Site specific growth of metal catalyzed silica nanowires for biological and chemical sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050°C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1μg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.

Fiber-optic vibration sensing of cantilevers immersed in fluids

An all fiber-optical method to monitor densities and viscosities of liquids utilizing a steel cantilever (4 x 0.3 x 0.08 cm3) is presented. The actuation is performed by photothermally heating the cantilever at its base with an intensity-modulated 808 nm diode laser. The cantilever vibrations are picked up by an in-fiber Fabry Perot cavity sensor attached along the length of the cantilever. The fluid properties can be related to the resonance characteristics of the cantilever, e.g. a shift in the resonance frequency corresponds to a change in fluid density, and the width of the resonance peak gives information on the dynamic viscosity after calibration of the system. Aqueous glycerol, sucrose and ethanol samples in the range of 0.79–1.32 gcm−3 (density) and 0.89–702 mPas (viscosity) were used to investigate the limits of the sensor. A good agreement with literature values could be found with an average deviation of around 10 % for the dynamic viscosities, and 5–16 % for the mass densities. A variety of clear and opaque commercial spirits and an unknown viscous sample, e.g. home-made maple syrup, were analyzed and compared to literature values. The unique detection mechanism allows for the characterization of opaque samples and is superior to conventional microcantilever sensors. The method is expected to be beneficial in various industrial sectors such as quality control of food samples.

The crowded magnetosphere of the post-common-envelope binary QS Virginis

We present high-speed photometry and high-resolution spectroscopy of the eclipsing post-common-envelope binary QS Virginis (QS Vir). Our Ultraviolet and Visual Echelle Spectrograph (UVES) spectra span multiple orbits over more than a year and reveal the presence of several large prominences passing in front of both the M star and its white dwarf companion, allowing us to triangulate their positions. Despite showing small variations on a time-scale of days, they persist for more than a year and may last decades. One large prominence extends almost three stellar radii from the M star. Roche tomography reveals that the M star is heavily spotted and that these spots are long-lived and in relatively fixed locations, preferentially found on the hemisphere facing the white dwarf. We also determine precise binary and physical parameters for the system. We find that the 14 220 ± 350 K white dwarf is relatively massive, 0.782 ± 0.013 M⊙, and has a radius of 0.010 68 ± 0.000 07 R⊙, consistent with evolutionary models. The tidally distorted M star has a mass of 0.382 ± 0.006 M⊙ and a radius of 0.381 ± 0.003 R⊙, also consistent with evolutionary models. We find that the magnesium absorption line from the white dwarf is broader than expected. This could be due to rotation (implying a spin period of only ˜700 s), or due to a weak (˜100 kG) magnetic field, we favour the latter interpretation. Since the M star's radius is still within its Roche lobe and there is no evidence that it is overinflated, we conclude that QS Vir is most likely a pre-cataclysmic binary just about to become semidetached.

Rotational velocities of single and binary O-type stars in the Tarantula Nebula

Rotation is a key parameter in the evolution of massive stars, affecting their evolution, chemical yields, ionizing photon budget, and final fate. We determined the projected rotational velocity, υ e sin i, of ~330 O-type objects, i.e. ~210 spectroscopic single stars and ~110 primaries in binary systems, in the Tarantula nebula or 30 Doradus (30 Dor) region. The observations were taken using VLT/FLAMES and constitute the largest homogeneous dataset of multi-epoch spectroscopy of O-type stars currently available. The most distinctive feature of the υ e sin i distributions of the presumed-single stars and primaries in 30 Dor is a low-velocity peak at around 100 km s^-1. Stellar winds are not expected to have spun-down the bulk of the stars significantly since their arrival on the main sequence and therefore the peak in the single star sample is likely to represent the outcome of the formation process. Whereas the spin distribution of presumed-single stars shows a well developed tail of stars rotating more rapidly than 300 km s^-1, the sample of primaries does not feature such a high-velocity tail. The tail of the presumed-single star distribution is attributed for the most part - and could potentially be completely due - to spun-up binary products that appear as single stars or that have merged. This would be consistent with the lack of such post-interaction products in the binary sample, that is expected to be dominated by pre-interaction systems. The peak in this distribution is broader and is shifted toward somewhat higher spin rates compared to the distribution of presumed-single stars. Systems displaying large radial velocity variations, typical for short period systems, appear mostly responsible for these differences.

Redox-dependent conformational switching of diphenylacetylenes

Herein we describe the design and synthesis of a redox-dependent single-molecule switch. Appending a ferrocene unit to a diphenylacetylene scaffold gives a redox-sensitive handle, which undergoes reversible one-electron oxidation, as demonstrated by cyclic voltammetry analysis. ¹H-NMR spectroscopy of the partially oxidized switch and control compounds suggests that oxidation to the ferrocenium cation induces a change in hydrogen bonding interactions that results in a conformational switch. 

Universality of weakly bound dimers and Efimov trimers close to Li-Cs Feshbach resonances

We study the interspecies scattering properties of ultracold Li-Cs mixtures in their two energetically lowest spin channels in the magnetic field range between 800 and 1000 G. Close to two broad Feshbach resonances (FR) we create weakly bound LiCs dimers by radio-frequency association and measure the dependence of their binding energy on the external magnetic field strength. Based on the binding energies and complementary atom loss spectroscopy of three other Li-Cs s-wave FRs we construct precise molecular singlet and triplet electronic ground state potentials using a coupled-channels calculation. We extract the Li-Cs interspecies scattering length as a function of the external field and obtain almost a ten-fold improvement in the precision of the values for the pole positions and widths of the s-wave FRs as compared to our previous work (Pires et al 2014 Phys. Rev. Lett. 112 250404). We discuss implications on the Efimov scenario and the universal geometric scaling for LiCsCs trimers.

Ultra high pressure homogenization (UHPH) inactivation of Bacillus amyloliquefaciens spores in phosphate buffered saline (PBS) and milk

Ultra high pressure homogenization (UHPH) opens up new areas for dynamic high pressure assisted thermal sterilization of liquids. Bacillus amyloliquefaciens spores are resistant to high isostatic pressure and temperature and were suggested as potential surrogate for high pressure thermal sterilization validation. B. amyloliquefaciens spores suspended in PBS buffer (0.01 M, pH 7.0), low fat milk (1.5%, pH 6.7), and whole milk (3.5%, pH 6.7) at initial concentration of similar to 10(6) CFU/mL were subjected to UHPH treatments at 200, 300, and 350 MPa with an inlet temperature at similar to 80 degrees C. Thermal inactivation kinetics of B. amyloliquefaciens spores in PBS and milk were assessed with thin wall glass capillaries and modeled using first-order and Weibull models. The residence time during UHPH treatments was estimated to determine the contribution of temperature to spore inactivation by UHPH. No sublethal injury was detected after UHPH treatments using sodium chloride as selective component in the nutrient agar medium. The inactivation profiles of spores in PBS buffer and milk were compared and fat provided no clear protective effect for spores against treatments. Treatment at 200 MPa with valve temperatures lower than 125 degrees C caused no reduction of spores. A reduction of 3.5 log(10)CFU/mL of B. amyloliquefaciens spores was achieved by treatment at 350 MPa with a valve temperature higher than 150 degrees C. The modeled thermal inactivation and observed inactivation during UHPH treatments suggest that temperature could be the main lethal effect driving inactivation.

On the interaction of bovine serum albumin with ionic surfactants: Temperature induced EPR changes of a maleimide nitroxide reflect local protein dynamics and probe solvent accessibility

The interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. EPR spectra simulation allows to monitor the protein dynamics at the labeling site and to estimate the changes in standard Gibbs free energy, enthalpy and entropy for transferring the nitroxide side chain from the more motionally restricted to the less restricted component. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all measured concentrations. HPS presented a smaller effect at concentrations above 1.5 mM. At 10 mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent as compared to the native protein, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the paramagnetic probe induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS data suggests that the temperature induced changes monitored by the nitroxide probe reflects local changes in the vicinity of the single thiol group of Cys-34 BSA residue. (C) 2011 Elsevier B.V. All rights reserved.

Síntese e caracterização do líquido iônico tetrafluoroborato de 1-metil-3-(2,6-(S)-dimetiloct-2-eno)-imidazol como eletrólito para produção de hidrogênio via eletrólise da água

Ionic liquids (ILs) are organic compounds liquid at room temperature, good electrical conductors, with the potential to form as a means for electrolyte on electrolysis of water, in which the electrodes would not be subjected to such extreme conditions demanding chemistry [1]. This paper describes the synthesis, characterization and study of the feasibility of ionic liquid ionic liquid 1-methyl-3(2,6-(S)-dimethyloct-2-ene)-imidazole tetrafluoroborate (MDI-BF4) as electrolyte to produce hydrogen through electrolysis of water. The MDI-BF4 synthesized was characterized by thermal methods of analysis (Thermogravimetric Analysis - TG and Differential Scanning Calorimetry - DSC), mid-infrared spectroscopy with Fourier transform by method of attenuated total reflectance (FTIR-ATR), nuclear magnetic resonance spectroscopy of hydrogen (NMR 1H) and cyclic voltammetry (CV). Where thermal methods were used to calculate the yield of the synthesis of MDI-BF4 which was 88.84%, characterized infrared spectroscopy functional groups of the compound and the binding B-F 1053 cm-1; the NMR 1H analyzed and compared with literature data defines the structure of MDI-BF4 and the current density achieved by MDI-BF4 in the voltammogram shows that the LI can conduct electrical current indicating that the MDI-BF4 is a good electrolyte, and that their behavior does not change with the increasing concentration of water

Site Specifc Growth of Metal Catalyzed Silica Nanowires for Biological and Chemical Sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050 ˚C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1µg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.

Development and optimization of techniques and design parameters for the engineering of atmospheric pressure plasma devices for biomedical applications and plasma medicine

In the last decades, the possibility to generate plasma at atmospheric pressure gave rise to a new emerging field called plasma medicine; it deals with the application of cold atmospheric pressure plasmas (CAPs) or plasma-activated solutions on or in the human body for therapeutic effects. Thanks to a blend of synergic biologically active agents and biocompatible temperatures, different CAP sources were successfully employed in many different biomedical applications such as dentistry, dermatology, wound healing, cancer treatment, blood coagulation, etc.… Despite their effectiveness has been verified in the above-mentioned biomedical applications, over the years, researchers throughout the world described numerous CAP sources which are still laboratory devices not optimized for the specific application. In this perspective, the aim of this dissertation was the development and the optimization of techniques and design parameters for the engineering of CAP sources for different biomedical applications and plasma medicine among which cancer treatment, dentistry and bioaerosol decontamination. In the first section, the discharge electrical parameters, the behavior of the plasma streamers and the liquid and the gas phase chemistry of a multiwire device for the treatment of liquids were performed. Moreover, two different plasma-activated liquids were used for the treatment of Epithelial Ovarian Cancer cells and fibroblasts to assess their selectivity. In the second section, in accordance with the most important standard regulations for medical devices, were reported the realization steps of a Plasma Gun device easy to handle and expected to be mounted on a tabletop device that could be used for dental clinical applications. In the third section, in relation to the current COVID-19 pandemic, were reported the first steps for the design, realization, and optimization of a dielectric barrier discharge source suitable for the treatment of different types of bioaerosol.

Construção de um calorímetro isotérmico diferencial de alta sensibilidade e baixo custo

The high cost of sensitivity commercial calorimeters may represent an obstacle for many calorimetric research groups. This work describes the construction and calibration of a batch differential heat conduction calorimeter with sample cells volumes of about 400 μL. The calorimeter was built using two small high sensibility square Peltier thermoelectric sensors and the total cost was estimated to be about US$ 500. The calorimeter was used to study the excess enthalpy of solution of binary mixtures of liquids, as a function of composition, for the following binary systems of solvents: water + 1,4-dioxane or + dimethylsulfoxide at 298,2 ± 0,5 K.

Estudo comparativo de algumas propriedades dinâmicas de líquidos e grãos na sala de aula

Visando entender as diferenças entre as propriedades dinâmicas dos materiais granulares e as propriedades dinâmicas dos líquidos, foram realizados experimentos usando água e grãos de arroz e açúcar. Os experimentos requerem poucos recursos e foram pensados para que possam ser desenvolvidos com facilidade na sala de aula ou num laboratório de ensino. Os resultados mostraram que o fluxo de grãos difere significativamente do fluxo de líquidos.

Abundances in the Galactic bulge: results from planetary nebulae and giant stars

Context. Our understanding of the chemical evolution (CE) of the Galactic bulge requires the determination of abundances in large samples of giant stars and planetary nebulae (PNe). Studies based on high resolution spectroscopy of giant stars in several fields of the Galactic bulge obtained with very large telescopes have allowed important progress. Aims. We discuss PNe abundances in the Galactic bulge and compare these results with those presented in the literature for giant stars. Methods. We present the largest, high-quality data-set available for PNe in the direction of the Galactic bulge (inner-disk/bulge). For comparison purposes, we also consider a sample of PNe in the Large Magellanic Cloud (LMC). We derive the element abundances in a consistent way for all the PNe studied. By comparing the abundances for the bulge, inner-disk, and LMC, we identify elements that have not been modified during the evolution of the PN progenitor and can be used to trace the bulge chemical enrichment history. We then compare the PN abundances with abundances of bulge field giant. Results. At the metallicity of the bulge, we find that the abundances of O and Ne are close to the values for the interstellar medium at the time of the PN progenitor formation, and hence these elements can be used as tracers of the bulge CE, in the same way as S and Ar, which are not expected to be affected by nucleosynthetic processes during the evolution of the PN progenitors. The PN oxygen abundance distribution is shifted to lower values by 0.3 dex with respect to the distribution given by giants. A similar shift appears to occur for Ne and S. We discuss possible reasons for this PNe-giant discrepancy and conclude that this is probably due to systematic errors in the abundance derivations in either giants or PNe (or both). We issue an important warning concerning the use of absolute abundances in CE studies.

Optical second harmonic generation in the centrosymmetric magnetic semiconductors EuTe and EuSe

The magnetic europium chalcogenide semiconductors EuTe and EuSe are investigated by the spectroscopy of second harmonic generation (SHG) in the vicinity of the optical band gap formed by transitions involving the 4f and 5d electronic orbitals of the magnetic Eu(2+) ions. In these materials with centrosymmetric crystal lattice the electric-dipole SHG process is symmetry forbidden so that no signal is observed in zero magnetic field. Signal appears, however, in applied magnetic field with the SHG intensity being proportional to the square of magnetization. The magnetic field and temperature dependencies of the induced SHG allow us to introduce a type of nonlinear optical susceptibility determined by the magnetic-dipole contribution in combination with a spontaneous or induced magnetization. The experimental results can be described qualitatively by a phenomenological model based on a symmetry analysis and are in good quantitative agreement with microscopic model calculations accounting for details of the electronic energy and spin structure.