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Biomedical subjects

Fernando Galembeck

Publications and source records attributed to Fernando Galembeck.

13 recordsLinked to original sources

Cationic latex formation by ionic modification.

Stable cationic latices were prepared by charge inversion of anionic styrene-acrylic copolymer latices upon binding Al3+ and Fe3+ ions. This is achieved by stabilizing the latices with a high-HLB (hydrophile-lypophile balance) nonionic surfactant that imparts strong steric stability to the latex, even in the presence of high concentrations of multivalent counterions while these are bound to the latex anionic sites. The cationic latices thus prepared have good stability properties, and the same procedure should be applicable to essentially any latex-carrying anionic sites. Analytical ESI-TEM images show that particle-bound iron is concentrated at the particle borders, but it is also found in the particle bulk.

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ESI-TEM imaging of surfactants and ions sorbed in Stöber silica nanoparticles.

The sorption of surfactants and NaCl in silica nanosized particles creates unexpected spatial distributions of solutes that were evidenced by electron spectroscopy imaging in the transmission electron microscope (ESI/TEM). The spectral images show that simple ions (Na(+), Cl(-), Br(-)) are actually absorbed within the particles irrespective of their charges, while surfactant chains are adsorbed at the particle surfaces. The expected effect of the surfactants on particle aggregation is also observed in the micrographs. In the case of salt, close-packed silica particle arrays are formed at low ionic strength, but only coarse aggregates form at higher salt concentrations. The particles absorb both Na(+) and Cl(-) ions in similar amounts, from 0.5 mol L(-)(1) NaCl, but Na(+) ions are depleted from the particles' immediate outer vicinity, where Cl(-) ions are in turn accumulated. These results confirm that Stöber silica nanoparticles are highly porous and reveal their potential usefulness as carriers of small molecules and ions, due to the small particle size, exceptional colloidal stability, and this newly found sorption behavior.

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Formation of calcium crystallites in dry natural rubber particles.

In this paper, the effects of drying and aging of natural rubber particles of Hevea brasiliensis are studied. The evolutions of the particle morphology and of the elemental distribution are investigated using electron-energy-loss spectroscopy imaging in a low-energy transmission electron microscope (ESI-TEM). It is found that when the sample is aged, calcium salt crystallites are formed around the particles. Fusion of these crystallites with time to form larger crystals shows evidence of ion mobility in the dry rubber matrix. Electron diffraction patterns and elemental mapping analysis indicate the crystals to be calcium sulfate. These crystallites are closely associated with membrane materials of the rubber particle and are surprisingly compatible with the hydrocarbon matrix of the rubber particle. It is proposed that polar sites on the membrane materials provide nucleation sites for the crystallization of calcium and sulfate ions from the latex serum.

Ammonia↗

Electrostatic patterning of a silica surface: a new model for charge build-up on a dielectric solid.

The polarization of interdigitated gold electrodes mounted over a silica thin film formed by oxidation of a Si wafer produces reproducible electrostatic patterns with overall excess negative charge, as observed by scanning electric potential microscopy. Domain charge concentrations as high as 76 charge units per square micrometer are obtained when a 5 V difference is applied to the electrodes thus producing fields in the 10(6) V m(-1) range. These patterns vanish when the electrodes are short-circuited and grounded. Characteristic times for pattern formation and relaxation are in the order of 10 min. The results are consistent with a model based on the discharge of H(+) ions at the negative electrodes, leaving behind immobile surface-bound SiO(-) groups and thus showing that chemisorption phenomena are decisive for electrostatic charging of insulators.

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Heterogeneity in styrene-butadiene latex films.

Low-Tg styrene-butadiene (SB) latex films were investigated by noncontact atomic force microscopy and scanning electric potential microscopy, revealing a number of different morphologies and electric potential patterns across films cast from the same SB latex dispersions under the same conditions. Surface leveling and charge dispersion throughout the films are, thus, restrained even at temperatures above Tg and the minimum film-formation temperature. An unprecedented electric pattern is observed, in which the particle cores are more positive than the contacting particle outer layers. Different packing patterns, including cubic and hexagonal arrays, coexist in neighboring areas. Zonal centrifugation of the SB latex in sucrose density gradient shows that particles cover a broad range of densities. Thus, film surface heterogeneity is at least partly due to particle heterogeneity. Fractal dimensions of topographic profiles are lower than those of the electric potential profiles, showing that charge mobility is much more restrained than polymer chain motion at the film surface and that it imposes a limit to the charged chain-ends motion.

Butadienes↗

Controlled nanoparticle assembly by dewetting of charged polymer solutions.

In this paper, we present an alternative approach for controlled nanoparticle organization on a solid substrate by applying dewetting patterns of charged polymer solutions as a templating system. Thin films of charged polymer solutions dewet a solid substrate to form complex dewetting patterns that depend on the polymer charge density. These patterns, ranging from polygonal networks to elongated structures that are stabilized by viscous forces during dewetting, serve as potential templates for two-dimensional nanoparticle organization on a solid substrate. Thus, while nanoparticles dried in pure water undergo self-assembly to form close-packed arrays, addition of charged polymer in the dispersion leads to the formation of open structures that are directed by the dewetting patterns of the polymer solution. In this study, we focus on the application of elongated structures resulting from dewetting of high-charge-density polymer solutions to align nanoparticles of silica and gold into long chains that are several micrometers in length. The particle ordering process is a two-step mechanism: an initial confinement of the nanoparticles in the dewetting structures and self-assembly of the particles within these structures upon further drying by lateral capillary attractions.

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Characterization of surface NH3+Cl- groups on poly(styrene-co-Boc-aminostyrene) microspheres obtained by controlled acidic treatment.

Different samples of aminated latex of poly(styrene-co-Boc-aminostyrene) microspheres with mean diameters varying from 0.7 to 1.0 microm were prepared by dispersion copolymerization of styrene (ST) and Boc-aminostyrene (Boc-AMST). The copolymer compositions determined by nuclear magnetic resonance (1H NMR) were Boc-AMST/ST 6.9/93.1 mol/mol % (BOC7 sample) and Boc-AMST/ST 31.3/68.7 mol/mol % (BOC30 sample). The average molecular weights determined by gel permeation chromatography were 126 kDa (BOC7 sample) and 51 kDa (BOC30 sample). The latex containing NH-carbo-tert-butoxy groups (NH-Boc) were treated with 2 M HCl in isopropyl alcohol/water (1:1 vol/vol), at 50 degrees C for 3, 6, 9, 24, and 30 h, in order to control the extent of deprotection reaction of the NH-Boc. The deprotection reaction resulted in the formation of NH3+Cl- groups on the particle surfaces. The kinetic of the deprotection reaction was investigated by 1H NMR analyses and the yield varied from 20 to 40%. The resulting -NH3+Cl- groups on the microsphere surfaces were examined, in particular, by electron spectroscopy imaging (ESI) using an energy-filtered transmission electron microscope (EFTEM) that clearly demonstrated the presence of Cl on the particle surfaces. Scanning electron photomicrographs recorded for the above samples showed that the particle morphology was maintained after the acidic treatment.

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Skim and cream natural rubber particles: colloidal properties, coalescence and film formation.

Cream and skim fractions of freshly tapped natural rubber latex have been studied using atomic force microscopy and scanning electric potential microscopy to elucidate the topology and charge properties in film formation. Elemental distribution maps of the particles have also been obtained using electron energy-loss imaging in a low-energy transmission electron microscope. The two rubber fractions are obtained by centrifugation. The cream fraction is stable while rapid coagulation occurs in the skim fraction. After removal of the coagulum, no further coagulation occurs and the remaining skim rubber particles are stable. The rubber particles from the cream rubber particles contain higher amount of adsorbed protein-phospholipid materials compared to those in the "self-cleaned" skim fraction. This difference in membrane property has a significant impact on the spreading of the cis-1,4-polyisoprene cores, their coalescence and film formation behavior. Coalescence of cream particles appears to be hindered by the membrane materials, forming a rough film that retains the topology of individual particles. Skim particles coalesce more readily, forming relatively smooth films.

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Latex film morphology and electrical potential pattern dependence on serum components: a scanning probe microscopy study.

Dry films formed by surfactant-stabilized, peroxide-initiated styrene-butyl acrylate latex were examined by atomic and electric force microscopy (AFM and EFM). The effects of latex serum components on the films were observed by subjecting the latex to extensive dialysis prior to film formation, and comparing the results to as-prepared latex. The films formed with the dialyzed latex are smoother (as evidenced by roughness and fractal dimension measurements) than the films from the as-prepared latex, but they display large electric force gradients between neighboring domains. The films made with the as-prepared latex have the highest electric uniformity, with a maximum potential variation lower than 80 mV, while this reaches 200 mV in the dialyzed latex film.

Dialysis↗

Elemental mapping in natural rubber latex films by electron energy loss spectroscopy associated with transmission electron microscopy.

Element distribution maps from Hevea brasiliensis natural rubber latex thin films were obtained, by electron energy-loss spectroscopic imaging in a low-energy (80 kV) transmission electron microscope. C, N, O, P, Na, Ca, Mg, Al, Si, and S maps are presented for latex fractionated by centrifugation, either followed by dialysis or not. Most elements forming non-carbon compounds are concentrated in small, electron-dense spots surrounded by a carbon-rich matrix of polymer, thus showing that the rubber is filled with small particles compatible with the polyisoprene matrix. Ca distribution is unique, since it closely parallels the C distribution, evidencing an important role for -COO(-)-Ca2+-COO- ionic bridges in the structure of natural rubber.

Dialysis↗

Coexistence of liquid phases in the sodium polyphosphate-chromium nitrate-water system.

The formation of coexisting liquid phases out of aqueous aluminum polyphosphate solutions was previously suggested as an essential step in aluminum polyphosphate nanoparticle formation. This hypothesis could not be directly verified because the separation of the two phases is very difficult, but a different situation was found in the case of chromium (III) polyphosphate. The phase diagram of the sodium polyphosphate-chromium nitrate-water system at 25 degrees C presents an extensive region with two coexisting liquid phases (L-L), together with a single liquid phase (L) and a solid-liquid (S-L) domain. Within the L-L region, admixture of the reagents produces initially a turbid liquid, out of which two transparent liquid phases separate in a short time, under gravity: one is dense, dark, and viscous while the other has a light color and a lower density. The amounts of the separated phases were determined, as well as their viscosities, densities, pH, UV-vis spectra, and relevant molalities: P (from polyphosphate), Cr(3+), NO(-)(3+), and Na(+). The two liquid phases undergo significant color, pH, and viscosity changes with time. The calculated phase diagrams display the major features of the experimental phase diagram.

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Nanocrystalline Domain Identification in Gold Films, by Backscattered Electron Imaging and Energy-Filtered Transmission Electron Microscopy.

Gold nanocrystallites dispersed in an inhomogeneous gold matrix are detected by high-resolution scanning electron microscopy using a field emission source and backscattered electron detection in the composition mode, as well as by energy-filtered transmission electron microscopy in the plasmon energy region. The identity of the nanocrystalline domains was established by observing the same evaporated gold film samples but using bright-field, dark-field, electron diffractogram, and electron energy loss spectroscopy images in the transmission electron microscope. Comparison of these images shows that backscattered electron and plasmon energy detection can be used to identify crystalline domains in an otherwise chemically uniform sample. Copyright 2001 Academic Press.

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Macrocrystal Swelling: AFM in Situ Observation of Particle and Film Deformation and Motion.

The surface of a poly(styrene-hydroxyethylmethacrylate), macrocrystalline film was observed by atomic force microscopy in the contact mode, before and during film immersion in water. The swelling effect on film morphology is strongly dependent on the quality of the macrocrystalline surface: film integrity is preserved or concerted many-particle displacement is observed in well-organized areas with few defects, but extensive particle displacement is observed in highly defective areas. The lateral particle dimensions increase by ca. 10-15% only and particle aspect ratio is unaltered in the highly crystalline areas. However, film roughness is greatly decreased, and flat mirror-like surface domains are obtained due to the concerted effects of particle swelling and latex-water interfacial tension. Copyright 2001 Academic Press.

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