A level II reliability approach to tunnel support design

A reliability approach to tunnel support design is presented in this paper. The aim of the work is the incorporation of classical Level II techniques to the current design method based on the study of the ground-support interaction diagram.

Applications of functional nucleic acids in imaging, sensing and drug delivery and investigations of DNAzyme-metal interactions

Functional nucleic acids (FNA), including nucleic acids catalysts (ribozymes and DNAzymes) and ligands (aptamers), have been discovered in nature or isolated in a laboratory through a process called in vitro selection. They are nucleic acids with functions similar to protein enzymes or antibodies. They have been developed into sensors with high sensitivity and selectivity; it is realized by converting the reaction catalyzed by a DNAzyme/ribozyme or the binding event of an aptamer to a fluorescent, colorimetric or electrochemical signal. While a number of studies have been reported for in vitro sensing using DNAzymes or aptamers, there are few reports on in vivo sensing or imaging. MRI is a non-invasive imaging technique; smart MRI contrast agents were synthesized for molecular imaging purposes. However, their rational design remains a challenge due to the difficulty to predict molecular interactions. Chapter 2 focuses on rational design of smart T1-weighted MRI contrast agents with high specificity based on DNAzymes and aptamers. It was realized by changing the molecular weight of the gadolinium conjugated DNA strand with the analytes, which lead to analyte-specific water proton relaxation responses and contrast changes on an MRI image. The designs are general; the high selectivity of FNA was retained. Most FNA-based fluorescent sensors require covalent labeling of fluorophore/quencher to FNAs, which incurrs extra expenses and could interfere the function of FNAs. Chapter 3 describes a new sensor design avoiding the covalent labeling of fluorophore and quencher. The fluorescence of malachite green (MG) was regulated by the presence of adenosine. Conjugate of aptamers of MG and adenosine and a bridge strand were annealed in a solution containing MG. The MG aptamer did not bind MG because of its hybridization to the bridge strand, resulting in low fluorescence signal of MG. The hybridization was weakened in the presence of adenosine, leading to the binding of MG to its aptamer and a fluorescence increase. The sensor has comparable detection limit (20 micromolar) and specificity to its labeled derivatives. Enzymatic activity of most DNAzymes requires metal cations. The research on the metal-DNAzyme interaction is of interest and challenge to scientists because of the lack of structural information. Chapters 4 presents the research on the characterization of the interaction between a Cu2+-dependent DNAzyme and Cu2+. Electron paramagnetic resonance (EPR) and UV-Vis spectroscopy were used to probe the binding of Cu2+ to the DNAzyme; circular dichroism was used to probe the conformational change of the DNAzyme induced by Cu2+. It was proposed that the conformational change by the Cu2+ binding is important for the activity of the DNAzyme. Chapter 5 reports the dependence of the activity of 8-17 DNAzyme on the presence of both Pb2+ and other metal cations including Zn2+, Cd2+ and Mg2+. It was discovered that presence of those metal cations can be cooperative or inhibitive to 8-17 activity. It is hypothesized that the 8-17 DNAzyme had multiple binding sites for metal cations based on the results. Cisplatin is effective killing tumor cells, but with significant side effects, which can be minimized by its targeted delivery. Chapter 6 focuses on the effort to functionalize liposomes encapsulating cisplatin by an aptamer that selectively bind nucleolin, an overexpressed protein by breast cancer cells. The study proved the selective cytotoxicity to breast cancer cells of the aptamer-functionalized liposome.

Pt/Carbon materials as Bi-Functional catalysts for N-decane hydroisomerization

The activity and selectivity of bi-functional carbon-supported platinum catalysts for the hydroisomerization of n-alkanes have been studied. The influence of the properties of the carbon support on the performance of the catalysts were investigated by incorporating the metallic function on a series of carbons with varied porosity (microporous: GL-50 from Norit, and mesoporous: CMK-3) and surface chemistry (modified by wet oxidation). The characterization results achieved with H-2 chemisorption and TEM showed differences in surface metal concentrations and metal-support interactions depending on the support composition. The highest metal dispersion was achieved after oxidation of the carbon matrix in concentrated nitric acid, suggesting that the presence of surface functional sites distributed in inner and outer surface favors a homogeneous metal distribution. On the other hand, the higher hydrogenating activity of the catalysts prepared with the mesoporous carbon pointed out that a fast molecular traffic inside the pores plays an important role in the catalysts performance. For n-decane hydroisomerization of long chain n-alkanes, higher activities were obtained for the catalysts with an optimized acidity and metal dispersion along with adequate porosity, pointing out the importance of the support properties in the performance of the catalysts.

Visible range plasmonic effect produced by aluminium nanoparticles embedded in amorphous silicon

We present results, obtained by means of an analytic study and a numerical simulation, about the resonant condition necessary to produce a Localized Surface Plasmonic Resonance (LSPR) effect at the surface of metal nanospheres embedded in an amorphous silicon matrix. The study is based on a Lorentz dispersive model for a-Si:H permittivity and a Drude model for the metals. Considering the absorption spectra of a-Si:H, the best choice for the metal nanoparticles appears to be aluminium, indium or magnesium. No difference has been observed when considering a-SiC:H. Finite-difference time-domain (FDTD) simulation of an Al nanosphere embedded into an amorphous silicon matrix shows an increased scattering radius and the presence of LSPR induced by the metal/semiconductor interaction under green light (560 nm) illumination. Further results include the effect of the nanoparticles shape (nano-ellipsoids) in controlling the wavelength suitable to produce LSPR. It has been shown that is possible to produce LSPR in the red part of the visible spectrum (the most critical for a-Si:H solar cells applications in terms of light absorption enhancement) with aluminium nano-ellipsoids. As an additional results we may conclude that the double Lorentz-Lorenz model for the optical functions of a-Si:H is numerically stable in 3D simulations and can be used safely in the FDTD algorithm. A further simulation study is directed to determine an optimal spatial distribution of Al nanoparticles, with variable shapes, capable to enhance light absorption in the red part of the visible spectrum, exploiting light trapping and plasmonic effects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fe3+-SELECTIVE ENHANCED FLUORESCENCE PROBE BASED ON A RHODAMINE DERIVATIVE

A novel Fe3+-selective and turn-on fluorescent probe 1 incorporating a rhodamine fluorophore and quinoline subunit was synthesized. Probe 1 displayed high selectivity for Fe3+ in CH3CN–H2O (95:5 v/v) in the presence of other relevant metal cations. Interaction with Fe3+ in 1:1 stoichiometry could trigger a significant fluorescence enhancement due to the formation of the ring-open form. The fluorescent response images were investigated by a novel Euclidean distance method based on red, green, and blue values. A linear relationship was observed between fluorescence intensity changes and Fe3+ concentrations from 7.3 × 10−7 to 3.6 × 10−5 mol L−1.

Examining human-centered design practice in the mobile apps era

Human-Centered Design (HCD) is a well-recognized approach to the design of interactive computing systems that supports everyday and professional lives of people. To that end, the HCD approach put central emphasis on the explicit understanding of users and context of use by involving users throughout the entire design and development process. With mobile computing, the diversity of users as well as the variety in the spatial, temporal, and social settings of the context of use has notably expanded, which affect the effort of interaction designers to understand users and context of use. The emergence of the mobile apps era in 2008 as a result of structural changes in the mobile industry and the profound enhanced capabilities of mobile devices, further intensify the embeddedness of technology in the daily life of people and the challenges that interaction designers face to cost-efficiently understand users and context of use. Supporting interaction designers in this challenge requires understanding of their existing practice, rationality, and work environment. The main objective of this dissertation is to contribute to interaction design theories by generating understanding on the HCD practice of mobile systems in the mobile apps era, as well as to explain the rationality of interaction designers in attending to users and context of use. To achieve that, a literature study is carried out, followed by a mixed-methods research that combines multiple qualitative interview studies and a quantitative questionnaire study. The dissertation contributes new insights regarding the evolving HCD practice at an important time of transition from stationary computing to mobile computing. Firstly, a gap is identified between interaction design as practiced in research and in the industry regarding the involvement of users in context; whereas the utilization of field evaluations, i.e. in real-life environments, has become more common in academic projects, interaction designers in the industry still rely, by large, on lab evaluations. Secondly, the findings indicate on new aspects that can explain this gap and the rationality of interaction designers in the industry in attending to users and context; essentially, the professional-client relationship was found to inhibit the involvement of users, while the mental distance between practitioners and users as well as the perceived innovativeness of the designed system are suggested in explaining the inclination to study users in situ. Thirdly, the research contributes the first explanatory model on the relation between the organizational context and HCD; essentially, innovation-focused organizational strategies greatly affect the cost-effective usage of data on users and context of use. Last, the findings suggest a change in the nature of HCD in the mobile apps era, at least with universal consumer systems; evidently, the central attention on the explicit understanding of users and context of use shifts from an early requirements phase and continual activities during design and development to follow-up activities. That is, the main effort to understand users is by collecting data on their actual usage of the system, either before or after the system is deployed. The findings inform both researchers and practitioners in interaction design. In particular, the dissertation suggest on action research as a useful approach to support interaction designers and further inform theories on interaction design. With regard to the interaction design practice, the dissertation highlights strategies that encourage a more cost-effective user- and context-informed interaction design process. With the continual embeddedness of computing into people’s life, e.g. with wearable devices and connected car systems, the dissertation provides a timely and valuable view on the evolving humancentered design.

Effect of some toxic metals on selected phytoplankton of Kerala water

The extraction and use of metals has been the mainstay for the sustained development and progress of a nation. Metals, though fairly stable in the natural environment are found in trace quantities in water bodies. Attention has therefore been focused to identify the metals that impair the water quality. In the last few decades the concern about the fate of these metals in the aquatic system has been gaining momentum, particularly in the industrial belts. The disasters caused by metal poisoning in recent times have prompted an indepth study of the interaction of metals with aquatic biota. Kerala, basically an agriculture oriented state has witnessed the upsurgence of various industries as a part of the nationwide economic development programme. Cochin has been identified as the industrial capital of the state.The present study is an attempt towards a better understanding of the metal-phytoplankton interactions with special reference to the physiological changes in the species. various parameters such as temperature, salinity, pH, nutrients, number of cells, photosynthetic pigments, carbohydrates, protein and lipid are studied to highlight the complexity of metal..phytoplankton interaction

Synthesis, Characterization and Catalytic Activity of Nanocrystalline Ceria Modified With Zirconia

The use of catalysts in chemical and refining processes has increased rapidly since 1945, when oil began to replace coal as the most important industrial raw material. Catalysis has a major impact on the quality of human life as well as economic development. The demand for catalysts is still increasing since catalysis is looked up as a solution to eliminate or replace polluting processes. Metal oxides represent one of the most important and widely employed classes of solid catalysts. Much effort has been spent in the preparation, characterization and application of metal oxides. Recently, great interest has been devoted to the cerium dioxide (CeO2) containing materials due to their broad range of applications in various fields, ranging from catalysis to ceramics, fuel cell technologies, gas sensors, solid state electrolytes, ceramic biomaterials, etc., in addition to the classical application of CeO2 as an additive in the so-called three way catalysts (TWC) for automotive exhaust treatment. Moreover, it can promote water gas shift and steam reforming reactions, favours catalytic activity at the interfacial metal-support sites. The solid solutions of ceria with Group IV transitional-metals deserve particular attention for their applicability in various technologically important catalytic processes. Mesoporous CeO2−ZrO2 solid solutions have been reported to be employed in various reactions which include CO oxidation, soot oxidation, water-gas shift reaction, and so on. Inspired by the unique and promising characteristics of ceria based mixed oxides and solid solutions for various applications, we have selected ceria-zirconia oxides for our studies. The focus of the work is the synthesis and investigation of the structural and catalytic properties of modified and pure ceria-zirconia mixed oxide.

Diorganoruthenium complexes incorporating noninnocent [C6H2(CH2ER2)2-3,5]22-(E = N, P) Bis-Pincer bridging ligands: synthesis, spectroelectrochemistry, and DFT studies

The dinuclear complex [(tpy)Ru-II(PCP-PCP)Ru-II(tPY)]Cl-2 (bridging PCP-PCP = 3,3',5,5'-tetrakis(diphenylphosphinomethyl)biphenyl, [C6H2(CH2PPh2)(2)-3,5](2)(2-)) was prepared via a transcyclometalation reaction of the bis-pincer ligand [PC(H)P-PC(H)P] and the Ru(II) precursor [Ru(NCN)(tpy)]Cl (NCN = [C6H3(CH2NMe2)(2)-2,6](-)) followed by a reaction with 2,2':6',2 ''-terpyridine (tpy). Electrochemical and spectroscopic properties of [(tpy)Ru-II(PCP-PCP)Ru-II(tPY)]Cl-2 are compared with those of the closely related [(tpy)Ru-II(NCN-NCN)Ru-II(tpy)](PF6)(2) (NCN-NCN = [C6H2(CH2- NMe2)(2)-3,5](2)(2-)) obtained by two-electron reduction of [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](PF6)(4). The molecular structure of the latter complex has been determined by single-crystal X-ray structure determination. One-electron reduction of [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](PF6)(4) and one-electron oxidation of [(tpy)Ru-II(PCP-PCP)RUII(tpy)]Cl-2 yielded the mixed-valence species [(tpy)Ru-III(NCN-NCN)RUII(tpy)](3+) and [(tpy)Ru-III(PCP-PCP)RUII(tpy)](3+), respectively. The comproportionation equilibrium constants K-c (900 and 748 for [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](4+) and [(tpy)Ru-II(PCP-PCP)RUII(tpy)](2+), respectively) determined from cyclic voltammetric data reveal comparable stability of the [Ru-III-Ru-II] state of both complexes. Spectroelectrochemical measurements and near-infrared (NIR) spectroscopy were employed to further characterize the different redox states with special focus on the mixed-valence species and their NIR bands. Analysis of these bands in the framework of Hush theory indicates that the mixed-valence complexes [(tpy)Ru-III(PCP-PCP)RUII(tpy)](3+) and [(tpy)Ru-III(NCN-NCN)RUII(tpy)](3+) belong to strongly coupled borderline Class II/Class III and intrinsically coupled Class III systems, respectively. Preliminary DFT calculations suggest that extensive delocalization of the spin density over the metal centers and the bridging ligand exists. TD-DFT calculations then suggested a substantial MLCT character of the NIR electronic transitions. The results obtained in this study point to a decreased metal-metal electronic interaction accommodated by the double-cyclometalated bis-pincer bridge when strong sigma-donor NMe2 groups are replaced by weak sigma-donor, pi-acceptor PPh2 groups

Photoluminescence behavior of Eu(3+) ion doped into gamma- and alpha-alumina systems prepared by combustion, ceramic and Pechini methods

Al(2)O(3):Eu(3+)(1%) samples were prepared by combustion, ceramic, and Pechini methods annealed from 400 to 1400 degrees C. XRD patterns indicate that samples heated up to 1000 degrees C present disordered character of activated alumina (gamma-Al(2)O(3)). However, alpha-Al(2)O(3) phase showed high crystallinity and thermostability at 1200-1400 degrees C. The sample characterizations were also carried out by means of infrared spectroscopy (IR), scanning electron microscopy (SEM) and specific surface areas analysis (BET method). Excitation spectra of Al(2)O(3):Eu(3+) samples present broaden bands attributed to defects of Al(2)O(3) matrices and to LMCT state of O -> Eu(3+), however, the narrow bands are assigned to (7)F(0) -> (5)D(J),(5)H(J) and (5)L(J) transitions of Eu(3+) ion. Emission spectra of samples calcined up to 1000 degrees C show broaden bands for (5)D(0) -> (7)F(J) transitions of Eu(3+) ion suggesting that the rare earth ion is in different symmetry sites showed by inhomogeneous line broadening of bands, confirming the predominance of the gamma-alumina phase. For all samples heated from 1200 to 1400 degrees C the spectra exhibit narrow (5)D(0) -> (7)F(J) transitions of Eu(3+) ion indicating the conversion of gamma to alpha-Al(2)O(3) phases, a high intensity narrow peak around 695 nm assigned to R lines of Cr(3+) ion is shown. Al(2)O(3):Eu(3+) heated up to 1100 degrees C presents an increase in the Omega(2) intensity parameter with the increase of temperatures enhancing the covalent character of metal-donor interaction. The disordered structural systems present the highest values of emission quantum efficiencies (eta). CIE coordinates of Al(2)O(3):Eu(3+) are also discussed. (C) 2007 Elsevier Inc. All rights reserved.

Effects of adding La and Ce to hydrotalcite-type Ni/Mg/Al catalyst precursors on ethanol steam reforming reactions

Catalyst precursors composed of Ni/Mg/Al oxides with added La and Ce were tested in ethanol steam reforming (ESR) reactions. La and Ce were added by anion-exchange. The oxides were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analysis. The catalyst precursors consist of a mixture of oxides, with the nickel in the form of NiO strongly interacting with the support Mg/Al. The XPS analysis showed a lanthanum-support interaction, but no interaction of Ce species with the support. The reaction data obtained with the active catalysts showed that the addition of Ce and La resulted in better H(2) production at 550 degrees C. The CeNi catalyst provided the higher ethanol conversion, with lower acetaldehyde production, possibly clue to a favoring of water adsorption on the weakly interacting clusters of CeO(2) on the surface. (C) 2010 Elsevier B.V. All rights reserved.

ADSORBATE SPECTRAL DENSITY FOR A GENERALIZED ANDERSON-NEWNS HAMILTONIAN

We discuss adsorbate-metal electrostatic interaction in the Anderson-Newns model.

Evaluation of shear bond strength at the interface of two porcelains and pure titanium injected into the casting mold at three different temperatures

Statement of problem. Titanium has physical and mechanical properties, which have led to its increased use in dental prostheses despite casting difficulties due to high melting point and formation of oxide layers which affect the metal-ceramic bond strength.Purpose. This in vitro study evaluated the shear bond strength of the interface of 2 dental porcelains and pure titanium injected into a mold at 3 different temperatures.Material and methods. Using commercially pure (cp) titanium bars (Titanium, Grade I) melted at 1668degreesC and cast at mold temperatures of 430degreesC, 700degreesC or 900degreesC, 60 specimens were machined to 4 x 4 mm, with a base of 5 x 1 mm. The 4-mm surfaces were airborne-particle abraded with 100 mum aluminum oxide before applying and firing the bonding agent and evaluating the 2 porcelains (Triceram/Triline ti and Vita Titankeramik). Ten specimens were prepared for each temperature and porcelain combination Shear bond testing was performed in a universal testing machine, with a 500-kg load cell and crosshead speed of 0.5 mm/min. The specimens were loaded until failure. The interfaces of representative fractured specimens of each temperature were examined with a scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). Data for shear bond strength (MPa) were statistically analyzed by 2-way ANOVA and the Tukey test (alpha = .05).Results. The results showed significant differences for the metal/porcelain interaction effect (P = .0464). There were no significant differences for the 2 porcelains (P = .4250). The Tukey test showed a significant difference between the pair cp Ti 430degreesC Triceram and cp Ti 900degreesC Triceram, with respective mean values and SDs of 59.74 +/- 11.62 and 34.03 +/- 10.35 MPa.Conclusion. Triceram porcelain showed a bond strength decrease with an increase in the mold temperature for casting titanium. The highest bond strength for Vita porcelain and the best metal-ceramic interface observed with the SEM were found with the mold temperature of 700degreesC.

Apresentação de um método experimental de traumatismo dentoalveolar em ratos para realização de experimentos de movimentação dentária induzida

Pós-graduação em Odontologia - FOA

Desenvolvimento de filtros solares a partir de complexos metálicos de Zn2+ e/ou Ce3+ com quercetina para protetores solares

Pós-graduação em Química - IQ