R. Martín Negri

Study of atmospheric particulate matter in Buenos Aires city

Abstract The data reported here constitute the results of the first long-term monitoring campaign of daily PM10 and PM2.5 concentration levels in Buenos Aires city. Twenty-four hour averages atmospheric concentrations of PM10 and PM2.5 were measured (not simultaneously) at a site near downtown Buenos Aires, since December 1998–September 1999. The values of PM2.5 concentrations correlate well with the concentrations of carbon monoxide (CO) during the winter period, indicating that direct traffic emissions have an important contribution to PM2.5. The data are less correlated for the case of PM10, indicating that the sources of the coarse fraction are not only traffic emissions, with an important contribution of other sources, for example re-suspended material. Scanning electron microscopy and atomic force microscopy images of atmospheric particles on nucleopore filters are shown. Information about the ion and metal content of these particles is reported.

Electronic nose based discrimination of a perfumery compound in a fragrance

Abstract An electronic nose (e-nose) device developed at the University of Buenos Aires was applied to detect the presence of a given perfumery compound (also so-called the perfumery note, refereed as mangone) in a fragrance, at very low weight percentages. The results were compared with sensorial analysis performed by trained panelists and gas chromatography mass spectroscopy (GCMS) measurements. The triangle test for detection of the perfumery note in the fragrance was performed by a set of 20 trained panelists. Less than 40% of the panelist could identify the presence of the strange note for concentration 10 −2 % (w/w), and similar percentages were obtained for lower concentrations. Detection by CGMS was difficult at those concentrations, because of the low percentages of the perfumery note and the similar retention times obtained for the note and other compounds included in the fragrance. The developed electronic nose provided fingerprints for different odors, associated to different samples that were used to build up an odor database. Then, two different multivariate data analysis were performed, the non-supervised principal component analysis (PCA) and an artificial neural network (ANN), in order to discriminate the samples with or without mangone. Measurements of several dilutions of mangone up to 10 −4 % (w/w) were performed to obtain the database. Both methods, PCA and ANN, were successful in the discrimination process of samples with from those without mangone. In particular a 100% success was obtained by using a radial basis function (RBF) artificial neural network, even when considering the more diluted samples.

Continuous measurement of gaseous pollutants in Buenos Aires city

Abstract Data on CO, NO, NO 2 and O 3 concentrations measured in Buenos Aires city using a continuous monitoring station are reported. This is the first systematic study of this kind carried out in the city, which is, together with its surroundings, the third more populated in Latin America. Measurements were performed during 12 months in one of the principal avenues near downtown. Results indicate that vehicular traffic is the principal source of CO and NO x . The concentration of O 3 is generally quite low and results from the mixing of clean air masses with exhaust gases containing high amounts of NO. The monthly averages of CO and NO decrease from Winter to Summer in correlation with the increase of the mean wind speed and average temperature. These results are compared with previous measurements on the spatial distribution of NO 2 in the whole city using passive diffusion tubes and with the concentration of CO, which is being continuously registered since several years in the downtown area. Measurements performed at a green, windy, low traffic area beneath the La Plata river are also shown.

Anisotropic magnetoresistance and piezoresistivity in structured Fe3O4-silver particles in PDMS elastomers at room temperature.

Magnetorheological elastomers, MREs, based on elastic organic matrices displaying anisotropic magnetoresistance and piezoresistivity at room temperature were prepared and characterized. These materials are dispersions of superparamagnetic magnetite forming cores of aggregated nanoparticles inside silver microparticles that are dispersed in an elastomeric polymer (poly(dimethylsiloxane), PDMS), curing the polymer in the presence of a uniform magnetic field. In this way, the elastic material becomes structured as the application of the field induces the formation of filaments of silver-covered inorganic material agglomerates (needles) aligned in the direction of the field (parallel to the field). Because the magnetic particles are covered with silver, the MREs are not only magnetic but also electrical conductors. The structuration induces elastic, magnetic, and electrical anisotropic properties. For example, with a low concentration of particles in the elastic matrix (5% w/w) it is possible to obtain resistances of a few ohms when measured parallel to the needles or several megaohms in the perpendicular direction. Magnetite nanoparticles (Fe(3)O(4) NP) were synthesized by the coprecipitation method, and then agglomerations of these NPs were covered with Ag. The average size of the obtained magnetite NPs was about 13 nm, and the magnetite-silver particles, referred to as Fe(3)O(4)@Ag, form micrometric aggregates (1.3 μm). Nanoparticles, microparticles, and the MREs were characterized by XRD, TEM, SEM, EDS, diffuse reflectance, voltammetry, VSM, and SQUID. At room temperature, the synthesized magnetite and Fe(3)O(4)@Ag particles are in a superparamagnetic state (T(B) = 205 and 179 K at 0.01 T as determined by SQUID). The elastic properties and Youngs modulus of the MREs were measured as a function of the orientation using a texture analysis device. The magnetic anisotropy in the MRE composite was investigated by FMR. The electrical conductivity of the MRE (σ) increases exponentially when a pressure, P, is applied, and the magnitude of the change strongly depends on what direction P is exerted (anisotropic piezoresistivity). In addition, at a fixed pressure, σ increases exponentially in the presence of an external magnetic field (H) only when the field H is applied in the collinear direction with respect to the electrical flux, J. Excellent fits of the experimental data σ versus H and P were achieved using a model that considers the intergrain electron transport where an H-dependent barrier was considered in addition to the intrinsic intergrain resistance in a percolation process. The H-dependent barrier decreases with the applied field, which is attributed to the increasing match of spin-polarization in the silver covers between grains. The effect is anisotropic (i.e., the sensitivity of the magnetoresistive effect is dependent on the relative orientation between H and the current flow J). In the case of Fe(3)O(4)@ Ag, when H and J are parallel to the needles in the PDMS matrix, we obtain changes in σ up to 50% for fields of 400 mT and with resistances on the order of 1-10 Ω. Magnetoresistive and magnetoelastic properties make these materials very interesting for applications in flexible electronics, electronic skins, anisotropic pressure, and magnetic field sensors.

CARBOXYLATED ZINC-PHTHALOCYANINE, INFLUENCE OF DIMERIZATION ON THE SPECTROSCOPIC PROPERTIES. AN ABSORPTION, EMISSION, AND THERMAL LENSING STUDY

Monomer and dimer absorption and emission spectra, and dimerization constants are reported for the diamide of the zinc‐tetracarboxyphthalocyanine in pure dimethylformamide (DMF) and in H2O/DMF mixtures at room temperature. The dimerization constant increases steadily with the water content. The monomer absorption Q‐band is insensitive to the solvent composition, whereas dimer spectra show great variations with the water content. Stationary emission measurements show that fluorescence originates exclusively from the monomers. The fluorescence spectrum as well as its absolute fluorescence quantum yield, measured by steady‐state thermal lensing, are also insensitive to the solvent composition. The thermal lensing method is discussed for the case of two absorbing species in equilibrium.

Identification of pollutant gases and its concentrations with a multisensor array

Abstract We have modeled the performance of an electronic nose, composed by tin dioxide commercial sensors, addressed to identify gases of relevance in polluted atmospheres. We analyze the possibilities of determining both the concentration and composition of a mixture of gases containing carbon monoxide, ethanol, methane or isobutane. We have modeled the theoretical response function of the array when sensing a mixture of gases, based on data from these commercial sensors, and designed an appropriate pattern recognition scheme for the simultaneous identification of a given gas and its concentration in the mixture.

Magnetic and elastic properties of CoFe2O4- polydimethylsiloxane magnetically oriented elastomer nanocomposites

Magnetic elastic structured composites were prepared by using CoFe2O4 ferromagnetic and superparamagnetic nanoparticles as fillers in polydimethylsiloxane (PDMS) matrixes, which were cured in the presence of a uniform magnetic field. Cobalt-iron oxide nanoparticles of three different average sizes (between 2 and 12 nm) were synthesized and characterized. The smallest nanoparticles presented superparamagnetic behavior, with a blocking temperature of approximately 75 K, while larger particles are already blocked at room temperature. Macroscopically structured-anisotropic PDMS-CoFe2O4 composites were obtained when curing the dispersion of the nanoparticles in the presence of a uniform magnetic field (0.3 T). The formation of the particle’s chains (needles) orientated in the direction of the magnetic field was observed only when loading with the larger magnetically blocked nanoparticles. The SEM images show that the needles are formed by groups of nanoparticles which retain their original average size. The Yo...

A model for the dependence of the electrical conductance with the applied stress in insulating-conducting composites

A model for the dependence of the electrical conductance, G, with the strain induced by external mechanical stress in conducting particles-polymer composites is presented. The model assumes that the percolation probability between neighboring particles must depart from a scale-invariant behavior but saturate at moderated-high strains, reaching percolation path’s saturation, with sigmoid dependence. This dependence is obtained by proposing a dynamic picture where contacts or bonds between neighboring particles are created but also destructed when a stress is applied and relatively moderated or high strains, e, are produced in the composite. The electrical conductance of prepared graphite-polydimethylsiloxane composites were measured as function of the applied pressure and fitted by the presented model. The elastic response to the uniaxial compression was studied using a texture analyzer. The possibility of nonuniversal effects in the conduction critical exponent, t, was taken into account. It is concluded ...

A flexible strain gauge exhibiting reversible piezoresistivity based on an anisotropic magnetorheological polymer

A flexible, anisotropic and portable stress sensor (logarithmic reversible response between 40–350 kPa) was fabricated, in which i) the sensing material, ii) the electrical contacts and iii) the encapsulating material, were based on polydimethylsiloxane (PDMS) composites. The sensing material is a slide of an anisotropic magnetorheological elastomer (MRE), formed by dispersing silver-covered magnetite particles (Fe3O4@Ag) in PDMS and by curing in the presence of a uniform magnetic field. Thus, the MRE is a structure of electrically conducting pseudo-chains (needles) aligned in a specific direction, in which electrical conductivity increases when stress is exclusively applied in the direction of the needles. Electrical conductivity appears only between contact points that face each other at both sides of the MRE slide. An array of electrical contacts was implemented based on PDMS-silver paint metallic composites. The array was encapsulated with PDMS. Using Fe3O4 superparamagnetic nanoparticles also opens up possibilities for a magnetic field sensor, due to the magnetoresistance effects.

Fluorescent Dimers of Merocyanine 540 (MC540) in the Gel Phase of Phosphatidylcholine Liposomes

Abstract— Fluorescence emission from merocyanine 540 (MC540) dimers was observed in dipalmitoylphosphatidylcholine (DPPC) vesicles. This unusual behavior was observed only for vesicles in the gel‐phase state. No dimer fluorescence was observed either in monopalmitoylphosphati‐dylcholine (C16PC) micelles or in liquid‐crystalline DPPC vesicles, indicating that dimer fluorescence efficiency increases in highly packed interfaces. The excitonic theory of Kasha was used to interpret the spectral features. The overall fluorescence quantum yield (φr) decreases with decreasing lipid: probe ratio, not only because of the presence of a weakly fluorescent dimer that absorbs a high fraction of the total absorbed light but also due to quenching of monomer emission. This suggests the existence of probe domains. The dimer fluorescence quantum yields (φm) were estimated in DPPC large unilamellar vesicles (LUV) and DPPC multilamellar vesicles. The dependence of φr with probe concentration is compatible with values of φm lower than 0.05. The dimerization equilibrium of MC540 in C16PC micelles and DPPC‐LUV was also studied. Apparent dimerization equilibrium constants, Kdapp and dimer absorption spectrum were calculated in C16PC micelles for the first time. The dimerization equilibrium constant in DPPC‐LUV was calculated and discussed in terms of the fraction of volume occupied by the lipid phase.