice.

Long-Range Lateral Dopant Diffusion in Tungsten Silicide Layers

Novel diode test structures have been manufactured to characterize long-range dopant diffusion in tungsten silicide layers. A tungsten silicide to p-type silicon contact has been characterized as a Schottky barrier rectifying contact with a silicide work function of 4.8 eV. Long-range diffusion of boron for an anneal at 900 °C for 30 min has been shown to alter this contact to become ohmic. Long-range diffusion of phosphorus with a similar anneal alters the contact to become a bipolar n-p diode. Bipolar diode action is demonstrated experimentally for anneal schedules of 30 min at 900 °C, indicating long-range diffusion of phosphorus (~38 µm), SIMS analysis shows dopant redistribution is adversely affected by segregation to the silicide/oxide interface. The concept of conduit diffusion has been demonstrated experimentally for application in advanced bipolar transistor technology. © 2009 IEEE.

Electroless nickel, alloy, composite and nano coatings - A critical review

The development of metal deposition processes based on electroless nickel, alloy and composite coatings on various surfaces has witnessed a surge in interest among researchers, with many recent applications made possible from many excellent properties. In recent years, these coatings have shown promising corrosion and wear resistance properties and large number of newer developments became most important from macro to nano level applications. After a brief review of the fundamental aspects underlying the coating processes, this paper discusses in detail about different electroless nickel alloy, composite, nano plating, bath techniques, preparation, characterization, new depositing mechanism and their recent applications, including brief notes on difficult substrate and waste treatment for green environment. Emphasis will be onto their recent progress, which will be discussed in detail and critically reviewed.

Lewis Superacidic Ionic Liquids with Tricoordinate Borenium Cations

The first examples of ionic liquids based on borenium cations, [BCl2L](+), are reported. These compounds form highly Lewis acidic liquids under solvent-free conditions. Their acidity was quantified by determining the Gutmann acceptor number (AN). Extremely high ANs were recorded (up to AN=182, delta(31P)=120 ppm), demonstrating that these borenium ionic liquids are the strongest Lewis superacids reported to date, with the acidity enhanced by the ionic liquid environment.

Electromechanical properties of engineered lead free potassium sodium niobate based materials

K0.5Na0.5NbO3 (KNN), is the most promising lead free material for substituting lead zirconate titanate (PZT) which is still the market leader used for sensors and actuators. To make KNN a real competitor, it is necessary to understand and to improve its properties. This goal is pursued in the present work via different approaches aiming to study KNN intrinsic properties and then to identify appropriate strategies like doping and texturing for designing better KNN materials for an intended application. Hence, polycrystalline KNN ceramics (undoped, non-stoichiometric; NST and doped), high-quality KNN single crystals and textured KNN based ceramics were successfully synthesized and characterized in this work. Polycrystalline undoped, non-stoichiometric (NST) and Mn doped KNN ceramics were prepared by conventional ceramic processing. Structure, microstructure and electrical properties were measured. It was observed that the window for mono-phasic compositions was very narrow for both NST ceramics and Mn doped ceramics. For NST ceramics the variation of A/B ratio influenced the polarization (P-E) hysteresis loop and better piezoelectric and dielectric responses could be found for small stoichiometry deviations (A/B = 0.97). Regarding Mn doping, as compared to undoped KNN which showed leaky polarization (P-E) hysteresis loops, B-site Mn doped ceramics showed a well saturated, less-leaky hysteresis loop and a significant properties improvement. Impedance spectroscopy was used to assess the role of Mn and a relation between charge transport – defects and ferroelectric response in K0.5Na0.5NbO3 (KNN) and Mn doped KNN ceramics could be established. At room temperature the conduction in KNN which is associated with holes transport is suppressed by Mn doping. Hence Mn addition increases the resistivity of the ceramic, which proved to be very helpful for improving the saturation of the P-E loop. At high temperatures the conduction is dominated by the motion of ionized oxygen vacancies whose concentration increases with Mn doping. Single crystals of potassium sodium niobate (KNN) were grown by a modified high temperature flux method. A boron-modified flux was used to obtain the crystals at a relatively low temperature. XRD, EDS and ICP analysis proved the chemical and crystallographic quality of the crystals. The grown KNN crystals exhibit higher dielectric permittivity (29,100) at the tetragonal-to-cubic phase transition temperature, higher remnant polarization (19.4 μC/cm2) and piezoelectric coefficient (160 pC/N) when compared with the standard KNN ceramics. KNN single crystals domain structure was characterized for the first time by piezoforce response microscopy. It could be observed that <001> - oriented potassium sodium niobate (KNN) single crystals reveal a long range ordered domain pattern of parallel 180° domains with zig-zag 90° domains. From the comparison of KNN Single crystals to ceramics, It is argued that the presence in KNN single crystal (and absence in KNN ceramics) of such a long range order specific domain pattern that is its fingerprint accounts for the improved properties of single crystals. These results have broad implications for the expanded use of KNN materials, by establishing a relation between the domain patterns and the dielectric and ferroelectric response of single crystals and ceramics and by indicating ways of achieving maximised properties in KNN materials. Polarized Raman analysis of ferroelectric potassium sodium niobate (K0.5Na0.5)NbO3 (KNN) single crystals was performed. For the first time, an evidence is provided that supports the assignment of KNN single crystals structure to the monoclinic symmetry at room temperature. Intensities of A′, A″ and mixed A′+A″ phonons have been theoretically calculated and compared with the experimental data in dependence of crystal rotation, which allowed the precise determination of the Raman tensor coefficients for (non-leaking) modes in monoclinic KNN. In relation to the previous literature, this study clarifies that assigning monoclinic phase is more suitable than the orthorhombic one. In addition, this study is the basis for non-destructive assessments of domain distribution by Raman spectroscopy in KNN-based lead-free ferroelectrics with complex structures. Searching a deeper understanding of the electrical behaviour of both KNN single crystal and polycrystalline materials for the sake of designing optimized KNN materials, a comparative study at the level of charge transport and point defects was carried out by impedance spectroscopy. KNN single crystals showed lower conductivity than polycrystals from room temperature up to 200 ºC, but above this temperature polycrystalline KNN displays lower conductivity. The low temperature (T < 200 ºC) behaviour reflects the different processing conditions of both ceramics and single crystals, which account for less defects prone to charge transport in the case of single crystals. As temperature increases (T > 200 ºC) single crystals become more conductive than polycrystalline samples, in which grain boundaries act as barriers to charge transport. For even higher temperatures the conductivity difference between both is increased due to the contribution of ionic conduction in single crystals. Indeed the values of activation energy calculated to the high temperature range (T > 300 ºC) were 1.60 and 0.97 eV, confirming the charge transport due to ionic conduction and ionized oxygen vacancies in single crystals and polycrystalline KNN, respectively. It is suggested that single crystals with low defects content and improved electromechanical properties could be a better choice for room temperature applications, though at high temperatures less conductive ceramics may be the choice, depending on the targeted use. Aiming at engineering the properties of KNN polycrystals towards the performance of single crystals, the preparation and properties study of (001) – oriented (K0.5Na0.5)0.98Li0.02NbO3 (KNNL) ceramics obtained by templated grain growth (TGG) using KNN single crystals as templates was undertaken. The choice of KNN single crystals templates is related with their better properties and to their unique domain structure which were envisaged as a tool for templating better properties in KNN ceramics too. X-ray diffraction analysis revealed for the templated ceramics a monoclinic structure at room temperature and a Lotgering factor (f) of 40% which confirmed texture development. These textured ceramics exhibit a long range ordered domain pattern consisting of 90º and 180º domains, similar to the one observed in the single crystals. Enhanced dielectric (13017 at TC), ferroelectric (2Pr = 42.8 μC/cm2) and piezoelectric (d33 = 280 pC/N) properties are observed for textured KNNL ceramics as compared to the randomly oriented ones. This behaviour is suggested to be due to the long range ordered domain patterns observed in the textured ceramics. The obtained results as compared with the data previously reported on texture KNN based ceramics confirm that superior properties were found due to ordered repeated domain pattern. This study provides an useful approach towards properties improvement of KNN-based piezoelectric ceramics. Overall, the present results bring a significant contribution to the pool of knowledge on the properties of sodium potassium niobate materials: a relation between the domain patterns and di-, ferro-, and piezo-electric response of single crystals and ceramics was demonstrated and ways of engineering maximised properties in KNN materials, for example by texturing were established. This contribution is envisaged to have broad implications for the expanded use of KNN over the alternative lead-based materials.

Diamond microelectrodes for corrosion studies

Este trabalho teve como objetivos a produção, caracterização e aplicação de microelétrodos (MEs) de diamante como sensores amperométricos e potenciométricos em sistemas de corrosão nos quais a agressividade do meio e a presença de produtos de corrosão, constituem obstáculos que podem diminuir o desempenho, ou inviabilizar a utilização, de outros tipos de sensores. Os microeléctrodos são baseados em filmes finos de diamante dopado com boro (BDD – Boron Doped Diamond) depositados sobre fios de tungsténio afiados, através do método de deposição química a partir da fase vapor, assistida por filamento quente (HFCVD – Hot Filament Chemical Vapor Deposition). A otimização das diversas etapas de fabricação dos MEs deu origem ao desenvolvimento de um novo sistema de afiamento eletroquímico para obtenção destes fios e a várias opções para a obtenção dos filmes de diamante condutor e seu isolamento com resinas para exposição apenas da ponta cilíndrica. A qualidade cristalina dos filmes de diamante foi avaliada por espectroscopia de Raman. Esta informação foi complementada com uma caracterização microestrutural dos filmes de diamante por microscopia eletrónica de varrimento (SEM), em que se fez a identificação da tipologia dos cristais como pertencendo às gamas de diamante nanocristalino ou microcristalino. Os filmes de BDD foram utilizados na sua forma não modificada, com terminações em hidrogénio e também com modificação da superfície através de tratamentos de plasma RF de CF4 e O2 indutores de terminações C-F no primeiro caso e de grupos C=O, C-O-C e C-OH no segundo, tal como determinado por XPS. A caracterização eletroquímica dos MEs não modificados revelou uma resposta voltamétrica com elevada razão sinal/ruído e baixa corrente capacitiva, numa gama de polarização quasi-ideal com extensão de 3 V a 4 V, dependente dos parâmetros de crescimento e pós-tratamentos de superfície. Estudou-se a reversibilidade de algumas reações heterogéneas com os pares redox Fe(CN)6 3-/4- e FcOH0/+ e verificou-se que a constante cinética, k0, é mais elevada em elétrodos com terminações em hidrogénio, nos quais não se procedeu a qualquer modificação da superfície. Estes MEs não modificados foram também testados na deteção de Zn2+ onde se observou, por voltametria cíclica, que a detecção da redução deste ião é linear numa escala log-log na gama de 10-5-10-2 M em 5 mM NaCl. Realizaram-se também estudos em sistemas de corrosão modelares, em que os microeléctrodos foram usados como sensores amperométricos para mapear a distribuição de oxigénio e Zn2+ sobre um par galvânico Zn-Fe, com recurso a um sistema SVET (Scanning Vibrating Electrode Technique). Foi possível detetar, com resolução lateral de 100 μm, um decréscimo da concentração de O2 junto a ambos os metais e produção de catiões de zinco no ânodo. Contudo verificou-se uma significativa deposição de zinco metálico na superfície dos ME utilizados. Os MEs com superfície modificada por plasma de CF4 foram testados como sensores de oxigénio dissolvido. A calibração dos microeléctrodos foi efetuada simultaneamente por voltametria cíclica e medição óptica através de um sensor de oxigénio comercial. Determinou-se uma sensibilidade de ~0.1422 nA/μM, com um limite de deteção de 0.63 μM. Os MEs modificados com CF4 foram também testados como sensores amperométricos com os quais se observou sensibilidade ao oxigénio dissolvido em solução, tendo sido igualmente utilizados durante a corrosão galvânica de pares Zn-Fe. Em alguns casos foi conseguida sensibilidade ao ião Zn2+ sem que o efeito da contaminação superficial com zinco metálico se fizesse sentir. Os microeléctrodos tratados em plasma de CF4 permitem uma boa deteção da distribuição de oxigénio, exibindo uma resposta mais rápida que os não tratados além de maior estabilidade de medição e durabilidade. Nos MEs em que a superfície foi modificada com plasma de O2 foi possível detetar, por cronopotenciometria a corrente nula, uma sensibilidade ao pH de ~51 mV/pH numa gama de pH 2 a pH 12. Este comportamento foi associado à contribuição determinante de grupos C-O e C=O, observados por XPS com uma razão O/C de 0,16. Estes MEs foram igualmente testados durante a corrosão galvânica do par Zn-Fe onde foi possível mapear a distribuição de pH associada ao desenvolvimento de regiões alcalinas causadas pela redução do oxigénio, acima da região catódica, e de regiões ácidas decorrentes da dissolução anódica do ânodo de zinco. Com o par galvânico imerso em 50 mM NaCl registou-se uma variação de pH aproximadamente entre 4,8 acima do ânodo de zinco a 9,3 sobre o cátodo de ferro. A utilização pioneira destes MEs como sensores de pH é uma alternativa promissora aos elétrodos baseados em membranas seletivas.

Contribution to fundamental aspects of biophysics, radiobiology, and modeling of cellular response to low radiation doses

Tese de doutoramento, Engenharia Biomédica e Biofísica, Universidade de Lisboa, Faculdade de Ciências, 2014

Boronic acids as partners in multicomponent reactions

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2014

Biological membranes : biophysical properties and aquaporin function

Tese de doutoramento, Farmácia (Bioquímica), Universidade de Lisboa, Faculdade de Farmácia, 2014