Extraction of polydispersity information from photon correlation data

Photon correlation spectroscopy (PCS) is a light-scattering technique for particle size diagnosis. It has been used mainly in the investigation of hydrosol particles since it is based on the measurement of the correlation function of the light scattered from the Brownian motion of suspended particles. Recently this technique also proved useful for studying soot particles in flames and similar aerosol systems. In the case of a polydispersed system the problem of recovering the particle size distribution can be reduced to the problem of inverting the Laplace transform. In this paper we review several methods introduced by the authors for the solution of this problem. We present some numerical results and we discuss the resolution limits characterizing the reconstruction of the size distributions. © 1989.

The catalytic role of water in CO oxidation

Water, one of the most popular species in our planet, can play a catalytic role in many reactions, including reactions in heterogeneous catalysis. In a recent experimental work, Bergeld, Kasemo, and Chakarov demonstrated that water is able to promote CO oxidation under low temperatures (similar to200 K). In this study, we choose CO oxidation on Pt(111) in the presence of water as a model system to address the catalytic role of water for surface reactions in general using density functional theory. Many elementary steps possibly involved in the CO oxidation on Pt(111) at low temperatures have been investigated. We find the following. First, in the presence of water, the CO oxidation barrier is reduced to 0.33 eV (without water the barrier is 0.80 eV). This barrier reduction is mainly due to the H-bonding between the H in the H2O and the O at the transition state (TS), which stabilizes the TS. Second, CO can readily react with OH with a barrier of 0.44 eV, while COOH dissociation to produce CO2 is not easy (the barrier is 1.02 eV). Third, in the H2O+OH mixed phase, CO can be easily converted into CO2. It occurs through two steps: CO reacts with OH, forming COOH; and COOH transfers the H to a nearby H2O and, at the same time, an H in the H2O transfers to a OH, leading to CO2 formation. The reaction barrier of this process is 0.60 eV under CO coverage of 1/6 ML and 0.33 eV under CO coverage of 1/3 ML. The mechanism of CO oxidation at low temperatures is discussed. On the basis of our calculations, we propose that the water promotion effect can in general be divided into two classes: (i) By H-bonding between the H of H2O and an electron negative species such as the O in the reaction of CO+O+H2O-->CO2+H2O, H2O can stabilize the TS of the reaction and hence reduce the barrier. (ii) H2O first dissociates into H and OH and then OH or H participates directly in the reaction to induce new reaction mechanism with more favorable routes, in which OH or H can act as an intermediate. (C) 2003 American Institute of Physics.

Therapeutics bioconjugates: evaluation of iminoboronates as payload delivery system for cancer

The advent of bioconjugation impacted deeply the world of sciences and technology. New biomolecules were found, biological processes were understood, and novel methodologies were formed due to the fast expansion of this area. The possibility of creating new effective therapies for diseases like cancer is one of big applications of this now big area of study. Off target toxicity was always the problem of potent small molecules with high activity towards specific tumour targets. However, chemotherapy is now selective due to powerful linkers that connect targeting molecules with affinity to interesting biological receptors and cytotoxic drugs. This linkers must have very specific properties, such as high stability in plasma, no toxicity, no interference with ligand affinity nor drug potency, and at the same time, be able to lyse once inside the target molecule to release the therapeutic warhead. Bipolar environments between tumour intracellular and extracellular medias are usually exploited by this linkers in order to complete this goal. The work done in this thesis explores a new model for that same task, specific cancer drug delivery. Iminoboronates were studied due to its remarkable selective stability towards a wide pH range and endogenous molecules. A fluorescence probe was design to validate this model by creating an Off/On system and determine the payload release location in situ. A process was optimized to synthetize the probe 8-(1-aminoethyl)-7-hydroxy-coumarin (1) through a reductive amination reaction in a microwave reactor with 61 % yield. A method to conjugate this probe to ABBA was also optimized, obtaining the iminoboronate in good yields in mild conditions. The iminoboronate model was studied regarding its stability in several simulated biological environments and each half-life time was determined, showing the conjugate is stable most of the cases except in tumour intracellular systems. The construction of folate-ABBA-coumarin bioconjugate have been made to complete this evaluation. The ability to be uptaken by a cancer cell through endocytosis process and the conjugation delivery of coumarin fluorescence payload are two features to hope for in this construct.

Derivation of an Efficient Rule System Pattern Matcher

Formalizing algorithm derivations is a necessary prerequisite for developing automated algorithm design systems. This report describes a derivation of an algorithm for incrementally matching conjunctive patterns against a growing database. This algorithm, which is modeled on the Rete matcher used in the OPS5 production system, forms a basis for efficiently implementing a rule system. The highlights of this derivation are: (1) a formal specification for the rule system matching problem, (2) derivation of an algorithm for this task using a lattice-theoretic model of conjunctive and disjunctive variable substitutions, and (3) optimization of this algorithm, using finite differencing, for incrementally processing new data.

Conditioning and preconditioning of the variational data assimilation problem

Numerical weather prediction (NWP) centres use numerical models of the atmospheric flow to forecast future weather states from an estimate of the current state. Variational data assimilation (VAR) is used commonly to determine an optimal state estimate that miminizes the errors between observations of the dynamical system and model predictions of the flow. The rate of convergence of the VAR scheme and the sensitivity of the solution to errors in the data are dependent on the condition number of the Hessian of the variational least-squares objective function. The traditional formulation of VAR is ill-conditioned and hence leads to slow convergence and an inaccurate solution. In practice, operational NWP centres precondition the system via a control variable transform to reduce the condition number of the Hessian. In this paper we investigate the conditioning of VAR for a single, periodic, spatially-distributed state variable. We present theoretical bounds on the condition number of the original and preconditioned Hessians and hence demonstrate the improvement produced by the preconditioning. We also investigate theoretically the effect of observation position and error variance on the preconditioned system and show that the problem becomes more ill-conditioned with increasingly dense and accurate observations. Finally, we confirm the theoretical results in an operational setting by giving experimental results from the Met Office variational system.

Genesis of quantum nonlocality

We revisit the problem of an otherwise classical particle immersed in the zero-point radiation field, with the purpose of tracing the origin of the nonlocality characteristic of Schrodinger`s equation. The Fokker-Planck-type equation in the particles phase-space leads to an infinite hierarchy of equations in configuration space. In the radiationless limit the first two equations decouple from the rest. The first is the continuity equation: the second one, for the particle flux, contains a nonlocal term due to the momentum fluctuations impressed by the field. These equations are shown to lead to Schrodinger`s equation. Nonlocality (obtained here for the one-particle system) appears thus as a property of the description, not of Nature. (C) 2011 Elsevier B.V. All rights reserved.

RELATIVISTIC 3-PARTICLE DYNAMICAL EQUATIONS .1. THEORETICAL DEVELOPMENT

Starting from the two-particle Bethe-Salpeter equation in the ladder approximation and integrating over the time component of momentum, we rederive three-dimensional scattering integral equations satisfying constraints of relativistic unitarity and convariance, first derived by Weinberg and by Blankenbecler and Sugar. These two-particle equations are shown to be related by a transformation of variables. Hence we show how to perform and relate identical dynamical calculation using these two equations. Similarly, starting from the Bethe-Salpeter-Faddeev equation for the three-particle system and integrating over the time component of momentum, we derive several three-dimensional three-particle scattering equations satisfying constraints of relativistic unitarity and convariance. We relate two of these three-particle equations by a transformation of variables as in the two-particle case. The three-particle equations we derive are very practical and suitable for performing relativistic scattering calculations. (C) 1994 Academic Press, Inc.

Optimal control problem for deflection plate with crack

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The stability evolution of a family of simply periodic lunar orbits

The present work deals with a family of simply periodic orbits around the Moon in the rotating Earth Moon-particle system. Taking the framework of the planar, circular, restricted three-body problem, we follow the evolution of this family of periodic orbits using the numerical technique of Poincaré surface of section. The maximum amplitude of oscillation about the periodic orbits are determined and can be used as a parameter to measure the degree of stability in the phase space for such orbits. Despite the fact that the whole family of periodic orbits remain stable, there is a dichotomy in the quasi-periodic ones at the Jacobi constant Cj = 2.85. The quasi-periodic orbits with Cj < 2.85 oscillate around the periodic orbits in a different way from those with Cj > 2.85. © 1999 Elsevier Science Ltd. All rights reserved.

Time analysis for temporary gravitational capture: Satellites of Uranus

We study the problem of gravitational capture in the framework of the Sun-Uranus-particle system. Part of the space of initial conditions is systematically explored, and the duration of temporary gravitational capture is measured. The location and size of different capture-time regions are given in terms of diagrams of initial semimajor axis versus eccentricity. The other initial orbital elements - inclination (i), longitude of the node (Ω), argument of pericenter (ω), and time of pericenter passage (τ) - are first taken to be zero. Then we investigate the cases with ω = 90°, 180°, and 270°. We also present a sample of results for Ω = 90°, considering the cases i = 60°, 120°, 150°, and 180°. Special attention is given to the influence of the initial orbital inclination, taking orbits initially in opposition at pericenter. In this case, the initial inclination is varied from 0° to 180° in steps of 10°. The success of the final stage of the capture problem, which involves the transformation of temporary captures into permanent ones, is highly dependent on the initial conditions associated with the longest capture times. The largest regions of the initial-conditions space with the longest capture times occur at inclinations of 60°-70° and 160°. The regions of possible stability as a function of initial inclination are also delimited. These regions include not only a known set of retrograde orbits, but also a new sort of prograde orbit with inclinations greater than zero.

An interplanetary mission to Neptune system: Gravitational capture and maneuvers around triton

The gravitational capture was initially used to understand the capture of planetary satellites. However, in the 90's decade, this phenomenon was applied in spacecraft trajectories. Belbruno and Miller studied missions in the Earth-Moon system that uses this technique to save fuel during the insertion of the spacecraft in its final orbit around the Moon. Using a parameter defined as twice the two-body energy of the planet-particle system, Yamakawa also studied the gravitational capture in the Earth-Moon system. In the present paper, this technique is used to study a mission that goes to the Neptune system and perform a gravitational capture in the satellite Triton. The results show direct and retrograde trajectories, for different values of the initial conditions.

Distribution system restoration in a DG environment using a heuristic constructive multi-start algorithm

This paper proposes a heuristic constructive multi-start algorithm (HCMA) to distribution system restoration in real time considering distributed generators installed in the system. The problem is modeled as nonlinear mixed integer and considers the two main goals of the restoration of distribution networks: minimizing the number of consumers without power and the number of switching. The proposed algorithm is implemented in C++ programming language and tested using a large real-life distribution system. The results show that the proposed algorithm is able to provide a set of feasible and good quality solutions in a suitable time for the problem. © 2011 IEEE.

Development of CAN-based distributed control system for variable rate technology in agricultural machinery

The number of electronic devices connected to agricultural machinery is increasing to support new agricultural practices tasks related to the Precision Agriculture such as spatial variability mapping and Variable Rate Technology (VRT). The Distributed Control System (DCS) is a suitable solution for decentralization of the data acquisition system and the Controller Area Network (CAN) is the major trend among the embedded communications protocols for agricultural machinery and vehicles. The application of soil correctives is a typical problem in Brazil. The efficiency of this correction process is highly dependent of the inputs way at soil and the occurrence of errors affects directly the agricultural yield. To handle this problem, this paper presents the development of a CAN-based distributed control system for a VRT system of soil corrective in agricultural machinery. The VRT system is composed by a tractor-implement that applies a desired rate of inputs according to the georeferenced prescription map of the farm field to support PA (Precision Agriculture). The performance evaluation of the CAN-based VRT system was done by experimental tests and analyzing the CAN messages transmitted in the operation of the entire system. The results of the control error according to the necessity of agricultural application allow conclude that the developed VRT system is suitable for the agricultural productions reaching an acceptable response time and application error. The CAN-Based DCS solution applied in the VRT system reduced the complexity of the control system, easing the installation and maintenance. The use of VRT system allowed applying only the required inputs, increasing the efficiency operation and minimizing the environmental impact.

An infinite level atom coupled to a heat bath

Wir untersuchen die Mathematik endlicher, an ein Wärmebad gekoppelter Teilchensysteme. Das Standard-Modell der Quantenelektrodynamik für Temperatur Null liefert einen Hamilton-Operator H, der die Energie von Teilchen beschreibt, welche mit Photonen wechselwirken. Im Heisenbergbild ist die Zeitevolution des physikalischen Systems durch die Wirkung einer Ein-Parameter-Gruppe auf eine Menge von Observablen A gegeben: Diese steht im Zusammenhang mit der Lösung der Schrödinger-Gleichung für H. Um Zustände von A, welche das physikalische System in der Nähe des thermischen Gleichgewichts zur Temperatur T darstellen, zu beschreiben, folgen wir dem Ansatz von Jaksic und Pillet, eine Darstellung von A zu konstruieren. Die Vektoren in dieser Darstellung definieren die Zustände, die Zeitentwicklung wird mit Hilfe des Standard Liouville-Operators L beschrieben. In dieser Doktorarbeit werden folgende Resultate bewiesen bzw. hergeleitet: - die Konstuktion einer Darstellung - die Selbstadjungiertheit des Standard Liouville-Operators - die Existenz eines Gleichgewichtszustandes in dieser Darstellung - der Limes des physikalischen Systems für große Zeiten.

Transport of nanoparticles into polymersomes : a minimal model system of particles passage through biological membranes

This thesis focuses on the design and characterization of a novel, artificial minimal model membrane system with chosen physical parameters to mimic a nanoparticle uptake process driven exclusively by adhesion and softness of the bilayer. The realization is based on polymersomes composed of poly(dimethylsiloxane)-b-poly(2-methyloxazoline) (PMDS-b-PMOXA) and nanoscopic colloidal particles (polystyrene, silica), and the utilization of powerful characterization techniques. rnPDMS-b-PMOXA polymersomes with a radius, Rh ~100 nm, a size polydispersity, PD = 1.1 and a membrane thickness, h = 16 nm, were prepared using the film rehydratation method. Due to the suitable mechanical properties (Young’s modulus of ~17 MPa and a bending modulus of ~7⋅10-8 J) along with the long-term stability and the modifiability, these kind of polymersomes can be used as model membranes to study physical and physicochemical aspects of transmembrane transport of nanoparticles. A combination of photon (PCS) and fluorescence (FCS) correlation spectroscopies optimizes species selectivity, necessary for a unique internalization study encompassing two main efforts. rnFor the proof of concepts, the first effort focused on the interaction of nanoparticles (Rh NP SiO2 = 14 nm, Rh NP PS = 16 nm; cNP = 0.1 gL-1) and polymersomes (Rh P = 112 nm; cP = 0.045 gL-1) with fixed size and concentration. Identification of a modified form factor of the polymersome entities, selectively seen in the PCS experiment, enabled a precise monitor and quantitative description of the incorporation process. Combining PCS and FCS led to the estimation of the incorporated particles per polymersome (about 8 in the examined system) and the development of an appropriate methodology for the kinetics and dynamics of the internalization process. rnThe second effort aimed at the establishment of the necessary phenomenology to facilitate comparison with theories. The size and concentration of the nanoparticles were chosen as the most important system variables (Rh NP = 14 - 57 nm; cNP = 0.05 - 0.2 gL-1). It was revealed that the incorporation process could be controlled to a significant extent by changing the nanoparticles size and concentration. Average number of 7 up to 11 NPs with Rh NP = 14 nm and 3 up to 6 NPs with Rh NP = 25 nm can be internalized into the present polymersomes by changing initial nanoparticles concentration in the range 0.1- 0.2 gL-1. Rapid internalization of the particles by polymersomes is observed only above a critical threshold particles concentration, dependent on the nanoparticle size. rnWith regard possible pathways for the particle uptake, cryogenic transmission electron microscopy (cryo-TEM) has revealed two different incorporation mechanisms depending on the size of the involved nanoparticles: cooperative incorporation of nanoparticles groups or single nanoparticles incorporation. Conditions for nanoparticle uptake and controlled filling of polymersomes were presented. rnIn the framework of this thesis, the experimental observation of transmembrane transport of spherical PS and SiO2 NPs into polymersomes via an internalization process was reported and examined quantitatively for the first time. rnIn a summary the work performed in frames of this thesis might have significant impact on cell model systems’ development and thus improved understanding of transmembrane transport processes. The present experimental findings help create the missing phenomenology necessary for a detailed understanding of a phenomenon with great relevance in transmembrane transport. The fact that transmembrane transport of nanoparticles can be performed by artificial model system without any additional stimuli has a fundamental impact on the understanding, not only of the nanoparticle invagination process but also of the interaction of nanoparticles with biological as well as polymeric membranes. rn