Time-resolved spectroscopy of the metal-to-metal charge transfer excited state in dinuclear cyano-bridged mixed-valence complexes

Visible pump-probe spectroscopy has been used to identify and characterize short-lived metal-to-metal charge transfer (MMCT) excited states in a group of cyano-bridged mixed-valence complexes of the formula [(LCoNCMII)-N-III(CN)(5)](-), where L is a pentadentate macrocyclic pentaamine (L-14) or triamine-dithiaether (L-14S) and M is Fe or Ru. Nanosecond pump-probe spectroscopy on frozen solutions of [(LCoNCFeII)-Co-14-N-III(CN)(5)](-) and [(LCoNCFeII)-Co-14S-N-III(CN)(5)](-) at 11 K enabled the construction of difference transient absorption spectra that featured a rise in absorbance in the region of 350-400 nm consistent with the generation of the ferricyanide chromophore of the photoexcited complex. The MMCT excited state of the Ru analogue [(LCoNCRuII)-Co-14-N-III(CN)(5)](-) was too short-lived to allow its detection. Femtosecond pump-probe spectroscopy on aqueous solutions of [(LCoNCFeII)-Co-14-N-III(CN)(5)](-) and [(LCoNCFeII)-Co-14S-N-III(CN)(5)](-) at room temperature enabled the lifetimes of their Co-II-Fe-III MMCT excited states to be determined as 0.8 and 1.3 ps, respectively.

Microanalysis of quenched and self-extinguished aluminium rods burned in oxygen

Promoted ignition tests and quench tests have been conducted and analysed for 3.2 mm aluminum rods in 99.995% oxygen. Tests have been conducted in oxygen pressures varying from 538 kPa to 773 kPa. Samples that self-extinguished or were quenched were selected for further analysis. The microstructure of the selected samples were analysed by electron microscopy, using energy dispersive spectrometry and electron back-scatter techniques, to identify and visualize, respectively, the species present. The grain structures of these samples were etched, viewed and photographed under polarized light by an optical microscope. From the micrographs produced by the post-test analysis, clearly defined boundaries between the oxide and the melted and resolidified metal have been observed. In both the melted and resolidified metal and the oxide layer, significant numbers of gas bubbles, solid inclusions and several diffuse oxide bubbles have been captured during the cooling process. It is concluded that convective movement is occurring within the molten drop and that analysis of quenched samples provides more useful information on the state of the burning droplet than samples allowed to cool slowly to room temperature. Recommendations are made regarding future investigations into aluminum burning, focusing on the transport of reactants through the liquid oxide layer.

Individual differences in cognitive style and their effects on task and social orientations of self-managed work teams

When assembling self-managing work teams, the personalities of team members are often overlooked. One personality variable known to be critical for effective decision making in teams is cognitive style. This study sought to examine how differences and similarities in analytic/intuitive cognitive styles affected the behavior of team members on the task/emotionally expressive dimension identified by Bales. As hypothesized, intuitive individuals and homogeneous intuitive teams were found to initiate more social-emotional acts. Contrary to expectations, intuitive rather than analytic individuals and homogeneous intuitive rather than analytic teams engaged in more task-oriented behaviors. Teams also tended to select intuitive individuals as leaders. The possibility that different combinations of styles may be important for overall team effectiveness was subsequently discussed, and it was suggested that this may depend on whether the nature of the work environment is relatively well structured and mechanistic or relatively unstructured and organic.

In situ studies of phase separation and crystallization directed by Marangoni instabilities during spin-coating

Results of a pioneering study are presented in which for the first time, crystallization, phase separation and Marangoni instabilities occurring during the spin-coating of polymer blends are directly visualized, in real-space and real-time. The results provide exciting new insights into the process of self-assembly, taking place during spin-coating, paving the way for the rational design of processing conditions, to allow desired morphologies to be obtained. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of the lateral diffuse metal-oxide semiconductor (LDMOS) power amplifier for cellular base stations

The primary purpose of this thesis was to present a theoretical large-signal analysis to study the power gain and efficiency of a microwave power amplifier for LS-band communications using software simulation. Power gain, efficiency, reliability, and stability are important characteristics in the power amplifier design process. These characteristics affect advance wireless systems, which require low-cost device amplification without sacrificing system performance. Large-signal modeling and input and output matching components are used for this thesis. Motorola's Electro Thermal LDMOS model is a new transistor model that includes self-heating affects and is capable of small-large signal simulations. It allows for most of the design considerations to be on stability, power gain, bandwidth, and DC requirements. The matching technique allows for the gain to be maximized at a specific target frequency. Calculations and simulations for the microwave power amplifier design were performed using Matlab and Microwave Office respectively. Microwave Office is the simulation software used in this thesis. The study demonstrated that Motorola's Electro Thermal LDMOS transistor in microwave power amplifier design process is a viable solution for common-source amplifier applications in high power base stations. The MET-LDMOS met the stability requirements for the specified frequency range without a stability-improvement model. The power gain of the amplifier circuit was improved through proper microwave matching design using input/output-matching techniques. The gain and efficiency of the amplifier improve approximately 4dB and 7.27% respectively. The gain value is roughly .89 dB higher than the maximum gain specified by the MRF21010 data sheet specifications. This work can lead to efficient modeling and development of high power LDMOS transistor implementations in commercial and industry applications.

Development of calix[4]arene-functionalized microcantilever array sensing system for the rapid, sensitive and simultaneous detection of metal ions in aqueous solutions

The work described in this thesis was conducted with the aim of: 1) investigating the binding capabilities of calix[4]arene-functionalized microcantilevers towards specific metal ions and 2) developing a new16-microcantilever array sensing system for the rapid, and simultaneous detection of metal ions in fresh water. Part I of this thesis reports on the use of three new bimodal calix[4]arenes (methoxy, ethoxy and crown) as potential host/guest sensing layers for detecting selected ions in dilute aqueous solutions using single microcantilever experimental system. In this work it was shown that modifying the upper rim of the calix[4]arenes with a thioacetate end group allow calix[4]arenes to self-assemble on Au(111) forming complete highly ordered monolayers. It was also found that incubating the microcantilevers coated with 5 nm of Inconel and 40 nm of Au for 1 h in a 1.0 M solution of calix[4]arene produced the highest sensitivity. Methoxy-functionalized microcantilevers showed a definite preference for Ca²⁺ ions over other cationic guests and were able to detect trace concentration as low as 10⁻¹² M in aqueous solutions. Microcantilevers modified with ethoxy calix[4]arene displayed their highest sensitivity towards Sr²⁺ and to a lesser extent Ca²⁺ ions. Crown calix[4]arene-modified microcantilevers were however found to bind selectively towards Cs⁺ ions. In addition, the counter anion was also found to contribute to the deflection. For example methoxy calix[4]arene-modified microcantilever was found to be more sensitive to CaCl₂ over other water-soluble calcium salts such as Ca(NO₃)₂ , CaBr₂ and CaI₂. These findings suggest that the response of calix[4]arene-modified microcantilevers should be attributed to the target ionic species as a whole instead of only considering the specific cation and/or anion. Part II presents the development of a 16-microcantilever sensor setup. The implementation of this system involved the creation of data analysis software that incorporates data from the motorized actuator and a two-axis photosensitive detector to obtain the deflection signal originating from each individual microcantilever in the array. The system was shown to be capable of simultaneous measurements of multiple microcantilevers with different coatings. A functionalization unit was also developed that allows four microcantilevers in the array to be coated with an individual sensing layer one at the time. Because of the variability of the spring constants of different cantilevers within the array, results presented were quoted in units of surface stress unit in order to compare values between the microcantilevers in the array.

Low-dimensional, hinged bar-code metal oxide layers and free-standing, ordered organic nanostructures from turbostratic vanadium oxide

Both low-dimensional bar-coded metal oxide layers, which exhibit molecular hinging, and free-standing organic nanostructures can be obtained from unique nanofibers of vanadium oxide (VOx). The nanofibers are successfully synthesized by a simple chemical route using an ethanolic solution of vanadium pentoxide xerogel and dodecanethiol resulting in a double bilayered laminar turbostratic structure. The formation of vanadium oxide nanofibers is observed after hydrothermal treatment of the thiol-intercalated xerogel, resulting in typical lengths in the range 2–6 µm and widths of about 50–500 nm. We observe concomitant hinging of the flexible nanofiber lamina at periodic hinge points in the final product on both the nanoscale and molecular level. Bar-coded nanofibers comprise alternating segments of organic–inorganic (thiols–VOx) material and are amenable to segmented, localized metal nanoparticle docking. Under certain conditions free-standing bilayered organic nanostructures are realized.

Growth and application of planar III-V semiconductor nanowires grown with MOCVD

The semiconductor nanowire has been widely studied over the past decade and identified as a promising nanotechnology building block with application in photonics and electronics. The flexible bottom-up approach to nanowire growth allows for straightforward fabrication of complex 1D nanostructures with interesting optical, electrical, and mechanical properties. III-V nanowires in particular are useful because of their direct bandgap, high carrier mobility, and ability to form heterojunctions and have been used to make devices such as light-emitting diodes, lasers, and field-effect transistors. However, crystal defects are widely reported for III-V nanowires when grown in the common out-of-plane <111>B direction. Furthermore, commercialization of nanowires has been limited by the difficulty of assembling nanowires with predetermined position and alignment on a wafer-scale. In this thesis, planar III-V nanowires are introduced as a low-defect and integratable nanotechnology building block grown with metalorganic chemical vapor deposition. Planar GaAs nanowires grown with gold seed particles self-align along the <110> direction on the (001) GaAs substrate. Transmission electron microscopy reveals that planar GaAs nanowires are nearly free of crystal defects and grow laterally and epitaxially on the substrate surface. The nanowire morphology is shown to be primarily controlled through growth temperature and an ideal growth window of 470 +\- 10 °C is identified for planar GaAs nanowires. Extension of the planar growth mode to other materials is demonstrated through growth of planar InAs nanowires. Using a sacrificial layer, the transfer of planar GaAs nanowires onto silicon substrates with control over the alignment and position is presented. A metal-semiconductor field-effect transistor fabricated with a planar GaAs nanowire shows bulk-like low-field electron transport characteristics with high mobility. The aligned planar geometry and excellent material quality of planar III-V nanowires may lead to highly integrated III-V nanophotonics and nanoelectronics.

Investigating wetting characteristics on microstructured surfaces for superhydrophobicity and metal microcasting

The engineering of liquid behavior on surfaces is important for infrastructure, transportation, manufacturing, and sensing. Surfaces can be rendered superhydrophobic by microstructuring, and superhydrophobic devices could lead to practical corrosion inhibition, self-cleaning, fluid flow control, and surface drag reduction. To more fully understand how liquid interacts with microstructured surfaces, this dissertation introduces a direct method for determining droplet solid-liquid-vapor interfacial geometry on microstructured surfaces. The technique performs metrology on molten metal droplets deposited onto microstructured surfaces and then frozen. Unlike other techniques, this visualization technique can be used on large areas of curved and opaque microstructured surfaces to determine contact line. This dissertation also presents measurements and models for how curvature and flexing of microstructured polymers affects hydrophobicity. Increasing curvature of microstructured surfaces leads to decreased slide angle for liquid droplets suspended on the surface asperities. For a surface with regularly spaced asperities, as curvature becomes more positive, droplets suspended on the tops of asperities are suspended on fewer asperities. Curvature affects superhydrophobicity because microscopic curvature changes solid-liquid interaction, pitch is altered, and curvature changes the shape of the three phase contact line. This dissertation presents a model of droplet interactions with curved microstructured surfaces that can be used to design microstructure geometries that maintain the suspension of a droplet when curved surfaces are covered with microstructured polymers. Controlling droplet dynamics could improve microfluidic devices and the shedding of liquids from expensive equipment, preventing corrosion and detrimental performance. This dissertation demonstrates redirection of dynamic droplet spray with anisotropic microstructures. Superhydrophobic microstructured surfaces can be economically fabricated using metal embossing masters, so this dissertation describes casting-based microfabrication of metal microstructures and nanostructures. Low melting temperature metal was cast into flexible silicone molds which were themselves cast from microfabricated silicon templates. The flexibility of the silicone mold permits casting of curved surfaces, which this dissertation demonstrates by fabricating a cylindrical metal roller with microstructures. The metal microstructures can be in turn used as a reusable molding tool. This dissertation also describes an industrial investment casting process to produce aluminum molds having integrated microstructures. Unlike conventional micromolding tools, the aluminum mold was large and had complex curved surfaces. The aluminum was cast into curved microstructured ceramic molds which were themselves cast from curved microstructured rubber. Many structures were successfully cast into the aluminum with excellent replication fidelity, including circular, square, and triangular holes. This dissertation demonstrates molding of large, curved surfaces having surface microstructures using the aluminum mold. This work contributes a more full understanding of the phenomenon of superhydrophobicity and techniques for the economic fabrication of superhydrophobic microstructures.

With or without you: does partner satisfaction and partner-directed violence influence the presence of a partner on women's Facebook cover profile photographs?

Social network sites (SNSs) provide new opportunities for online self-presentation of millions of users. The cover profile photograph (CPP) along with written information regarding relationship status is a central component of online self-presentation, although their associations with actual romantic relationships are not clear. We investigated relationships between the presence of a current romantic partner on the CPP and the displayed relationship status and partner satisfaction, partner-directed violence and women's intrasexual competition with peers. A total of 28 % of the 158 women with a Facebook profile and being involved in a romantic relationship had their romantic partners on their CPP. As predicted, women with their partners on the CPP were more satisfied with their romantic relationship than others. Furthermore, women who did not have their partner on the CPP tended to conceal or lie in their displayed mating status suggesting that this may be a strategy how to attract another potential mate. The partner-directed violence and intrasexual competition hypotheses were not supported. Overall, the CPP and an honestly displayed relationship status is an expression of relationship satisfaction amongst women.

Exploring coordination-driven self-assembly with autonomous chemical robots

The work presented herein focused on the automation of coordination-driven self assembly, exploring methods that allow syntheses to be followed more closely while forming new ligands, as part of the fundamental study of the digitization of chemical synthesis and discovery. Whilst the control and understanding of the principle of pre-organization and self-sorting under non-equilibrium conditions remains a key goal, a clear gap has been identified in the absence of approaches that can permit fast screening and real-time observation of the reaction process under different conditions. A firm emphasis was thus placed on the realization of an autonomous chemical robot, which can not only monitor and manipulate coordination chemistry in real-time, but can also allow the exploration of a large chemical parameter space defined by the ligand building blocks and the metal to coordinate. The self-assembly of imine ligands with copper and nickel cations has been studied in a multi-step approach using a self-built flow system capable of automatically controlling the liquid-handling and collecting data in real-time using a benchtop MS and NMR spectrometer. This study led to the identification of a transient Cu(I) species in situ which allows for the formation of dimeric and trimeric carbonato bridged Cu(II) assemblies. Furthermore, new Ni(II) complexes and more remarkably also a new binuclear Cu(I) complex, which usually requires long and laborious inert conditions, could be isolated. The study was then expanded to the autonomous optimization of the ligand synthesis by enabling feedback control on the chemical system via benchtop NMR. The synthesis of new polydentate ligands has emerged as a result of the study aiming to enhance the complexity of the chemical system to accelerate the discovery of new complexes. This type of ligand consists of 1-pyridinyl-4-imino-1,2,3-triazole units, which can coordinate with different metal salts. The studies to test for the CuAAC synthesis via microwave lead to the discovery of four new Cu complexes, one of them being a coordination polymer obtained from a solvent dependent crystallization technique. With the goal of easier integration into an automated system, copper tubing has been exploited as the chemical reactor for the synthesis of this ligand, as it efficiently enhances the rate of the triazole formation and consequently promotes the formation of the full ligand in high yields within two hours. Lastly, the digitization of coordination-driven self-assembly has been realized for the first time using an in-house autonomous chemical robot, herein named the ‘Finder’. The chemical parameter space to explore was defined by the selection of six variables, which consist of the ligand precursors necessary to form complex ligands (aldehydes, alkineamines and azides), of the metal salt solutions and of other reaction parameters – duration, temperature and reagent volumes. The platform was assembled using rounded bottom flasks, flow syringe pumps, copper tubing, as an active reactor, and in-line analytics – a pH meter probe, a UV-vis flow cell and a benchtop MS. The control over the system was then obtained with an algorithm capable of autonomously focusing the experiments on the most reactive region (by avoiding areas of low interest) of the chemical parameter space to explore. This study led to interesting observations, such as metal exchange phenomena, and also to the autonomous discovery of self assembled structures in solution and solid state – such as 1-pyridinyl-4-imino-1,2,3-triazole based Fe complexes and two helicates based on the same ligand coordination motif.

Effects of two teaching strategies on the relationship between nursing students’ self-efficacy and performance in BLS/AED

Purpose: Nurses and nursing students are often first responders to in-hospital cardiac arrest events; thus they are expected to perform Basic Life Support (BLS) and use an automated external defibrillator (AED) without delay. The aim of this study was to explore the relationship between nursing students’ self-efficacy and performance before and after receiving a particular training intervention in BLS/AED. Materials and methods: Explanatory correlational study. 177 nursing students received a 4-h training session in BLS/AED after being randomized to either a self-directed (SDG) or an instructor-directed teaching group (IDG).1 A validated self-efficacy scale, the Cardiff Test and Laerdal SkillReporter® software were used to assess students’ self-efficacy and performance in BLS/AED at pre-test, post-test and 3-month retention-test. Independent t-test analysis was performed to compare the differences between groups at pre-test. Pearson coefficient (r) was used to calculate the strength of the relationship between self-efficacy and performance in both groups at pre-test, post-test and retention-test. Results: Independent t-tests analysis showed that there were non-significant differences (p-values > 0.05) between groups for any of the variables measured. At pre-test, results showed that correlation between self-efficacy and performance was moderate for the IDG (r = 0.53; p < 0.05) and the SDG (r = 0.49; p < 0.05). At post-test, correlation between self-efficacy and performance was much higher for the SDG (r = 0.81; p < 0.05) than for the IDG (r = 0.32; p < 0.05), which in fact was weaker than at pre-test. Finally, it was found that whereas the correlation between self-efficacy and performance increased from the post-test to the retention-test to almost reach baseline levels for the ILG (r = 0.52; p < 0.05), it slightly decreased in this phase for the SDG (r = 0.77; p < 0.05). Conclusion: Student-directed strategies may be more effective than instructor-directed strategies at promoting self-assessment and, therefore, may help to improve and maintain the relationship between nursing student self-efficacy and actual ability to perform BLS/AED.

SERR spectroelectrochemical study of cytochrome cd1 nitrite reductase co-immobilized with physiological redox partner cytochrome c552 on biocompatible metal electrodes

© 2015 Silveira et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

NEW METAL-BASED MICELLES AS ANTICANCER AGENTS

Cancer is a leader cause of death worldwide. One of the problems associated with the current chemotherapeutic options is the noxious side effects caused by the lack of selectivity. In this frame, our research group has been committed to the development of a new Ru and Fe macrometallodrugs.[1] The data obtained so far shows that these compounds present an intrinsic selectivity towards cancer cells (relatively to healthy cells) due to the incorporation of polymeric ligands that promote a passive targeting through the cancer cell membrane. These results prompted us to the development of new macrometallodrugs bearing bioessential metals such as Fe, Zn and Co. We used a ‘M(bipy) 3 ’ scaffold (bipy = 2,2’-bipyridine derivatives) for the synthesis of the new compounds due to the promising cytotoxicity results observed for related compounds.[2] As polymeric ligands we have chosen the polylactide-co-polyethylene glycol amphiphilic copolymer that is able to self-assemble into micelles in water, keeping the metal center hidden, like a Trojan horse. We will present the synthesis and characterization of the new compounds and some preliminary data on their ability to form stable micelles (Figure 1).