Neoempirismo y dos nuevos dogmas

En el presente trabajo intentaremos ofrecer una evaluación crítica de las dos tesis en el marco de la interpretación de Greenwood esbozando al mismo tiempo nuestras propias conclusiones

Structural characterization of biocompatible reverse micelles using Small-Angle X-ray Scattering, 31P Nuclear Magnetic Resonance, and Fluorescence Spectroscopy

The most critical problem regarding the use of reverse micelles (RMs) in several fields is the toxicity of their partial components. In this sense, many efforts have been made to characterize nontoxic RM formulations on the basis of biological amphiphiles and/or different oils. In this contribution, the microstructure of biocompatible mixed RMs formulated by sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) and tri-n-octylphosphine oxide (TOPO) surfactants dispersed in the friendly solvent methyl laurate was studied by using SAXS and 31P NMR and by following the solvatochromic behavior of the molecular probe 4-aminophthalimide (4-AP). The results indicated the presence of RM aggregates upon TOPO incorporation with a droplet size reduction and an increase in the interfacial fluidity in comparison with pure AOT RMs. When confined inside the mixed systems, 4-AP showed a red-edge excitation shift and confirmed the increment of interfacial fluidity upon TOPO addition. Also, the partition between the external nonpolar solvent and the RM interface and an increase in both the local micropolarity and the capability to form a hydrogen bond interaction between 4-AP and a mixed interface were observed. The findings have been explained in terms of the nonionic surfactant structure and its complexing nature expressed at the interfacial level. Notably, we show how two different approaches, i.e., SAXS and the solvatochromism of the probe 4-AP, can be used in a complementary way to enhance our understanding of the interfacial fluidity of RMs, a parameter that is difficult to measure directly.Fil: Odella, Emmanuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Falcone, Ruben Dario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Ceolín, Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Silber, Juana J.. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Correa, Nestor Mariano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentin

Cretaceous-lower Paleogene ostracods from the Pelotas Basin, Brazil

Cretaceous and Cretaceous/Paleogene marine ostracod assemblages from the Pelotas Basin and their paleoecology are studied. A total of 479 cutting samples from five wells were analized. Ninety-eight specimens belonging to 9 families, 21 genera and 34 species were recovered. The most representative Cretaceous species are: Cytherella cf. C. araucana Bertels, Cytherelloidea spirocostata Bertels, Bairdoppilata triangulata Edwards, Actinocythereis indigena Bertels, Brachycythere gr. sapucariensis Krömmelbein, Wichmannella araucana Bertels and Wichmannella meridionalis Bertels. The Turonian was the most ostracod-rich interval with significant presence of the genera Brachycythere and Cytherella. The Cretaceous-Paleogene boundary is marked by a faunal change with the local disappearance of the genera Cytherelloidea, Argilloecia, Cythereis, Brachycythere, Majungaella, Pondoina and Rostrocytheridea, and the first local occurrence of Neonesidea, Bairdoppilata, Ambocythere, Buntonia, Langiella?, Trachyleberis and Krithe. The Cretaceous ostracod associations in the Pelotas Basin suggest a neritic marine environment with warm water.Simposio VI: Microfósiles del Mesozoico y Cenozoico de América del Sur y Antártida. Nuevas aplicaciones y problemáticas asociadasFacultad de Ciencias Naturales y Muse

Study of the modifications of the electric field gradient in hexafluorohafnates of transition metals above room temperature

The temperature dependence above room temperature of the hyperfine quadrupole interactions measured by the time differential perturbed angular correlations technique at hafnium sites in AHfF6·nH2O, with A=Co and Zn andn=6, 4 and 0, is presented. The different steps of the dehydration process are reflected by modifications on the hyperfine quadrupole parameters at increasing temperature. The changes in the electric field gradient as water molecules are lost are interpreted in terms of distortions induced in the [HfF6]2− octahedrons.Facultad de Ciencias Exacta

Solvent Effects on the Structure−Property Relationship of Redox-Active Self-Assembled Nanoparticle−Polyelectrolyte−Surfactant Composite Thin Films: Implications for the Generation of Bioelectrocatalytic Signals in Enzyme-Containing Assemblies

The search for strategies to improve the performance of bioelectrochemical platforms based on supramolecular materials has received increasing attention within the materials science community, where the main objective is to develop low-cost and flexible routes using self-assembly as a key enabling process. Important contributions to the performance of such bioelectrochemical devices have been made based on the integration and supramolecular organization of redox-active polyelectrolyte−surfactant complexes on electrode supports. Here, we examine the influence of the processing solvent on the interplay between the supramolecular mesoorganization and the bioelectrochemical properties of redox-active self-assembled nanoparticle−polyelectrolyte−surfactant nanocomposite thin films. Our studies reveal that the solvent used in processing the supramolecular films and the presence of metal nanoparticles not only have a substantial influence in determining the mesoscale organization and morphological characteristics of the film but also have a strong influence on the efficiency and performance of the bioelectrochemical system. In particular, a higher bioelectrochemical response is observed when nanocomposite supramolecular films were cast from aqueous solutions. These observations seem to be associated with the fact that the use of aqueous solvents increases the hydrophilicity of the film, thus favoring the access of glucose, particularly at low concentrations. We believe that these results improve our current understanding of supramolecular nanocomposite materials generated via polyelectrolyte−surfactant complexes, in order to use the processing conditions as a variable to improve the performance of bioelectrochemical devices.Facultad de Ciencias ExactasInstituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Fatty acid transfer from Yarrowia lipolytica sterol carrier protein 2 to phospholipid membranes

Sterol carrier protein 2 (SCP2) is an intracellular protein domain found in all forms of life. It was originally identified as a sterol transfer protein, but was recently shown to also bind phospholipids, fatty acids, and fatty-acyl-CoA with high affinity. Based on studies carried out in higher eukaryotes, it is believed that SCP2 targets its ligands to compartmentalized intracellular pools and participates in lipid traffic, signaling, and metabolism. However, the biological functions of SCP2 are incompletely characterized and may be different in microorganisms. Herein, we demonstrate the preferential localization of SCP2 of Yarrowia lipolytica (YLSCP2) in peroxisome-enriched fractions and examine the rate and mechanism of transfer of anthroyloxy fatty acid from YLSCP2 to a variety of phospholipid membranes using a fluorescence resonance energy transfer assay. The results show that fatty acids are transferred by a collision-mediated mechanism, and that negative charges on the membrane surface are important for establishing a "collisional complex". Phospholipids, which are major constituents of peroxisome and mitochondria, induce special effects on the rates of transfer. In conclusion, YLSCP2 may function as a fatty acid transporter with some degree of specificity, and probably diverts fatty acids to the peroxisomal metabolism.Instituto de Investigaciones Bioquímicas de La PlataInstituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Architecture - behaviour - properties relationship in Star-shaped MPA-PMMA and MPA-PS hyper-branched copolymers

The molecular architecture of polymers is a crucial feature in the moment of think the relationship between properties and applications. The same polymer can present important differences according to its architecture and leads to different possible applications. In this paper, we describe the well preparation of hyperbranched copolymers based on bis (HydroxylMethyl) propionic acid polyester (MPA). The co-monomers introduced via atom transfer radical polymerization were methyl methacrylate (MMA) and styrene (St). In order to study the effect of confinement, linear PMMA and PSt have been prepared, and moreover different levels of branching of each polymer were prepared. The synthesised star PMPA-PMMA and PMPA-PSt copolymers have been characterized and identified by infrared spectroscopy and nuclear magnetic resonance spectroscopy. Thermal transitions in solid state were studied using differential scanning calorimetry, and the thermal stability was evaluated by thermogravimetric analysis. Finally, solution properties have been evaluated thought Dynamic Light Scattering. Our results, obtained by a meticulous and systematic comparative study, showed a clear tendency between architectural level and thermal properties. Moreover, properties in solution revealed interesting response due to the modification of solvent nature.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Supramolecular Networks Obtained by Block Copolymer Self-Assembly in a Polymer Matrix: Crystallization Behavior and Its Effect on the Mechanical Response

In recent years, there has been growing interest in the study of supramolecular networks obtained by self-assembly of amphiphilic molecules due to their responsive behavior to different external stimuli. The possibility of embedding supramolecular networks into polymer matrices opens access to a new generation of functional polymers with great potential for various applications. However, very little is known about how the dynamics of the supramolecular network is affected by diffusional and topological limitations imposed by the polymer matrix. In this work, we investigate the behavior of supramolecular networks embedded into a rubbery polymer. Crystallization-driven self-assembly of a poly(ethylene-block-ethylene oxide) (PE-b-PEO) diblock copolymer was used to generate supramolecular networks in dimethacrylate monomers, which were then photopolymerized at room temperature. PE-b-PEO self-assembles into nanoribbons with a semicrystalline PE core bordered by coronal chains of PEO, and the nanoribbons, in turn, bundle into lamellar aggregates with an average stacking period of around 45 nm. The nanoribbons are interconnected through crystalline nodes in a 3D network structure. Small-angle X-ray scattering experiments show that the polymer matrix preserves the structure of the supramolecular network and avoids its disintegration when the material is heated above the melting temperature of PE cores. Successive self-nucleation and annealing studies reveal that the polymer matrix does not influence the crystallization–melting processes of PE, which take place through the interconnected cores of the supramolecular network. In contrast, the matrix imposes strong effects of topological confinement on the crystallization of PEO, limiting the dimensions of the crystalline lamellae that can be formed. Mechanical tests show that the deformation capacity of these materials can be precisely tuned by programming the temperature within the melting range of the supramolecular network. This behavior was also characterized by shape memory cyclic tests.The financial support of the following institutions is gratefully acknowledged: National Research Council (CONICET, Argentina), National Agency for the Promotion of Research, Technological Development and Innovation (AgenciaI + D + i, Argentina), and University of Mar del Plata. This work has received funding from the Basque Government through grant IT1503-22. R.N.S. thanks Iberoamerican Association of Postgraduate Universities (AUIP) for a mobility fellowship

Highly-organized stacked multilayers: Via layer-by-layer assembly of lipid-like surfactants and polyelectrolytes : Stratified supramolecular structures for (bio)electrochemical nanoarchitectonics

Supramolecular self-assembly is of paramount importance for the development of novel functional materials with molecular-level feature control. In particular, the interest in creating well-defined stratified multilayers through simple methods using readily available building blocks is motivated by a multitude of research activities in the field of "nanoarchitectonics" as well as evolving technological applications. Herein, we report on the facile preparation and application of highly organized stacked multilayers via layer-by-layer assembly of lipid-like surfactants and polyelectrolytes. Polyelectrolyte multilayers with high degree of stratification of the internal structure were constructed through consecutive assembly of polyallylamine and dodecyl phosphate, a lipid-like surfactant that act as a structure-directing agent. We show that multilayers form well-defined lamellar hydrophilic/hydrophobic domains oriented parallel to the substrate. More important, X-ray reflectivity characterization conclusively revealed the presence of Bragg peaks up to fourth order, evidencing the highly stratified structure of the multilayer. Additionally, hydrophobic lamellar domains were used as hosts for ferrocene in order to create an electrochemically active film displaying spatially-addressed redox units. Stacked multilayers were then assembled integrating redox-tagged polyallylamine and glucose oxidase into the stratified hydrophilic domains. Bioelectrocatalysis and "redox wiring" in the presence of glucose was demonstrated to occur inside the stratified multilayer.Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasConsejo Nacional de Investigaciones Científicas y Técnica

Novel animal defenses against predation: a snail egg neurotoxin combining lectin and pore-forming chains that resembles plant defense and bacteria attack toxins

Although most eggs are intensely predated, the aerial egg clutches from the aquatic snail Pomacea canaliculata have only one reported predator due to unparalleled biochemical defenses. These include two storage-proteins: ovorubin that provides a conspicuous (presumably warning) coloration and has antinutritive and antidigestive properties, and PcPV2 a neurotoxin with lethal effect on rodents. We sequenced PcPV2 and studied whether it was able to withstand the gastrointestinal environment and reach circulation of a potential predator. Capacity to resist digestion was assayed using small-angle X-ray scattering (SAXS), fluorescence spectroscopy and simulated gastrointestinal proteolysis. PcPV2 oligomer is antinutritive, withstanding proteinase digestion and displaying structural stability between pH 4.0-10.0. cDNA sequencing and protein domain search showed that its two subunits share homology with membrane attack complex/perforin (MACPF)-like toxins and tachylectin-like lectins, a previously unknown structure that resembles plant Type-2 ribosome-inactivating proteins and bacterial botulinum toxins. The protomer has therefore a novel AB toxin combination of a MACPF-like chain linked by disulfide bonds to a lectin-like chain, indicating a delivery system for the former. This was further supported by observing PcPV2 binding to glycocalix of enterocytes in vivo and in culture, and by its hemaggutinating, but not hemolytic activity, which suggested an interaction with surface oligosaccharides. PcPV2 is able to get into predator's body as evidenced in rats and mice by the presence of circulating antibodies in response to sublethal oral doses. To our knowledge, a lectin-pore-forming toxin has not been reported before, providing the first evidence of a neurotoxic lectin in animals, and a novel function for ancient and widely distributed proteins. The acquisition of this unique neurotoxic/antinutritive/storage protein may confer the eggs a survival advantage, opening new perspectives in the study of the evolution of animal defensive strategies.Facultad de Ciencias Veterinaria