Reduced fluoresceinamine as a fluorescent sensor for nitric oxide

A new fluorescent sensor for nitric oxide (NO) is presented that is based on its reaction with a non fluorescent substance, reduced fluoresceinamine, producing the highly fluorescent fluoresceinamine. Using a portable homemade stabilized light source consisting of 450 nm LED and fiber optics to guide the light, the sensor responds linearly within seconds in the NO concentration range between about 10–750 µM with a limit of detection (LOD) of about 1 µM. The system generated precise intensity readings, with a relative standard deviation of less than 1%. The suitability of the sensor was assessed by monitoring the NO generated by either the nitrous acid decomposition reaction or from a NO-releasing compound. Using relatively high incubation times, the sensor also responds quantitatively to hydrogen peroxide and potassium superoxide, however, using transient signal measurements results in no interfering species.

Vertical CNT-Si Photodiode Array

Agências financiadoras: National Natural Science Foundation of China - 61204077; Shenzhen Science and Technology Innovation Commission - JCYJ20120614150521967

Benzo[c]thiophene chromophores linked to cationic Fe and Ru derivatives for NLO materials: synthesis characterization and quadratic hyperpolarizabilities

5-Monocyclopentadienyliron(II)/ruthenium(II) complexes of the general formula [M(5-C5H5)(PP)(L1)][PF6] {M = Fe, PP = dppe; M = Ru, PP = dppe or 2PPh3; L1 = 5-[3-(thiophen-2-yl)benzo[c]thiophenyl]thiophene-2-carbonitrile} have been synthesized and studied to evaluate their molecular quadratic hyperpolarizabilities. The compounds were fully characterized by NMR, FTIR and UV/Vis spectroscopy and their electrochemical behaviour studied by cyclic voltammetry. Quadratic hyperpolarizabilities () were determined by hyper-Rayleigh scattering measurements at a fundamental wavelength of 1500 nm. Density functional theory calculations were employed to rationalize the second-order non-linear optical properties of these complexes.

Optical fiber sensor for Hg(II) based on carbon dots

An optical fiber sensor for Hg(II) in aqueous solution based on sol–gel immobilized carbon dots nanoparticles functionalized with PEG200 and N-acetyl-l-cysteine is described. This sol–gel method generated a thin (about 750 nm), homogenous and smooth (roughness of 2.7±0.7 a˚ ) filmthat immobilizes the carbon dots and allows reversible sensing of Hg(II) in aqueous solution. A fast (less than 10 s), reversible and stable (the fluorescence intensity measurements oscillate less than 1% after several calibration cycles) sensor system was obtained. The sensor allow the detection of submicron molar concentrations of Hg(II) in aqueous solution. The fluorescence intensity of the immobilized carbon dots is quenched by the presence of Hg(II) with a Stern-Volmer constant (pH = 6.8) of 5.3×105M−1.

Luminol-doped nanostructured composite materials for chemiluminescent sensing of hydrogen peroxide

Silica based nanostructured composite materials doped with luminol and cobalt(II) ion were synthesized and characterized, resulting in a highly chemiluminescent material in the presence of hydrogen peroxide. A detection system with the CL light guided from the reaction tube to the photomultiplier tube using a one millimeter glass optical fiber was developed and assessed. A linear response was observed using a semi-logarithm calibration between 50–2000 µM hydrogen peroxide with 1 µM as the limit of detection.

Estudo do processo de reorientacão do campo do director por acção de um campo magnético numa fase nemática confinada

Estudamos teoricamente as transi ções de Fr éedericksz nas geometrias interm édias entre: (i) afunilamento e tor ção (ii) tor ção e flexão; e (iii) fexão e afunilamento. Foram determinadas as condi ções em que a transi ção entre o estado não deformado e o estado homogeneamente deformado (transi ção de Fr éedericksz usual) e substituída pela transi ção entre o estado não deformado e o estado deformado com estrutura peri ódica. Tamb ém estudamos te órica e experimentalmente a dinâmica de reorienta ção do campo do director ap os rota ção s ubita da amostra num campo magn ético uniforme. Consideramos monodomí nios de cristais l íquidos nem áticos uniaxiais não quirais diamagnéticos de baixo peso molecular, contidos entre duas fronteiras planas uniformes paralelas e r ígidas com alinhamento planar. Simulamos e reproduzimos, na geometria de tor ção toda a evolu ção do campo do director desde o momento em que se impõe uma rota ção s úbita e at é ao instante em que se observa a forma ção de bandas.

Synthesis, characterization and reactivity of new cobalt, palladium and nickel complexes bearing α-diimines and P, O ligands

This work describes the synthesis and characterization of a series of new α-diimine and P,O, β-keto and acetamide phosphines ligands, and their complexation to Ni(II), Co(II),Co(III) and Pd(II) to obtain a series of new compounds aiming to study their structural characteristics and to test their catalytic activity. All the compounds synthesized were characterized by the usual spectroscopic and spectrometric techniques: Elemental Analysis, MALDI-TOF-MS spectrometry, IR, UV-vis, 1H, 13C and 31P NMR spectroscopies. Some of the paramagnetic compounds were also characterized by EPR. For the majority of the compounds it was possible to solve their solid state structure by single crystal X-ray diffraction. Tests for olefin polymerization were performed in order to determine the catalytic activity of the Co(II) complexes. Chapter I presents a brief introduction to homogenous catalysis, highlighting the reactions catalyzed by the type of compounds described in this thesis, namely olefin polymerization and oligomerization and reactions catalyzed by the complexes bearing α-diimines and P,O type ligands. Chapter II is dedicated to the description of the synthesis of new α-diimines cobalt (II) complexes, of general formula [CoX2(α-diimine)], where X = Cl or I and the α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (Ar-DAB). Structures solved by single crystal X-ray diffraction were obtained for all the described complexes. For some of the compounds, X-band EPR measurements were performed on polycrystalline samples, showing a high-spin Co(II) (S = 3/2) ion, in a distorted axial environment. EPR single crystal experiments on two of the compounds allowed us to determine the g tensor orientation in the molecular structure. In Chapter III we continue with the synthesis and characterization of more cobalt (II)complexes bearing α-diimines of general formula [CoX2(α-diimine)], with X = Cl or I and α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl- 1,4-diaza-1,3-butadiene (Ar-DAB). The structures of three of the new compounds synthesized were determined by single crystal X-ray diffraction. A NMR paramagnetic characterization of all the compounds described is presented. Ethylene polymerization tests were done to determine the catalytic activity of several of the Co(II) complexes described in Chapter II and III and their results are shown. In Chapter IV a new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, and its complexes with Zn(II) and Pd(II), were synthesized. Both the ligand and its complexes show syn and anti isomers. Structures of the ligand and the anti isomer of the Pd(II) complex were solved by single crystal X-ray diffraction. All the compounds were characterized by elemental analysis, MALDI-TOF-MS spectrometry, and by IR, UV-vis, 1H, 13C, 1H-1H COSY, 1H-13C HSQC, 1H-13C HSQC-TOCSY and 1H-1H NOESY NMR when necessary. DFT studies showed that both conformers of [PdCl2(BIAN)] are isoenergetics and can be obtain experimentally. However, we can predict that the isomerization process is not available in square-planar complex, but is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected. Chapter V describes the synthesis of new P, O type ligands, β-keto phosphine, R2PCH2C(O)Ph, and acetamide phosphine R2PNHC(O)Me, as well as a series of new cobalt(III) complexes namely [(η5-C5H5)CoI2{Ph2PCH2C(O)Ph}], and [(η5- C5H5)CoI2{Ph2PNHC(O)Me}]. Treating these Co(III) compounds with an excess of Et3N, resulted in complexes η2-phosphinoenolate [(η5-C5H5)CoI{Ph2PCH…C(…O)Ph}] and η2- acetamide phosphine [(η5-C5H5)CoI{Ph2PN…C(…O)Me}]. Nickel (II) complexes were also obtained: cis-[Ni(Ph2PN…C(…O)Me)2] and cis-[Ni((i-Pr)2PN…C(…O)Me)2]. Their geometry and isomerism were discussed. Seven structures of the compounds described in this chapter were determined by single crystal X-ray diffraction. The general conclusions of this work can be found in Chapter VI.

Comparative study about heating systems for pultrusion process

Different heating systems have been used in pultrusion, where the most widely used heaters are planar resistances. The primary objective of this study was to develop an improved heating system and compare its performance with that of a system with planar resistances. In this study, thermography was used to better understand the temperature profile along the die. Finite element analysis was performed to determine the amount of energy consumed by the heating systems. Improvements were made to the die to test the new heating system, and it was found that the new system reduced the setup time and energy consumption by approximately 57%.

A fractional approach for the motion planning of redundant and hyper-redundant manipulators

The trajectory planning of redundant robots through the pseudoinverse control leads to undesirable drift in the joint space. This paper presents a new technique to solve the inverse kinematics problem of redundant manipulators, which uses a fractional differential of order α to control the joint positions. Two performance measures are defined to examine the strength and weakness of the proposed method. The positional error index measures the precision of the manipulator's end-effector at the target position. The repeatability performance index is adopted to evaluate if the joint positions are repetitive when the manipulator execute repetitive trajectories in the operational workspace. Redundant and hyper-redundant planar manipulators reveal that it is possible to choose in a large range of possible values of α in order to get repetitive trajectories in the joint space.

Internal structure of the nanogratings generated inside bulk fused sílica by ultrafast laser direct writing

The aim of the present work was to characterize the internal structure of nanogratings generated inside bulk fused silica by ultrafast laser processing and to study the influence of diluted hydrofluoric acid etching on their structure. The nanogratings were inscribed at a depth of 100 mu m within fused silica wafers by a direct writing method, using 1030 nm radiation wavelength and the following processing parameters: E = 5 mu J, tau = 560 fs, f = 10 kHz, and v = 100 mu m/s. The results achieved show that the laser-affected regions are elongated ellipsoids with a typical major diameter of about 30 mu m and a minor diameter of about 6 mu m. The nanogratings within these regions are composed of alternating nanoplanes of damaged and undamaged material, with an average periodicity of 351 +/- 21 nm. The damaged nanoplanes contain nanopores randomly dispersed in a material containing a large density of defects. These nanopores present a roughly bimodal size distribution with average dimensions for each class of pores 65 +/- 20 x 16 +/- 8 x 69 +/- 16 nm(3) and 367 +/- 239 x 16 +/- 8 x 360 +/- 194 nm(3), respectively. The number and size of the nanopores increases drastically when an hydrofluoric acid treatment is performed, leading to the coalescence of these voids into large planar discontinuities parallel to the nanoplanes. The preferential etching of the damaged material by the hydrofluoric acid solution, which is responsible for the pores growth and coalescence, confirms its high defect density. (C) 2014 AIP Publishing LLC.

Micro – and nanofibers and liquid crystals for ligth-scattering shutters: Simulation of electrp-optical properties

This work demonstrates the feasibility of using polymeric micro- and nanofiber-composed films and liquid crystals as electrically switchable scattering light shutters. We present a concept of electro-optic device based on an innovative combination of two mature technologies: optics of nematic liquid crystals and electrospinning of nanofibers. These devices have electric and optical characteristics far superior to other comparable methods. The simulation presented shows results that are highly consistent with those of experiments and that explain the working mechanism of the devices.

Neural-network approach to modeling liquid crystals in complex confinement

Finding the structure of a confined liquid crystal is a difficult task since both the density and order parameter profiles are nonuniform. Starting from a microscopic model and density-functional theory, one has to either (i) solve a nonlinear, integral Euler-Lagrange equation, or (ii) perform a direct multidimensional free energy minimization. The traditional implementations of both approaches are computationally expensive and plagued with convergence problems. Here, as an alternative, we introduce an unsupervised variant of the multilayer perceptron (MLP) artificial neural network for minimizing the free energy of a fluid of hard nonspherical particles confined between planar substrates of variable penetrability. We then test our algorithm by comparing its results for the structure (density-orientation profiles) and equilibrium free energy with those obtained by standard iterative solution of the Euler-Lagrange equations and with Monte Carlo simulation results. Very good agreement is found and the MLP method proves competitively fast, flexible, and refinable. Furthermore, it can be readily generalized to the richer experimental patterned-substrate geometries that are now experimentally realizable but very problematic to conventional theoretical treatments.

An evolutionary approach for the motion planning of redundant and hyper-redundant manipulators

The trajectory planning of redundant robots is an important area of research and efficient optimization algorithms are needed. The pseudoinverse control is not repeatable, causing drift in joint space which is undesirable for physical control. This paper presents a new technique that combines the closed-loop pseudoinverse method with genetic algorithms, leading to an optimization criterion for repeatable control of redundant manipulators, and avoiding the joint angle drift problem. Computer simulations performed based on redundant and hyper-redundant planar manipulators show that, when the end-effector traces a closed path in the workspace, the robot returns to its initial configuration. The solution is repeatable for a workspace with and without obstacles in the sense that, after executing several cycles, the initial and final states of the manipulator are very close.

Invariant integrals applied to nematic liquid crystals with small Ericksen number and topological defects

Invariant integrals are derived for nematic liquid crystals and applied to materials with small Ericksen number and topological defects. The nematic material is confined between two infinite plates located at y = -h and y = h (h is an element of R+) with a semi-infinite plate at y = 0 and x < 0. Planar and homeotropic strong anchoring boundary conditions to the director field are assumed at these two infinite and semi-infinite plates, respectively. Thus, a line disclination appears in the system which coincides with the z-axis. Analytical solutions to the director field in the neighbourhood of the singularity are obtained. However, these solutions depend on an arbitrary parameter. The nematic elastic force is thus evaluated from an invariant integral of the energy-momentum tensor around a closed surface which does not contain the singularity. This allows one to determine this parameter which is a function of the nematic cell thickness and the strength of the disclination. Analytical solutions are also deduced for the director field in the whole region using the conformal mapping method. (C) 2013 Elsevier Ltd. All rights reserved.

Halting the fuse discharge propagation using optical fiber microwires

We report and analyze the halting of the fuse effect propagation in optical fiber microwires. The increase of the mode field diameter in the tapered region decreases the optical intensity resulting in the extinction of the fuse effect. This fiber element presents a low insertion loss and can be introduced in the optical network in order to protect the active equipment from the damage caused by the fuse effect.