Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

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.

Porous self-protonating spiropyran-based NIPAAm gels with improved reswelling kinetics

The final publication is available at Springer via http://dx.doi.org/[10.1007/s10853-015-9458-2]

Spectral self-action of THz emission from ionizing two-color laser pulses in gases

The spectrum of terahertz (THz) emission in gases via ionizing two-color femtosecond pulses is analyzed by means of a semi-analytic model and numerical simulations in 1D, 2D and 3D geometries taking into account propagation effects of both pump and THz fields. We show that produced THz signals interact with free electron trajectories and thus significantly influence further THz generation upon propagation, i.e., make the process inherently nonlocal. This self-action contributes to the observed strong spectral broadening of the generated THz field. We show that diffraction of the generated THz radiation is the limiting factor for the co-propagating low frequency amplitudes and thus for the self-action mechanism in 2D and 3D geometries.

STUDIES OF FUNCTIONALIZED NANOPARTICLES FOR SMART SELF-ASSEMBLY AND AS CONTROLLED DRUG DELIVERY

This dissertation is related to the studies of functionalized nanoparticles for self-assembly and as controlled drug delivery system. The whole topic is composed of two parts. In the first part, the research was conducted to design and synthesize a new type of ionic peptide-functionalized copolymer conjugates for self-assembly into nanoparticle fibers and 3D scaffolds with the ability of multi-drug loading and governing the release rate of each drug for tissue engineering. The self-assembly study confirmed that such peptide-functionalized amphiphilic copolymers underwent different self-assembly behavior. The bigger nanoparticles were more easily assembled into nanoparticle fibers and 3D scaffolds with larger pore size, while the smaller nanoparticle underwent faster self-assembly to form more compact 3D scaffolds with smaller porosity but more stable structure. Controlled release studies confirmed the ability of governing simultaneous release of different model drugs with independent release rate from a same scaffold. Cytotoxicity tests showed that all synthesized peptides, copolymers and peptide-copolymer conjugates were biocompatible with SW-620 cell lines and NIH3T3 cell lines. This new type of self-assembled scaffolds combined the advantages of peptide nanofibers and versatile controlled release of polymeric nanoparticles to achieve simultaneous multi-drug loading and controlled release of each drug, uniform distribution and flexibility of hydrogel scaffolds. The investigations in second part were first to design and synthesize organic biocide-loaded nanoparticles for low-leaching wood preservation using a cost-effective one-pot method to synthesize amphiphilic chitosan-g-PMMA nanoparticles loading with ~25-28 wt.% of the fungicide tebuconazole with particle size of ~100 nm diameter by FESEM. FESEM analysis confirmed efficient penetration of nanoparticles throughout the treated wooden stake with dimension of 19 × 19 × 455 mm^3. Leaching studies showed that biocide introduced into sapwood via nanoparticles leached only ~9% compared with the amount leached from tebuconazole solution-treated control, while soil jar tests showed that the nanoparticle-treated wood blocks were effectively protected from biological decay tested against G. trabeum, a brown rot fungus. Copper oxide nanoparticles with and without polymer stabilizers were also investigated to use as inorganic wood preservatives to clarify the factor affecting copper leaching from treated wood. Copper oxide nanoparticles with uniform diameters of ~10 nm and ~50 nm were prepared, and the leachates from southern pine sapwood treated with these nanoparticles were analyzed. It was found by TEM and EDS analysis that significant numbers of nanoparticles leached from the treated wood. The 50 nm nanoparticles leached slightly less than a soluble copper salt control, but 10 nm nanoparticles leached substantially more than the control. The effect of polymer stabilizers on nanoparticle leaching was also investigated. Results showed that polymer stabilizers increased leaching. The trends showed that nanoparticle size was a major factor in copper leaching.

Agents and SCT based self* control architecture for production systems

Otto-von-Guericke-Universität Magdeburg, Fakultät für Maschinenbau, Dissertation, 2016

Social-cognitive Antecedents of Ambidextrous Orientation in Family-owned Startups: The Role of Family Ties, Achievement Motivation, and Internal Locus of Control

Regulatory Focus Theory predicts that the motivation to self-regulate goal-directed thought and behavior depends on two distinct regulation strategies: a promotion focus based on attaining gains and a prevention focus based on avoiding losses. This study took a social-cognitive approach predicting that regulatory focus has an impact on how family startups (several family related founders) explore “new ideas”, exploit “old certainties” and achieve the balance of both (ambidexterity), compared to lone founder startups (only one founder present). It was proposed that the social context of family ties among founders leads them to a prevention focus concerned with avoiding the loss of the socio-emotional benefits of those ties. In order to avoid such a loss, family founders were expected to increase their risk perceptions and thus, explore less than lone founders, who lack such socio-emotional ties. It was also proposed that two commonly used psychological traits in entrepreneurship research --achievement motivation and internal locus of control, predispose entrepreneurs to a promotion focus. Founders with a promotion focus, in turn, were hypothesized to lead startups to more risk-seeking behaviors and to more explorative orientation. The previous argument was used as a springboard to derive hypotheses about ambidexterity (the ability to exploit and explore simultaneously) and survival hazards. Using Regulatory Focus Theory, exploitative orientation, conceptualized as the motivational strength to continue on previous paths of action, was hypothesized to be not significantly different from that of lone founder startups. Taking previous arguments together, lone founder startups were hypothesized to be more ambidextrous than family startups. Finally, ambidexterity and internal locus of control were hypothesized to reduce survival hazards in family startups. The findings suggested that family startups explore less than lone founder startups even after controlling for group effects. Interesting but contradictory findings revealed that internal locus of control have both a positive direct effect and a positive interaction that increases the explorative and ambidextrous orientation gap of family startups over lone founder startups. As expected, ambidexterity and internal locus of control reduced survival hazards on family startups. Implications for practitioners were derived based on a sample of 470 nascent entrepreneurs.

Self-healing thermal annealing: surface morphological restructuring control of GaN nanorods

With advances in nanolithography and dry etching, top-down methods of nanostructuring have become a widely used tool for improving the efficiency of optoelectronics. These nano dimensions can offer various benefits to the device performance in terms of light extraction and efficiency, but often at the expense of emission color quality. Broadening of the target emission peak and unwanted yellow luminescence are characteristic defect-related effects due to the ion beam etching damage, particularly for III–N based materials. In this article we focus on GaN based nanorods, showing that through thermal annealing the surface roughness and deformities of the crystal structure can be “self-healed”. Correlative electron microscopy and atomic force microscopy show the change from spherical nanorods to faceted hexagonal structures, revealing the temperature-dependent surface morphology faceting evolution. The faceted nanorods were shown to be strain- and defect-free by cathodoluminescence hyperspectral imaging, micro-Raman, and transmission electron microscopy (TEM). In-situ TEM thermal annealing experiments allowed for real time observation of dislocation movements and surface restructuring observed in ex-situ annealing TEM sampling. This thermal annealing investigation gives new insight into the redistribution path of GaN material and dislocation movement post growth, allowing for improved understanding and in turn advances in optoelectronic device processing of compound semiconductors.

Autonomous formation flying: unified control and collision avoidance methods for close manoeuvring spacecraft

The idea of spacecraft formations, flying in tight configurations with maximum baselines of a few hundred meters in low-Earth orbits, has generated widespread interest over the last several years. Nevertheless, controlling the movement of spacecraft in formation poses difficulties, such as in-orbit high-computing demand and collision avoidance capabilities, which escalate as the number of units in the formation is increased and complicated nonlinear effects are imposed to the dynamics, together with uncertainty which may arise from the lack of knowledge of system parameters. These requirements have led to the need of reliable linear and nonlinear controllers in terms of relative and absolute dynamics. The objective of this thesis is, therefore, to introduce new control methods to allow spacecraft in formation, with circular/elliptical reference orbits, to efficiently execute safe autonomous manoeuvres. These controllers distinguish from the bulk of literature in that they merge guidance laws never applied before to spacecraft formation flying and collision avoidance capacities into a single control strategy. For this purpose, three control schemes are presented: linear optimal regulation, linear optimal estimation and adaptive nonlinear control. In general terms, the proposed control approaches command the dynamical performance of one or several followers with respect to a leader to asymptotically track a time-varying nominal trajectory (TVNT), while the threat of collision between the followers is reduced by repelling accelerations obtained from the collision avoidance scheme during the periods of closest proximity. Linear optimal regulation is achieved through a Riccati-based tracking controller. Within this control strategy, the controller provides guidance and tracking toward a desired TVNT, optimizing fuel consumption by Riccati procedure using a non-infinite cost function defined in terms of the desired TVNT, while repelling accelerations generated from the CAS will ensure evasive actions between the elements of the formation. The relative dynamics model, suitable for circular and eccentric low-Earth reference orbits, is based on the Tschauner and Hempel equations, and includes a control input and a nonlinear term corresponding to the CAS repelling accelerations. Linear optimal estimation is built on the forward-in-time separation principle. This controller encompasses two stages: regulation and estimation. The first stage requires the design of a full state feedback controller using the state vector reconstructed by means of the estimator. The second stage requires the design of an additional dynamical system, the estimator, to obtain the states which cannot be measured in order to approximately reconstruct the full state vector. Then, the separation principle states that an observer built for a known input can also be used to estimate the state of the system and to generate the control input. This allows the design of the observer and the feedback independently, by exploiting the advantages of linear quadratic regulator theory, in order to estimate the states of a dynamical system with model and sensor uncertainty. The relative dynamics is described with the linear system used in the previous controller, with a control input and nonlinearities entering via the repelling accelerations from the CAS during collision avoidance events. Moreover, sensor uncertainty is added to the control process by considering carrier-phase differential GPS (CDGPS) velocity measurement error. An adaptive control law capable of delivering superior closed-loop performance when compared to the certainty-equivalence (CE) adaptive controllers is finally presented. A novel noncertainty-equivalence controller based on the Immersion and Invariance paradigm for close-manoeuvring spacecraft formation flying in both circular and elliptical low-Earth reference orbits is introduced. The proposed control scheme achieves stabilization by immersing the plant dynamics into a target dynamical system (or manifold) that captures the desired dynamical behaviour. They key feature of this methodology is the addition of a new term to the classical certainty-equivalence control approach that, in conjunction with the parameter update law, is designed to achieve adaptive stabilization. This parameter has the ultimate task of shaping the manifold into which the adaptive system is immersed. The performance of the controller is proven stable via a Lyapunov-based analysis and Barbalat’s lemma. In order to evaluate the design of the controllers, test cases based on the physical and orbital features of the Prototype Research Instruments and Space Mission Technology Advancement (PRISMA) are implemented, extending the number of elements in the formation into scenarios with reconfigurations and on-orbit position switching in elliptical low-Earth reference orbits. An extensive analysis and comparison of the performance of the controllers in terms of total Δv and fuel consumption, with and without the effects of the CAS, is presented. These results show that the three proposed controllers allow the followers to asymptotically track the desired nominal trajectory and, additionally, those simulations including CAS show an effective decrease of collision risk during the performance of the manoeuvre.

Self-care in Patients with Heart Failure

Objectives: To adapt for the Portuguese language the Self-Care of Heart Failure Index V6.2, analyse the self-care in maintenance, management skills and self-confidence of patients with heart failure who attend the nursing consultation of two Hospitals. Method: Explo- ratory study, sample 110 patients who frequented the nursing consultation for patients with heart failure of two Portuguese hospitals, conducted in the period of 6 months. He appea- led to the descriptive statistics and psychometric tests. Results: Internal consistency similar to the original scale. Mostly elderly, low literacy patients in self-care, low values associated with physical activity to the control of salt in meals taken away from home and inadequate control of signs and symptoms. Conclusion: Patients’ present difficulties in maintenance and management of the disease are self-confident face anyway. This instrument allows for individualized assessment leading to decision-making and action adjusted.

Integrated control of two tortricid (Lepidoptera) pests in apple orchards with sex pheromones and insecticides.

The apple is attacked by a significant number of insect pests in Brazilian commercial orchards, including Bonagota salubricola and Grapholita molesta (Lepidoptera: Tortricidae). Sexual disruption of B. salubricola and G. molesta was evaluated in apple orchard using the flowable pheromone formulations, SPLAT Grafo+Bona (SG+B), SPLAT Attract and Kill Grafo+Bona (SAKG+B), and compared with the standard insecticides used for management in the Integrated Apple Production (IAP) system. Both formulations were applied at a rate of 1kg/ha on October 10, 2005 and December 13, 2005 using 300 and 1000 point sources/ha of SG+B and SAKG+B, respectively in experimental units of 7 ha. Adult male captures of B. salubricola and G. molesta were evaluated weekly in Delta traps with specific synthetic sex pheromone from October 10, 2005 to February 14, 2006. Damage to fruits was evaluated on November 21 and December 21, 2005, and January 25 and February 14, 2006. In the SPLAT treated experimental units a significant reduction was observed in the number of B. salubricola and G. molesta males caught in Delta traps compared to the experimental unit IAP. Damage by B. salubricola at harvest ranged from 1.63 to 4.75% with no differences between treatments, while damage by G. molesta was near zero in all experimental units. Mating disruption using SG+B and SAKG+B was sufficient to control B. salubricola and G. molesta with results equivalent to IAP guidelines. This technology is promising for management of both pests in Brazilian apple orchards with immediate reduction of 43% in the number of insecticide applications.

Teacher’s Role in the Promotion of Two Emotional Intelligence Competencies in Fifth-Grade Children

This paper presents the results of a qualitative study aimed at analyzing the teacher’s role in promoting awareness and management of emotions in fifth-graders, as competencies of emotional intelligence. This resulted in a very significant study since, from the psychopedagogic perspective, it aims at breaking with the traditional role of teachers exclusively focused on transmitting knowledge, leaving aside the much-needed emotional support. Children demonstrated a poor vocabulary, as well as difficulty to identify some emotions and differentiate between them. This means a limitation for children to be aware of their own emotions and to control them.  As a conclusion, it is important to maximize the emotional capacities of students; it should be a primary task in the education centers, where teachers play a key role as a model and as a promoter of emotional intelligence.