Selective oxidation of allylic alcohols over highly ordered Pd/meso-Al2 O3 catalysts

Highly ordered mesoporous alumina was prepared via evaporation induced self assembly and was impregnated to afford a family of Pd/meso-Al2O3 catalysts for the aerobic selective oxidation (selox) of allylic alcohols under mild reaction conditions. CO chemisorption and XPS identify the presence of highly dispersed (0.9–2 nm) nanoparticles comprising heavily oxidised PdO surfaces, evidencing a strong palladium-alumina interaction. Surface PdO is confirmed as the catalytically active phase responsible for allylic alcohol selox, with initial rates for Pd/meso-Al2O3 far exceeding those achievable for palladium over either amorphous alumina or mesoporous silica supports. Pd/meso-Al2O3 is exceptionally active for the atom efficient selox of diverse allylic alcohols, with activity inversely proportional to alcohol mass.

Internal quantum efficiency and tunable colour temperature in monolithic white InGaN/GaN LED

Internal Quantum Efficiency (IQE) of two-colour monolithic white light emitting diode (LED) was measured by temperature dependant electro-luminescence (TDEL) and analysed with modified rate equation based on ABC model. External, internal and injection efficiencies of blue and green quantum wells were analysed separately. Monolithic white LED contained one green InGaN QW and two blue QWs being separated by GaN barrier. This paper reports also the tunable behaviour of correlated colour temperature (CCT) in pulsed operation mode and effect of self-heating on device performance. © 2014 SPIE.

VisibleZ: A Mainframe Architecture Emulator for Computing Education

This paper describes a PC-based mainframe computer emulator called VisibleZ and its use in teaching mainframe Computer Organization and Assembly Programming classes. VisibleZ models IBM’s z/Architecture and allows direct interpretation of mainframe assembly language object code in a graphical user interface environment that was developed in Java. The VisibleZ emulator acts as an interactive visualization tool to simulate enterprise computer architecture. The provided architectural components include main storage, CPU, registers, Program Status Word (PSW), and I/O Channels. Particular attention is given to providing visual clues to the user by color-coding screen components, machine instruction execution, and animation of the machine architecture components. Students interact with VisibleZ by executing machine instructions in a step-by-step mode, simultaneously observing the contents of memory, registers, and changes in the PSW during the fetch-decode-execute machine instruction cycle. The object-oriented design and implementation of VisibleZ allows students to develop their own instruction semantics by coding Java for existing specific z/Architecture machine instructions or design and implement new machine instructions. The use of VisibleZ in lectures, labs, and assignments is described in the paper and supported by a website that hosts an extensive collection of related materials. VisibleZ has been proven a useful tool in mainframe Assembly Language Programming and Computer Organization classes. Using VisibleZ, students develop a better understanding of mainframe concepts, components, and how the mainframe computer works. ACM Computing Classification System (1998): C.0, K.3.2.

Hierarchical ZnO “rod like” architecture synthesized via reverse micellar route for improved photocatalytic activity

Hierarchical ZnO “rod like” architecture was successfully synthesized via reverse micellar route and characterized by various techniques. The FESEM studies show controlled decomposition of zinc oxalate into ZnO “rod like” architecture at 500 °C with slow heat rate at 1°/min. Interestingly, improved photocatalytic activity was observed for the degradation of Rhodamine B, due to the self assembly of hexagonal nanoparticles of zinc oxide forming hierarchical ZnO “rod like” architecture which can greatly enhance the light utilization rate due to its special architecture and enlarge the specific surface area, providing more reaction sites and promoting mass transfer. More importantly, the reusability studies of this architecture were most economical.

Pattern of nutrient availability and plant community assemblage in Everglades Tree Islands, Florida, USA

We address the relative importance of nutrient availability in relation to other physical and biological factors in determining plant community assemblages around Everglades Tree Islands (Everglades National Park, Florida, USA). We carried out a one-time survey of elevation, soil, water level and vegetation structure and composition at 138 plots located along transects in three tree islands in the Park’s major drainage basin. We used an RDA variance partitioning technique to assess the relative importance of nutrient availability (soil N and P) and other factors in explaining herb and tree assemblages of tree island tail and surrounded marshes. The upland areas of the tree islands accumulate P and show low N concentration, producing a strong island-wide gradient in soil N:P ratio. While soil N:P ratio plays a significant role in determining herb layer and tree layer community assemblage in tree island tails, nevertheless part of its variance is shared with hydrology. The total species variance explained by the predictors is very low. We define a strong gradient in nutrient availability (soil N:P ratio) closely related to hydrology. Hydrology and nutrient availability are both factors influencing community assemblages around tree islands, nevertheless both seem to be acting together and in a complex mechanism. Future research should be focused on segregating these two factors in order to determine whether nutrient leaching from tree islands is a factor determining community assemblages and local landscape pattern in the Everglades, and how this process might be affected by water management.

Effects of sex, third grade reading achievement and motivation as predictors of fourth grade reading achievement of Hispanic students: A path analysis

This study explored the topic of motivation for intermediate students combining both an objective criterion measure (i.e., standardized test scores) and the self-report of students on self-concept and value of reading. The purpose of this study was to examine how third grade reading achievement correlated with the motivation of fourth grade boys and girls, and, in turn, how motivation related to fourth grade reading achievement. The participants were fourth grade students (n=207) attending two public, elementary schools in Miami-Dade County who were of primarily Hispanic origin or descent. Data were collected using the Reading Survey portion of the Motivation to Read Profile (1996) which measures self-concept and value of reading in order to measure motivation and the Third and Fourth Grade Reading Florida Comprehensive Assessment Tests 2.0 (FCAT 2.0) to assess achievement. First, a one way Analysis of Variance (ANOVA) was conducted to determine whether motivation differed significantly between fourth grade boys and girls. Second, a path analysis was used to determine whether motivation mediated or moderated the association between FCAT 2.0 third and fourth grade scores. Results of the ANOVA indicated that motivation, as measured by the Motivation to Read Profile did not differ significantly by sex. Results from the path analysis indicated that the model was significant and that third grade FCAT 2.0 scores accounted for a significant amount of the variance in fourth grade FCAT 2.0 scores once motivation was entered. Results of the study demonstrated that motivation partially mediates, but does not moderate the relationship between FCAT 2.0 third and fourth grade scores. In conclusion, it can be determined that past student achievement for fourth grade students plays a role in current student achievement when motivation is also considered. It is therefore important in order to improve the quality of fourth grade student's current performance to take into account a student's motivation and past achievement. An effort must be made to address students' motivational needs whether through school wide programs or at the classroom level in addition or in conjunction with cognition. Future research on the effect of self-concept in reading achievement is recommended.

Nano-grids of Yeast Cytochrome C

One innovative thought in biomolecular electronics is the exploitation of electron transfer proteins. Using nature's self assembly techniques, proteins can build highly organized edifices with retained functional activity, and they can serve as platforms for biosensors. In this research work, Yeast Cytochrome C (YCC) is immobilized with a help of a linker molecule, 3-Mercaptopropyltrimethoxysilane (3-MPTS) on a hydroxylated surface of a silicon substrate. Atomic Force Microscopy (AFM) is used for characterization. AFM data shows immobilization of one YCC molecule in between eight grids that are formed by the linker molecules. 3-MPTS monolayers are organized in grids that are 1.2 nm apart. Immobilization of 3-MPTS was optimized using a concentration of 5 mM in a completely dehydrated state for 30 minutes. The functionally active grids of YCC can now be incorporated with Cytochrome C oxidase on a Platinum electrode surface for transfer of electrons in development of biosensors, such as nitrate sensor, that are small in size, cheaper, and easier to manufacture than the top-down approach of fabrication of molecular biodevices

Fabrication of a two-terminal super conducting device with a poled ferroelectric control layer

The discovery of High-Temperature Superconductors (HTSCs) has spurred the need for the fabrication of superconducting electronic devices able to match the performance of today's semiconductor devices. While there are several HTSCs in use today, YBaCuO7-x (YBCO) is the better characterized and more widely used material for small electronic applications. This thesis explores the fabrication of a Two-Terminal device with a superconductor and a painted on electrode as the terminals and a ferroelectric, BaTiO 3 (BTO), in between. The methods used to construct such a device and the challenges faced with the fabrication of a viable device will be examined. The ferroelectric layer of the devices that proved adequate for use were poled by the application of an electric field. Temperature Bias Poling used an applied field of 105V/cm at a temperature of approximately 135*C. High Potential Poling used an applied field of 106V/cm at room temperature (20*C). The devices were then tested for a change in their superconducting critical temperature, Tc. A shift of 1-2K in the Tc(onset) of YBCO was observed for Temperature Bias Poling and a shift of 2-6K for High Potential Poling. These are the first reported results of the field effect using BTO on YBCO. The mechanism involved in the shifting of Tc will be discussed along with possible applications.

A escrita dos professores de língua portuguesa: desvelando dizeres e saberes

This documental research in a qualitative and interpretative nature is inserted in the field of Applied Linguistics and its object of study is teachers‟ writing in a literacy event (public exam) held for teachers of Portuguese Language by municipality in Natal city - RN in 2008. Overall, we have aimed to investigate the textual production of these teachers, considering their knowledge about writing, their sayings in relation to themselves and their views on new technologies and teaching. Specifically, we have chosen the following objectives: a) identifying what knowledge about writing have emerged from teachers' written text; b) analyzing the written text production of teachers, considering the knowledge they have revealed about themselves; c) mapping the sayings of the teachers about the teaching profession and new technologies. Our discussion is grounded theoretically by Bakhtin studies of language (BAKHTIN [1934], 1990; [1952-1953], 2000; BAKHTIN; VOLOSHINOV [1929], 1999); in studies of critical literacy as formulated by STREET (1984, 1995, 2006, 2010, 2014); KLEIMAN (1995, 2005, 2006, 2008); (BARTON, HAMILTON, 1998; BARTON; Ivanic, 1991); studies on teacher training in critical educational perspective (GIROUX, 1986; 1987; 1997; 1999) FREIRE, 1999; 2001). The corpus of this study is consisted of written texts by participants of this examination about the Writing Test, in which they were asked to produce an opinion paper. The research has allowed us to realize that, in relation to the writing, despite the recurring negative discourse on literacy teachers, especially the Portuguese ones, these, in the fabric of their texts, both have revealed to have dominion over the formal structure, particularly in respect to prototypical schema of argumentative sequence, as proposed by Adam (1992, 2008) and the mechanisms of textualization postulated by Bronckart (2007), and on those enunciation-discursive strategies relating to opinion genre. The relevance of this research is justified by seeking to understand the teacher‟s writing beyond the language system, i.e, writing as speech, assuming it as a contrapalavra (BAKHTIN, [1934], 1990) to those voices that insist on underestimating literacy teachers and they do so much harm to society, to the extent that foster a sense of disbelief in the qualification of teachers' work and distrust of the social role of these professionals in the preparation of future generations

Qual é a sua tribo? O uso do TAI online no desvelamento de conhecimentos sociais ocultos

The Implicit Association Test (IAT) has succeeded in accessing mental phenomena hardly exposed through self-report and explicit measures well known in the traditional studies on psychology. Although this measurement technique is among the most consistent in international publications, the few articles in Brazil have not deepened on theoretical issues that underlie the practice. This created a gap between the spread of this measure in the country and the production seen in international laboratories, both at quantitative and qualitative terms. In this context, the online labs implemented in several countries, including Brazil, created unique opportunities to overcome these disparities. Our work sought theoretical and conceptual clarification, contextualized to the historical development of the IAT and its online version, displaying affordably an unprecedented presentation of the virtual tool adapted to the Brazilian public. In a second step, we investigated empirically the data obtained by the Brazilian electronic portal "Countries", analyzing the degree of implicit and explicit nationalism of 2271 Brazilian subjects collected from early 2009 to late 2014. Our goal was to determine whether the data results obtained in a time of major sporting confrontation (FIFA World Cup 2010 and 2014) differ from periods when the tournament did not happen. Analyzes showed differences on the eve of the sporting confrontation, when the increase in the implicit nationalism was clearly superior, even with no effect by self-reports. In an independent analysis of a cultural context, there is an oscillation of explicit nationalism over the years, but not for the implicit action. In addition, it was found in women greater degree of implicit and explicit nationalism than in men, with both sexes presenting their preferences towards Brazil. In an end section, we suggest that nationalism may be a by-product of universal mental mechanisms that evolved to identify of the belonging group categorization, corroborating with the group favoritism. We propose that the intensification of the group preference on the eve of the competition has as its ancestral function strengthen the cohesion of the group in preparation to confrontational situations. We pointed out the need for studies on the differences between the sexes in matters relating to group membership belonging. It was expected largest nationalist attitudes in men reflecting the maintenance of cohesive groups in ancient societies. Thus, it appears a singular importance impart the traditional TAI studies with its online version for future investigations of human behavior in various areas of knowledge.

Qual é a sua tribo? O uso do TAI online no desvelamento de conhecimentos sociais ocultos

The Implicit Association Test (IAT) has succeeded in accessing mental phenomena hardly exposed through self-report and explicit measures well known in the traditional studies on psychology. Although this measurement technique is among the most consistent in international publications, the few articles in Brazil have not deepened on theoretical issues that underlie the practice. This created a gap between the spread of this measure in the country and the production seen in international laboratories, both at quantitative and qualitative terms. In this context, the online labs implemented in several countries, including Brazil, created unique opportunities to overcome these disparities. Our work sought theoretical and conceptual clarification, contextualized to the historical development of the IAT and its online version, displaying affordably an unprecedented presentation of the virtual tool adapted to the Brazilian public. In a second step, we investigated empirically the data obtained by the Brazilian electronic portal "Countries", analyzing the degree of implicit and explicit nationalism of 2271 Brazilian subjects collected from early 2009 to late 2014. Our goal was to determine whether the data results obtained in a time of major sporting confrontation (FIFA World Cup 2010 and 2014) differ from periods when the tournament did not happen. Analyzes showed differences on the eve of the sporting confrontation, when the increase in the implicit nationalism was clearly superior, even with no effect by self-reports. In an independent analysis of a cultural context, there is an oscillation of explicit nationalism over the years, but not for the implicit action. In addition, it was found in women greater degree of implicit and explicit nationalism than in men, with both sexes presenting their preferences towards Brazil. In an end section, we suggest that nationalism may be a by-product of universal mental mechanisms that evolved to identify of the belonging group categorization, corroborating with the group favoritism. We propose that the intensification of the group preference on the eve of the competition has as its ancestral function strengthen the cohesion of the group in preparation to confrontational situations. We pointed out the need for studies on the differences between the sexes in matters relating to group membership belonging. It was expected largest nationalist attitudes in men reflecting the maintenance of cohesive groups in ancient societies. Thus, it appears a singular importance impart the traditional TAI studies with its online version for future investigations of human behavior in various areas of knowledge.

The automation of protein crystal presentation for x ray diffraction experiments using standing acoustic waves in a microfluidic chip environment

As the pressure continues to grow on Diamond and the world's synchrotrons for higher throughput of diffraction experiments, new and novel techniques are required for presenting micron dimension crystals to the X ray beam. Currently this task is both labour intensive and primarily a serial process. Diffraction measurements typically take milliseconds but sample preparation and presentation can reduce throughput down to 4 measurements an hour. With beamline waiting times as long as two years it is of key importance for researchers to capitalize on available beam time, generating as much data as possible. Other approaches detailed in the literature [1] [2] [3] are very much skewed towards automating, with robotics, the actions of a human protocols. The work detailed here is the development and discussion of a bottom up approach relying on SSAW self assembly, including material selection, microfluidic integration and tuning of the acoustic cavity to order the protein crystals.

The automation of protein crystal presentation for X ray diffraction experiments using standing acoustic waves in a microfluidic chip environment

As the pressure continues to grow on Diamond and the world's synchrotrons for higher throughput of diffraction experiments, new and novel techniques are required for presenting micron dimension crystals to the X ray beam. Currently this task is both labour intensive and primarily a serial process. Diffraction measurements typically take milliseconds but sample preparation and presentation can reduce throughput down to 4 measurements an hour. With beamline waiting times as long as two years it is of key importance for researchers to capitalize on available beam time, generating as much data as possible. Other approaches detailed in the literature [1] [2] [3] are very much skewed towards automating, with robotics, the actions of a human protocols. The work detailed here is the development and discussion of a bottom up approach relying on SSAW self assembly, including material selection, microfluidic integration and tuning of the acoustic cavity to order the protein crystals.

Physics of Hexagonal Limit-Periodic Phases: Thermodynamics, Formation and Vibrational Modes

Limit-periodic (LP) structures exhibit a type of nonperiodic order yet to be found in a natural material. A recent result in tiling theory, however, has shown that LP order can spontaneously emerge in a two-dimensional (2D) lattice model with nearest-and next-nearest-neighbor interactions. In this dissertation, we explore the question of what types of interactions can lead to a LP state and address the issue of whether the formation of a LP structure in experiments is possible. We study emergence of LP order in three-dimensional (3D) tiling models and bring the subject into the physical realm by investigating systems with realistic Hamiltonians and low energy LP states. Finally, we present studies of the vibrational modes of a simple LP ball and spring model whose results indicate that LP materials would exhibit novel physical properties.

A 2D lattice model defined on a triangular lattice with nearest- and next-nearest-neighbor interactions based on the Taylor-Socolar (TS) monotile is known to have a LP ground state. The system reaches that state during a slow quench through an infinite sequence of phase transitions. Surprisingly, even when the strength of the next-nearest-neighbor interactions is zero, in which case there is a large degenerate class of both crystalline and LP ground states, a slow quench yields the LP state. The first study in this dissertation introduces 3D models closely related to the 2D models that exhibit LP phases. The particular 3D models were designed such that next-nearest-neighbor interactions of the TS type are implemented using only nearest-neighbor interactions. For one of the 3D models, we show that the phase transitions are first order, with equilibrium structures that can be more complex than in the 2D case.

In the second study, we investigate systems with physical Hamiltonians based on one of the 2D tiling models with the goal of stimulating attempts to create a LP structure in experiments. We explore physically realizable particle designs while being mindful of particular features that may make the assembly of a LP structure in an experimental system difficult. Through Monte Carlo (MC) simulations, we have found that one particle design in particular is a promising template for a physical particle; a 2D system of identical disks with embedded dipoles is observed to undergo the series of phase transitions which leads to the LP state.

LP structures are well ordered but nonperiodic, and hence have nontrivial vibrational modes. In the third section of this dissertation, we study a ball and spring model with a LP pattern of spring stiffnesses and identify a set of extended modes with arbitrarily low participation ratios, a situation that appears to be unique to LP systems. The balls that oscillate with large amplitude in these modes live on periodic nets with arbitrarily large lattice constants. By studying periodic approximants to the LP structure, we present numerical evidence for the existence of such modes, and we give a heuristic explanation of their structure.

Investigation of electrically active defects at the interface of high-k dielectrics and compound semiconductors

As silicon based devices in integrated circuits reach the fundamental limits of dimensional scaling there is growing research interest in the use of high electron mobility channel materials, such as indium gallium arsenide (InGaAs), in conjunction with high dielectric constant (high-k) gate oxides, for Metal-Oxide-Semiconductor Field Effect Transistor (MOSFET) based devices. The motivation for employing high mobility channel materials is to reduce power dissipation in integrated circuits while also providing improved performance. One of the primary challenges to date in the field of III-V semiconductors has been the observation of high levels of defect densities at the high-k/III-V interface, which prevents surface inversion of the semiconductor. The work presented in this PhD thesis details the characterization of MOS devices incorporating high-k dielectrics on III-V semiconductors. The analysis examines the effect of modifying the semiconductor bandgap in MOS structures incorporating InxGa1-xAs (x: 0, 0.15. 0.3, 0.53) layers, the optimization of device passivation procedures designed to reduce interface defect densities, and analysis of such electrically active interface defect states for the high-k/InGaAs system. Devices are characterized primarily through capacitance-voltage (CV) and conductance-voltage (GV) measurements of MOS structures both as a function of frequency and temperature. In particular, the density of electrically active interface states was reduced to the level which allowed the observation of true surface inversion behavior in the In0.53Ga0.47As MOS system. This was achieved by developing an optimized (NH4)2S passivation, minimized air exposure, and atomic layer deposition of an Al2O3 gate oxide. An extraction of activation energies allows discrimination of the mechanisms responsible for the inversion response. Finally a new approach is described to determine the minority carrier generation lifetime and the oxide capacitance in MOS structures. The method is demonstrated for an In0.53Ga0.47As system, but is generally applicable to any MOS structure exhibiting a minority carrier response in inversion.