Spatiotemporal control over the co-conformational switching in pH-responsive flavylium-based multistate pseudorotaxanes

A multistate molecular dyad containing flavylium and viologen units was synthesized and the pH dependent thermodynamics of the network completely characterized by a variety of spectroscopic techniques such as NMR, UV-vis and stopped-flow. The flavylium cation is only stable at acidic pH values. Above pH ≈ 5 the hydration of the flavylium leads to the formation of the hemiketal followed by ring-opening tautomerization to give the cis-chalcone. Finally, this last species isomerizes to give the trans-chalcone. For the present system only the flavylium cation and the trans-chalcone species could be detected as being thermodynamically stable. The hemiketal and the cis-chalcone are kinetic intermediates with negligible concentrations at the equilibrium. All stable species of the network were found to form 1 : 1 and 2 : 1 host : guest complexes with cucurbit[7]uril (CB7) with association constants in the ranges 10(5)-10(8) M(-1) and 10(3)-10(4) M(-1), respectively. The 1 : 1 complexes were particularly interesting to devise pH responsive bistable pseudorotaxanes: at basic pH values (≈12) the flavylium cation interconverts into the deprotonated trans-chalcone in a few minutes and under these conditions the CB7 wheel was found to be located around the viologen unit. A decrease in pH to values around 1 regenerates the flavylium cation in seconds and the macrocycle is translocated to the middle of the axle. On the other hand, if the pH is decreased to 6, the deprotonated trans-chalcone is neutralized to give a metastable species that evolves to the thermodynamically stable flavylium cation in ca. 20 hours. By taking advantage of the pH-dependent kinetics of the trans-chalcone/flavylium interconversion, spatiotemporal control of the molecular organization in pseudorotaxane systems can be achieved.

Comparação do controle do inversor trifásico conectado à rede com filtro LCL considerando o amortecimento passivo e ativo

Distributed generation systems must fulfill standards specifications of current harmonics injected to the grid. In order to satisfy these grid requirements, passive filters are connected between inverter and grid. This work compares the characteristic response of the traditional inductive (L) filter with the inductive-capacitive-inductive (LCL) filter. It is shown that increasing the inductance L leads to a good ripple current suppression around the inverter switching frequency. The LCL filter provides better harmonic attenuation and reduces the filter size. The main drawback is the LCL filter impedance, which is characterized by a typical resonance peak, which must be damped to avoid instability. Passive or active techniques can be used to damp the LCL resonance. To address this issue, this dissertation presents a comparison of current control for PV grid-tied inverters with L filter and LCL filter and also discuss the use of active and passive damping for different regions of resonance frequency. From the mathematical models, a design methodology of the controllers was developed and the dynamic behavior of the system operating in closed loop was investigated. To validate the studies developed during this work, experimental results are presented using a three-phase 5kW experimental platform. The main components and their functions are discussed in this work. Experimental results are given to support the theoretical analysis and to illustrate the performance of grid-connected PV inverter system. It is shown that the resonant frequency of the system, and sampling frequency can be associated in order to calculate a critical frequency, below which is essential to perform the damping of the LCL filter. Also, the experimental results show that the active buffer per virtual resistor, although with a simple development, is effective to damp the resonance of the LCL filter and allow the system to operate stable within predetermined parameters.

Projeto, implementação e análise de um conversor CC-CC de alto ganho e alto rendimento para aplicações fotovoltaicas

In recent years the photovoltaic generation has had greater insertion in the energy mix of the most developed countries, growing at annual rates of over 30%. The pressure for the reduction of pollutant emissions, diversification of the energy mix and the drop in prices are the main factors driving this growth. Grid tied systems plays an important role in alleviating the energy crisis and diversification of energy sources. Among the grid tied systems, building integrated photovoltaic systems suffers from partial shading of the photovoltaic modules and consequently the energy yield is reduced. In such cases, classical forms of modules connection do not produce good results and new techniques have been developed to increase the amount of energy produced by a set of modules. In the parallel connection technique of photovoltaic modules, a high voltage gain DC-DC converter is required, which is relatively complex to build with high efficiency. The current-fed isolated converters explored in this work have some desirable characteristics for this type of application, such as: low input current ripple and input voltage ripple, high voltage gain, galvanic isolation, feature high power capacity and it achieve soft switching in a wide operating range. This study presents contributions to the study of a high gain and high efficiency DC-DC converter for use in a parallel system of photovoltaic generation, being possible the use in a microinverter or with central inverter. The main contributions of this work are: analysis of the active clamping circuit operation proposing that the clamp capacitor connection must be done on the negative node of the power supply to reduce the input current ripple and thus reduce the filter requirements; use of a voltage doubler in the output rectifier to reduce the number of components and to extend the gain of the converter; detailed study of the converter components in order to raise the efficiency; obtaining the AC equivalent model and control system design. As a result, a DC-DC converter with high gain, high efficiency and without electrolytic capacitors in the power stage was developed. In the final part of this work the DC-DC converter operation connected to an inverter is presented. Besides, the DC bus controller is designed and are implemented two maximum power point tracking algorithms. Experimental results of full system operation connected to an emulator and subsequently to a real photovoltaic module are also given.

Analysis of cyclic variations during mode switching between spark ignition and controlled auto-ignition combustion operations

© IMechE 2014. Controlled auto-ignition, also known as homogeneous charge compression ignition, has been the subject of extensive research because of their ability to provide simultaneous reductions in fuel consumption and NOx emissions from a gasoline engine. However, due to its limited operation range, switching between controlled auto-ignition and spark ignition combustion is needed to cover the complete operating range of a gasoline engine for passenger car applications. Previous research has shown that the spark ignition -controlled auto-ignition hybrid combustion (SCHC) has the potential to control the ignition timing and heat release process during the mode transition operations. However, it was found that the SCHC is often characterized with large cycle-to-cycle variations. The cyclic variations in the in-cylinder pressure are particularly noticeable in terms of both their peak values and timings while the coefficient of variation in the indicated mean effective pressure is much less. In this work, the cyclic variations in SCHC operations were analyzed by means of in-cylinder pressure and heat release analysis in a single-cylinder gasoline engine equipped with Variable Valve Actuation (VVA) systems. First, characteristics of the in-cylinder pressure traces during the spark ignition-controlled auto-ignition hybrid combustion operation are presented and their heat release processes analyzed. In order to clarify the contribution to heat release and cyclic variation in SCHC, a new method is introduced to identify the occurrence of auto-ignition combustion and its subsequent heat release process. Based on the new method developed, the characteristics of cyclic variations in the maximum rate of pressure rise and different stages of heat release process have been analyzed and discussed.

High On/Off ratio memristive switching of manganite/cuprate bilayer by interfacial magnetoelectricity

Memristive switching serves as the basis for a new generation of electronic devices. Memristors are two-terminal devices in which the current is turned on and off by redistributing point defects, e.g., vacancies, which is difficult to control. Memristors based on alternative mechanisms have been explored, but achieving both the high On/Off ratio and the low switching energy desirable for use in electronics remains a challenge. Here we report memristive switching in a La_(0.7)Ca_(0.3)MnO_(3)/PrBa_(2)Cu_(3)O_(7) bilayer with an On/Off ratio greater than 103 and demonstrate that the phenomenon originates from a new type of interfacial magnetoelectricity. Using results from firstprinciples calculations, we show that an external electric-field induces subtle displacements of the interfacial Mn ions, which switches on/off an interfacial magnetic “dead” layer, resulting in memristive behavior for spin-polarized electron transport across the bilayer. The interfacial nature of the switching entails low energy cost about of a tenth of atto Joule for write/erase a “bit”. Our results indicate new opportunities for manganite/cuprate systems and other transition-metal-oxide junctions in memristive applications.

A Thermal Management Solution for Compact Power Converters

Regulated Transformer Rectifier Units contain several power electronic boards to facilitate AC to DC power conversion. As these units become smaller, the number of devices on each board increases while their distance from each other decreases, making active cooling essential to maintaining reliable operation. Although it is widely accepted that liquid is a far superior heat transfer medium to air, the latter is still capable of yielding low device operating temperatures with proper heat sink and airflow design. The purpose of this study is to describe the models and methods used to design and build the thermal management system for one of the power electronic boards in a compact, high power regulated transformer rectifier unit. Maximum device temperature, available pressure drop and manufacturability were assessed when selecting the final design for testing. Once constructed, the thermal management system’s performance was experimentally verified at three different power levels.

Functions of code-switching in multilingual student community

Dissertação de Mestrado, Ciências da Linguagem, Faculdade de Ciências Humanas e Sociais, Universidade do Algarve, 2013

Estimating the in-vivo HIV template switching and recombination rate

BACKGROUND: HIV recombination has been estimated in vitro using a variety of approaches, and shows a high rate of template switching per reverse transcription event. In-vivo studies of recombination generally measure the accumulation of recombinant strains over time, and thus do not directly estimate a comparable template switching rate. METHOD: To examine whether the estimated in-vitro template switching rate is representative of the rate that occurs during HIV infection in vivo, we adopted a novel approach, analysing single genome sequences from early founder viruses to study the in-vivo template switching rate in the env region of HIV. RESULTS: We estimated the in-vivo per cycle template switching rate to be between 0.5 and 1.5/1000 nt, or approximately 5-14 recombination events over the length of the HIV genome. CONCLUSION: The in-vivo estimated template switching rate is close to the in-vitro estimated rate found in primary T lymphocytes but not macrophages, which is consistent with the majority of HIV infection occurring in T lymphocytes.

Cross-strand disulfides in the non-hydrogen bonding site of antiparallel β-sheet (aCSDns): poised for biological switching

Forbidden disulfides are stressed disulfides found in recognisable protein contexts previously defined as structurally forbidden. The torsional strain of forbidden disulfides is typically higher than for structural disulfides, but not so high as to render them immediately susceptible to reduction under physionormal conditions. The meta-stability of forbidden disulfides makes them likely candidates as redox switches. Here we mined the Protein Data Bank for examples of the most common forbidden disulfide, the aCSDn. This is a canonical motif in which disulfide-bonded cysteine residues are positioned directly opposite each other on adjacent anti-parallel β-strands such that the backbone hydrogen bonded moieties are directed away from each other. We grouped these aCSDns into homologous clusters and performed an extensive physicochemical and informatic analysis of the examples found. We estimated their torsional energies using quantum chemical calculations and studied differences between the preferred conformations of the computational model and disulfides found in solved protein structures to understand the interaction between the forces imposed by the disulfide linkage and typical constraints of the surrounding β-sheet. In particular, we assessed the twisting, shearing and buckling of aCSDn-containing β-sheets, as well as the structural and energetic relaxation when hydrogen bonds in the motif are broken. We show the strong preference of aCSDns for the right-handed staple conformation likely arises from its compatibility with the twist, shear and Cα separation of canonical β-sheet. The disulfide can be accommodated with minimal distortion of the sheet, with almost all the strain present as torsional strain within the disulfide itself. For each aCSDn cluster, we summarise the structural and strain data, taxonomic conservation and any evidence of redox activity. aCSDns are known substrates of thioredoxin-like enzymes. This, together with their meta-stability, means they are ideally suited to biological switching roles and are likely to play important roles in the molecular pathways of oxidative stress.

Reversing diet-induced metabolic dysregulation by diet switching leads to altered hepatic de novo lipogenesis and glycerolipid synthesis

In humans, low-energy diets rapidly reduce hepatic fat and improve/normalise glycemic control. Due to difficulties in obtaining human liver, little is known about changes to the lipid species and pathway fluxes that occur under these conditions. Using a combination of stable isotope, and targeted metabolomic approaches we investigated the acute (7–9 days) hepatic effects of switching high-fat high-sucrose diet (HFD) fed obese mice back to a chow diet. Upon the switch, energy intake was reduced, resulting in reductions of fat mass and hepatic triacyl- and diacylglycerol. However, these parameters were still elevated compared to chow fed mice, thus representing an intermediate phenotype. Nonetheless, glucose intolerance and hyperinsulinemia were completely normalized. The diet reversal resulted in marked reductions in hepatic de novo lipogenesis when compared to the chow and HFD groups. Compared with HFD, glycerolipid synthesis was reduced in the reversal animals, however it remained elevated above that of chow controls, indicating that despite experiencing a net loss in lipid stores, the liver was still actively esterifying available fatty acids at rates higher than that in chow control mice. This effect likely promotes the re-esterification of excess free fatty acids released from the breakdown of adipose depots during the weight loss period.

Robust adaptive backstepping controller design for DC-DC buck converters with external disturbances

In modern power electronic systems, DC-DC converter is one of the main controlled power sources for driving DC systems. But the inherent nonlinear and time-varying characteristics often result in some difficulties mostly related to the control issue. This paper presents a robust nonlinear adaptive controller design with a recursive methodology based on the pulse width modulation (PWM) to drive a DC-DC buck converter. The proposed controller is designed based on the dynamical model of the buck converter where all parameters within the model are assumed as unknown. These unknown parameters are estimated through the adaptation laws and the stability of these laws are ensured by formulating suitable control Lyapunov functions (CLFs) at different stages. The proposed control scheme also provides robustness against external disturbances as these disturbances are considered within the model. One of the main features of the proposed scheme is that it overcomes the over-parameterization problems of unknown parameters which usually appear in some conventional adaptive methods. Finally, the effectiveness of the proposed control scheme is verified through the simulation results and compared to that of an existing adaptive backstepping controller. Simulation results clearly indicate the performance improvement in terms of a faster output voltage tracking response.

AN ENERGY BASED MINIMUM-TIME OPTIMAL CONTROL OF DC-DC CONVERTERS

Time-optimal response is an important and sometimes necessary characteristic of dynamic systems for specific applications. Power converters are widely used in different electrical systems and their dynamic response will affect the whole system. In many electrical systems like microgrids or voltage regulators which supplies sensitive loads fast dynamic response is a must. Minimum time is the fastest converter to compensate the step output reference or load change. Boost converters as one of the wildly used power converters in the electrical systems are aimed to be controlled in optimal time in this study. Linear controllers are not able to provide the optimal response for a boost converter however they are still useful and functional for other applications like reference tracking or stabilization. To obtain the fastest possible response from boost converters, a nonlinear control approach based on the total energy of the system is studied in this research. Total energy of the system considers as the basis for developing the presented method, since it is easy and accurate to measure besides that the total energy of the system represents the actual operating condition of the boost converter. The detailed model of a boost converter is simulated in MATLAB/Simulink to achieve the time optimal response of the boost converter by applying the developed method. The simulation results confirmed the ability of the presented method to secure the time optimal response of the boost converter under four different scenarios.

SVPWM SWITCHING PATTERN FOR Z-SOURCE INVERTER, SIMULATION AND APPLICATION

The voltage source inverter (VSI) and current voltage source inverter (CSI) are widely used in industrial application. But the traditional VSIs and CSIs have one common problem: can’t boost or buck the voltage come from battery, which make them impossible to be used alone in Hybrid Electric Vehicle (HEV/EV) motor drive application, other issue is the traditional inverter need to add the dead-band time into the control sequence, but it will cause the output waveform distortion. This report presents an impedance source (Z-source network) topology to overcome these problems, it can use one stage instead of two stages (VSI or CSI + boost converter) to buck/boost the voltage come from battery in inverter system. Therefore, the Z-source topology hardware design can reduce switching element, entire system size and weight, minimize the system cost and increase the system efficiency. Also, a modified space vector pulse-width modulation (SVPWM) control method has been selected with the Z-source network together to achieve the best efficiency and lower total harmonic distortion (THD) at different modulation indexes. Finally, the Z-source inverter controlling will modulate under two control sequences: sinusoidal pulse width modulation (SPWM) and SVPWM, and their output voltage, ripple and THD will be compared.

Development of Physics-based Models and Design Optimization of Power Electronic Conversion Systems

The main objective for physics based modeling of the power converter components is to design the whole converter with respect to physical and operational constraints. Therefore, all the elements and components of the energy conversion system are modeled numerically and combined together to achieve the whole system behavioral model. Previously proposed high frequency (HF) models of power converters are based on circuit models that are only related to the parasitic inner parameters of the power devices and the connections between the components. This dissertation aims to obtain appropriate physics-based models for power conversion systems, which not only can represent the steady state behavior of the components, but also can predict their high frequency characteristics. The developed physics-based model would represent the physical device with a high level of accuracy in predicting its operating condition. The proposed physics-based model enables us to accurately develop components such as; effective EMI filters, switching algorithms and circuit topologies [7]. One of the applications of the developed modeling technique is design of new sets of topologies for high-frequency, high efficiency converters for variable speed drives. The main advantage of the modeling method, presented in this dissertation, is the practical design of an inverter for high power applications with the ability to overcome the blocking voltage limitations of available power semiconductor devices. Another advantage is selection of the best matching topology with inherent reduction of switching losses which can be utilized to improve the overall efficiency. The physics-based modeling approach, in this dissertation, makes it possible to design any power electronic conversion system to meet electromagnetic standards and design constraints. This includes physical characteristics such as; decreasing the size and weight of the package, optimized interactions with the neighboring components and higher power density. In addition, the electromagnetic behaviors and signatures can be evaluated including the study of conducted and radiated EMI interactions in addition to the design of attenuation measures and enclosures.

A Markov switching unobserved component analysis of the CDX index term premium

Using a Markov switching unobserved component model we decompose the term premium of the North American CDX index into a permanent and a stationary component. We establish that the inversion of the CDX term premium is induced by sudden changes in the unobserved stationary component, which represents the evolution of the fundamentals underpinning the probability of default in the economy. We find evidence that the monetary policy response from the Fed during the crisis period was effective in reducing the volatility of the term premium. We also show that equity returns make a substantial contribution to the term premium over the entire sample period.