Study of thermal spin crossover in [Fe(II)(isoxazole)6](BF4)2 with Mössbauer spectroscopy

57Fe Mössbauer spectroscopy of the mononuclear [Fe(II)(isoxazole)6](BF4) 2compound has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S = 0) and high-spin (S = 2) states. A temperature-dependent spin transition curve has been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures in the 240-60K range during the cooling and heating cycle. The compound exhibits a temperature-dependent two-step spin transition phenomenon with Tsco (step 1) = 92 and Tsco (step2) = 191K. The compound has three high-spin Fe(II) sites at the highest temperature of study; among them, two have slightly different coordination environments. These two Fe(II) sites are found to undergo a spin transition, while the third Fe(II) site retains the high-spin state over the whole temperature range. Possible reasons for the formation of the two steps in the spin transition curve are discussed. The observations made from the present study are in complete agreement with those envisaged from earlier magnetic and structural studies made on [Fe(II)(isoxazole)6](BF4)2, but highlights the nature of the spin crossover mechanism.

In situ growth strategy for highly efficient Ag2CO3/g-C3N4 hetero/nanojunctions with enhanced photocatalytic activity under sunlight irradiation

Developing novel heterojunction photocatalysts is a powerful strategy for improving the separation efficiency of photogenerated charge carriers, which is attracting the intense research interest in photocatalysis. Herein we report a highly efficient hetero/nanojunction consisting of Ag2CO3 nanoparticles grown on layered g-C3N4 nanosheets synthesized via a facile and template free in situ precipitation method. The UV–vis diffuse reflectance studies revealed that the synthesized Ag2CO3/g-C3N4 hetero/nanojunctions exhibit a broader and stronger light absorption in the visible light region, which is highly beneficial for absorbing the visible light in the solar spectrum. The optimum photocatalytic activity of Ag2CO3/g-C3N4 at a weight content of 10% Ag2CO3 for the degradation of Rhodamine B was almost 5.5 and 4 times as high as that of the pure Ag2CO3 and g-C3N4, respectively. The enhanced photocatalytic activity of the Ag2CO3/g-C3N4 hetero/nanojunctions is due to synergistic effects including the strong visible light absorption, large specific surface area, and high charge transfer and separation efficiency. More importantly, the high photostability and low use of the noble metal silver which reduces the cost of the material. Therefore, the synthesized Ag2CO3/g-C3N4 hetero/nanojunction photocatalyst is a promising candidate for energy storage and environment protection applications.

Platinum-catalysed cinnamaldehyde hydrogenation in continuous flow

Platinum is one of the most widely used hydrogenation catalysts. Here we describe the translation of batch reactions to continuous flow, affording tunable C=O versus C=C hydrogenation over a Pt/SiO2 catalyst, resulting in high steady state activity and single-pass yields in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol under mild conditions. Negligible catalyst deactivation occurs under extended flow operation due to removal of reactively-formed poisons from the reaction zone. Process intensification imparts a four-fold enhancement in cinnamyl alcohol productivity.

Synthesis of a novel and stable g-C3N4–Ag3PO4 hybrid nanocomposite photocatalyst and study of the photocatalytic activity under visible light irradiation

A facile and reproducible template free in situ precipitation method has been developed for the synthesis of Ag3PO4 nanoparticles on the surface of a g-C3N4 photocatalyst at room temperature. The g-C3N4–Ag3PO4 organic–inorganic hybrid nanocomposite photocatalysts were characterized by various techniques. TEM results show the in situ growth of finely distributed Ag3PO4 nanoparticles on the surface of the g-C3N4 sheet. The optimum photocatalytic activity of g-C3N4–Ag3PO4 at 25 wt% of g-C3N4 under visible light is almost 5 and 3.5 times higher than pure g-C3N4 and Ag3PO4 respectively. More attractively, the stability of Ag3PO4 was improved due to the in situ deposition of Ag3PO4 nanoparticles on the surface of the g-C3N4 sheet. The improved performance of the g-C3N4–Ag3PO4 hybrid nanocomposite photocatalysts under visible light irradiation was induced by a synergistic effect, including high charge separation efficiency of the photoinduced electron–hole pair, the smaller particle size, relatively high surface area and the energy band structure. Interestingly, the heterostructured g-C3N4–Ag3PO4 nanocomposite significantly reduces the use of the noble metal silver, thereby effectively reducing the cost of the Ag3PO4 based photocatalyst.

Expectation Modulates Episodic Memory Formation via Dopaminergic Circuitry

Episodic memory formation is shaped by expectation. Events that generate expectations have the capacity to influence memory. Additionally, whether subsequent events meet or violate expectations has consequences for memory. However, clarification is still required to illuminate the circumstances and direction of memory modulation. In the brain, the mechanisms by which expectation modulates memory formation also require consideration. The dopamine system has been implicated in signaling events associated with different states of expectancy; it has also been shown to modulate episodic memory formation in the hippocampus. Thus, the studies included in this dissertation utilized both functional magnetic resonance imaging (fMRI) and behavioral testing to examine when and how the dopaminergic system supports the modulation of memory by expectation. The work aimed to characterize the activation of dopaminergic circuitry in response to cues that generate expectancy, during periods of anticipation, and in response to outcomes that resolve expectancy. The studies also examined how each of these event types influenced episodic memory formation. The present findings demonstrated that novelty and expectancy violation both drive dopaminergic circuitry capable of contributing to memory formation. Consistent with elevated dopaminergic midbrain and hippocampus activation for each, expected versus expectancy violating novelty did not differentially affect memory success. We also showed that high curiosity expectancy states drive memory formation. This was supported by activation in dopaminergic circuitry that was greater for subsequently remembered information only in the high curiosity state. Finally, we showed that cues that generate high expected reward value versus high reward uncertainty differentially modulate memory formation during reward anticipation. This behavioral result was consistent with distinct temporal profiles of dopaminergic action having differential downstream effects on episodic memory formation. Integrating the present studies with previous research suggests that dopaminergic circuitry signals events that are unpredicted, whether cuing or resolving expectations. It also suggests that contextual differences change the contribution of the dopaminergic system during anticipation, depending on the nature of the expectation. And finally, this work is consistent with a model in which dopamine elevation in response to expectancy events positively modulates episodic memory formation.

Micro-Fabricated Surface Trap and Cavity Integration for Trapped Ion Quantum Computing

Atomic ions trapped in micro-fabricated surface traps can be utilized as a physical platform with which to build a quantum computer. They possess many of the desirable qualities of such a device, including high fidelity state preparation and readout, universal logic gates, long coherence times, and can be readily entangled with each other through photonic interconnects. The use of optical cavities integrated with trapped ion qubits as a photonic interface presents the possibility for order of magnitude improvements in performance in several key areas of their use in quantum computation. The first part of this thesis describes the design and fabrication of a novel surface trap for integration with an optical cavity. The trap is custom made on a highly reflective mirror surface and includes the capability of moving the ion trap location along all three trap axes with nanometer scale precision. The second part of this thesis demonstrates the suitability of small micro-cavities formed from laser ablated fused silica substrates with radii of curvature in the 300-500 micron range for use with the mirror trap as part of an integrated ion trap cavity system. Quantum computing applications for such a system include dramatic improvements in the photonic entanglement rate up to 10 kHz, the qubit measurement time down to 1 microsecond, and the measurement error rates down to the 10e-5 range. The final part of this thesis details a performance simulator for exploring the physical resource requirements and performance demands to scale such a quantum computer to sizes capable of performing quantum algorithms beyond the limits of classical computation.

Strain-Tunable Spin Moment in Ni-Doped Graphene

Graphene, due to its exceptional properties, is a promising material for nanotechnology applications. In this context, the ability to tune the properties of graphene-based materials and devices with the incorporation of defects and impurities can be of extraordinary importance. Here we investigate the effect of uniaxial tensile strain on the electronic and magnetic properties of graphene doped with substitutional Ni impurities (Ni_sub). We have found that, although Ni_sub defects are non-magnetic in the relaxed layer, uniaxial strain induces a spin moment in the system. The spin moment increases with the applied strain up to values of 0.3-0.4 \mu_B per Ni_sub, until a critical strain of ~6.5% is reached. At this point, a sharp transition to a high-spin state (~1.9 \mu_B) is observed. This magnetoelastic effect could be utilized to design strain-tunable spin devices based on Ni-doped graphene.

Parasitoses internas e frequência de desparasitação em cães do concelho de Vila Franca de Xira, Portugal

Dissertação de Mestrado Integrado em Medicina Veterinária

Charge transport and density of trap states in balanced high mobility ambipolar organic thin-film transistors

We report on charge transport and density of trap states (trap DOS) in ambipolar diketopyrrolopyrrole-benzothiadiazole copolymer thin-film transistors. This semiconductor possesses high electron and hole field-effect mobilities of up to 0.6 cm 2/V-s. Temperature and gate-bias dependent field-effect mobility measurements are employed to extract the activation energies and trap DOS to understand its unique high mobility balanced ambipolar charge transport properties. The symmetry between the electron and hole transport characteristics, parameters and activation energies is remarkable. We believe that our work is the first charge transport study of an ambipolar organic/polymer based field-effect transistor with room temperature mobility higher than 0.1 cm 2/V-s in both electrons and holes.

Charge carrier velocity distributions in high mobility polymer field-effect transistors

In this letter, the velocity distributions of charge carriers in high-mobility polymer thin-film transistors (TFTs) with a diketopyrrolopyrrole- naphthalene copolymer (PDPP-TNT) semiconductor active layer are reported. The velocity distributions are found to be strongly dependent on measurement temperatures as well as annealing conditions. Considerable inhomogeneity is evident at low measurement temperatures and for low annealing temperatures. Such transient transport measurements can provide additional information about charge carrier transport in TFTs which are unavailable using steady-state transport measurements.

Charge transport study of high mobility polymer thin-film transistors based on thiophene substituted diketopyrrolopyrrole copolymers

In this paper, we report on the device physics and charge transport characteristics of high-mobility dual-gated polymer thin-film transistors with active semiconductor layers consisting of thiophene flanked DPP with thienylene-vinylene-thienylene (PDPP-TVT) alternating copolymers. Room temperature mobilities in these devices are high and can exceed 2 cm2 V-1 s-1. Steady-state and non-quasi-static measurements have been performed to extract key transport parameters and velocity distributions of charge carriers in this copolymer. Charge transport in this polymer semiconductor can be explained using a Multiple-Trap-and-Release or Monroe-type model. We also compare the activation energy vs. field-effect mobility in a few important polymer semiconductors to gain a better understanding of transport of DPP systems and make appropriate comparisons.

The nature of the charge-ordered state in Y0.5Ca0.5MnO3 with a very small average radius of the A-site cations

A detailed investigation of Y0.5Ca0.5MnO3 with a very small radius of the A-site cations ([r(A)] approximate to 1.13 Angstrom reveals the occurrence of a charge-ordering transition in the paramagnetic state, at a relatively high temperature of 260 K. The orthorhombic lattice distortion, as measured by the dimensionless index D, is large (similar to 1.75%) over the entire 300-100 K range, but the antiferromagnetic interactions become prominent only at low temperatures (< 160 K). The charge-ordering gap in Y0.5Ca0.5MnO3, measured by low-temperature vacuum tunnelling spectroscopy, is large (similar to 0.5 eV) and the charge-ordered state is unaffected by the application of a magnetic field of 6 T. The study indicates that the nature of charge-ordering in Y0.5Ca0.5MnO3 which is dominated by the cooperative Jahn-Teller effect and the associated lattice distortion is distinctly different from analogous manganates with larger [r(A)].

Lead-acid batteries for partial-state-of-charge applications

2 V/40 Ah valve-regulated lead-acid (VRLA) cells have been constructed with negative plates employing carbon black as well as an admixture of carbon black fumed silica as additives in negative active material for partial-state-of-charge (PSoC) applications. Electrical performance of such cells is compared with conventional 2 V/40 Ah VRLA cells for PSoC operation. Active material utilization has been found to be higher for carbon-black fumed-silica mixed negative plates while formation is faster for cells with carbon-black mixed negative plates. Both faradaic efficiency and percentage capacity delivered have been found to be higher for cells with carbon-black + fumed-silica mixed negative plates. However, a high self-discharge rate is observed for cells with carbon-black + fumed-silica mixed negative plates.

Impedance parameters and the state-of-charge. III. Zinc-manganese dioxide and magnesium-manganese dioxide dry batteries

The problem of non-destructive determination of the state-of-charge of zinc- and magnesium-manganese dioxide dry batteries is examined experimentally from the viewpoint of internal impedance and open-circuit voltage at equilibrium. It is shown that the impedance is mainly charge-transfer controlled at relatively high states-of-charge and progressively changes over to diffusion control as the state-of-charge decreases in the case of zinc-manganese dioxide dry batteries. On the other hand, the impedance is mainly diffusion controlled for undischarged batteries but becomes charge-transfer controlled as soon as there is some discharge in the case of magnesium-manganese dioxide batteries. It is concluded that the determination of state-of-charge is not possible for both types of batteries by the measurement of impedance parameters due to film-induced fluctuations of these parameters. The measurement of open-circuit voltage at equilibrium can be used as a state-of-charge indicator for Zn-MnO2 batteries but not for Mg-MnO2 batteries.

Electrochemical studies of polyaniline in a gel polymer electrolyte - High energy and high power characteristics of a solid-state redox supercapacitor

Studies on redox supercapacitors employing electronically conducting polymers are of great importance for hybrid power sources and pulse power applications. In the present study, polyaniline (PANI) has been potentiodynamically deposited on stainless steel substrate and characterized in a gel polymer electrolyte (GPE). Use of the GPE facilitates a voltage limit of the capacitor to 1 V, instead of 0.75 V in aqueous electrolytes. From charge-discharge studies of the solid-state PANI capacitors, a specific capacitance of 250 F g(-1) has been obtained at a specific power of 7.5 kW kg(-1) of PANI. The values of specific capacitance and specific power are considerably higher than those reported in the literature. High energy and high power characteristics of the PANI are presented. (C) 2002 The Electrochemical Society.