Effect of humidity and solvent vapor phase on cellulose esters films

In the present study the effect of relative humidity (RH) during spin-coating process on the structural characteristics of cellulose acetate (CA), cellulose acetate phthalate (C-A-P), cellulose acetate butyrate (CAB) and carboxymethyl cellulose acetate butyrate (CMCAB) films was investigated by means of atomic force microscopy (AFM), ellipsometry and contact angle measurements. All polymer solutions were prepared in tetrahydrofuran (THF), which is a good solvent for all cellulose esters, and used for spin-coating at RH of (35 +/- A 5)%, (55 +/- A 5)% or (75 +/- A 5)%. The structural features were correlated with the molecular characteristics of each cellulose ester and with the balance between surface energies of water and THF and interface energy between water and THF. CA, CAB, CMCAB and C-A-P films spin-coated at RH of (55 +/- A 5)% were exposed to THF vapor during 3, 6, 9, 60 and 720 min. The structural changes on the cellulose esters films due to THF vapor exposition were monitored by means of AFM and ellipsometry. THF vapor enabled the mobility of cellulose esters chains, causing considerable changes in the film morphology. In the case of CA films, which are thermodynamically unstable, dewetting was observed after 6 min exposure to THF vapor. On the other hand, porous structures observed for C-A-P, CAB and CMCAB turned smooth and homogeneous after only 3 min exposure to THF vapor.

Robust tori-like Lagrangian coherent structures

In general the term "Lagrangian coherent structure" (LCS) is used to make reference about structures whose properties are similar to a time-dependent analog of stable and unstable manifolds from a hyperbolic fixed point in Hamiltonian systems. Recently, the term LCS was used to describe a different type of structure, whose properties are similar to those of invariant tori in certain classes of two-dimensional incompressible flows. A new kind of LCS was obtained. It consists of barriers, called robust tori that block the trajectories in certain regions of the phase space. We used the Double-Gyre Flow system as the model. In this system, the robust tori play the role of a skeleton for the dynamics and block, horizontally, vortices that come from different parts of the phase space. (C) 2012 Elsevier B.V. All rights reserved.

Ordovician klippen structures of the Sierra de Umango: New insights on Tectonic evolution of the Western Sierras Pampeanas, Argentina

The basement rock of the Pampean flat-slab (Sierras Pampeanas) in the Central Andes was uplifted and rotated in the Cenozoic era. The Western Sierras Pampeanas are characterised by meta-igneous rocks of Grenvillian Mesoproterozoic age and metasedimentary units metamorphosed in the Ordovician period. These rocks, known as the northern Cuyania composite terrane, were derived from Laurentia and accreted toward Western Gondwana during the Early Paleozoic. The Sierra de Umango is the westernmost range of the Western Sierras Pampeanas.This range is bounded by the Devonian sedimentary rocks of the Precordillera on the western side and Tertiary rocks from the Sierra de Maz and Sierra del Espinal on the eastern side and contains igneous and sedimentary rocks outcroppings from the Famatina System on the far eastern side. The Sierra de Umango evolved during a period of polyphase tectonic activity, including an Ordovician collisional event, a Devonian compressional deformation, Late Paleozoic and Mesozoic extensional faulting and sedimentation (Paganzo and Ischigualasto basins) and compressional deformation of the Andean foreland during the Cenozoic. A Nappe System and an important shear zone, La Puntilla-La Falda Shear Zone (PFSZ), characterise the Ordovician collisional event, which was related to the accretion of Cuyania Terrane to the proto-Andean margin of Gondwana. Three continuous deformational phases are recognised for this event: the D1 phase is distinguished by relics of 51 preserved as internal foliation within interkinematic staurolite por-phyroblasts and likely represents the progressive metamorphic stage; the D2 phase exhibits P-T conditions close to the metamorphic peak that were recorded in an 52 transposition or a mylonitic foliation and determine the main structure of Umango; and the D3 phase is described as a set of tight to recumbent folds with S3 axial plane foliation, often related to thrust faults, indicating the retrogressive metamorphic stage. The Nappe System shows a top-to-the S/SW sense direction of movement, and the PFSZ served as a right lateral ramp in the exhumation process. This structural pattern is indicative of an oblique collision, with the Cuyania Terrane subducting under the proto-Andean margin of Gondwana in the NE direction. This continental subduction and exhumation lasted at least 30 million years, nearly the entire Ordovician period, and produced metamorphic conditions of upper amphibolite-to-granulite facies in medium- to high-pressure regimes. At least two later events deformed the earlier structures: D4 and D5 deformational phases. The D4 deformational phase corresponds to upright folding, with wavelengths of approximately 10 km and a general N-S orientation. These folds modified the S2 surface in an approximately cylindrical manner and are associated with exposed, discrete shear zones in the Silurian Guandacolinos Granite. The cylindrical pattern and subhorizontal axis of the D4 folds indicates that the S2 surface was originally flat-lying. The D4 folds are responsible for preserving the basement unit Juchi Orthogneiss synformal klippen. This deformation corresponds to the Chanica Tectonic during the interval between the Devonian and Carboniferous periods. The D5 deformational phase comprehends cuspate-lobate shaped open plunging folds with E W high-angle axes (D5 folds) and sub-vertical spaced cleavage. The D5 folds and related spaced cleavage deformed the previous structures and could be associated with uplifting during the Andean Cycle. (C) 2012 Elsevier Ltd. All rights reserved.

Stripe-tetragonal phase transition in the two-dimensional Ising model with dipole interactions: Partition function zeros approach

We have performed multicanonical simulations to study the critical behavior of the two-dimensional Ising model with dipole interactions. This study concerns the thermodynamic phase transitions in the range of the interaction delta where the phase characterized by striped configurations of width h = 1 is observed. Controversial results obtained from local update algorithms have been reported for this region, including the claimed existence of a second-order phase transition line that becomes first order above a tricritical point located somewhere between delta = 0.85 and 1. Our analysis relies on the complex partition function zeros obtained with high statistics from multicanonical simulations. Finite size scaling relations for the leading partition function zeros yield critical exponents. that are clearly consistent with a single second-order phase transition line, thus excluding such a tricritical point in that region of the phase diagram. This conclusion is further supported by analysis of the specific heat and susceptibility of the orientational order parameter.

Corrole isomers: intrinsic gas-phase shapes via traveling wave ion mobility mass spectrometry and dissociation chemistries via tandem mass spectrometry

Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most "confused" isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH3, allowing its prompt differentiation from the other isomers.

Celecoxib treatment does not alter recruitment and activation of osteoclasts in the initial phase of experimental tooth movement

In a previous study, we reported that the short-term treatment with celecoxib, a nonsteroidal anti-inflammatory drug (NSAID) attenuates the activation of brain structures related to nociception and does not interfere with orthodontic incisor separation in rats. The conclusion was that celecoxib could possibly be prescribed for pain in orthodontic patients. However, we did not analyze the effects of this drug in periodontium. The aim of this follow-up study was to analyze effects of celecoxib treatment on recruitment and activation of osteoclasts and alveolar bone resorption after inserting an activated orthodontic appliance between the incisors in our rat model. Twenty rats (400420 g) were pretreated through oral gavage with celecoxib (50 mg/kg) or vehicle (carboxymethylcellulose 0.4%). After 30 min, they received an activated (30 g) orthodontic appliance, set not to cause any palate disjunction. In sham animals, the appliance was immediately removed after introduction. All animals received ground food and, every 12 h, celecoxib or vehicle. After 48 h, they were anesthetized and transcardiacally perfused through the aorta with 4% formaldehyde. Subsequently, maxillae were removed, post-fixed and processed for histomorphometry or immunohistochemical analyses. As expected, incisor distalization induced an inflammatory response with certain histological changes, including an increase in the number of active osteoclasts at the compression side in group treated with vehicle (appliance: 32.2 +/- 2.49 vs sham: 4.8 +/- 1.79, P<0.05) and celecoxib (appliance: 31.0 +/- 1.45 vs sham: 4.6 +/- 1.82, P<0.05). The treatment with celecoxib did not modify substantially the histological alterations and the number of active osteoclasts after activation of orthodontic appliance. Moreover, we did not see any difference between the groups with respect to percentage of bone resorption area. Taken together with our previous results we conclude that short-term treatment with celecoxib can indeed be a therapeutic alternative for pain relieve during orthodontic procedures.

Use of a Single L1 GPS Receiver for Monitoring Structures: First Results of the Detection of Millimetric Dynamic Oscillations

This paper presents preliminary results to determine small displacements of a global positioning system (GPS) antenna fastened to a structure using only one L1 GPS receiver. Vibrations, periodic or not, are common in large structures, such as bridges, footbridges, tall buildings, and towers under dynamic loads. The behavior in time and frequency leads to structural analysis studies. The hypothesis of this article is that any large structure that presents vibrations in the centimeter-to-millimeter range can be monitored by phase measurements of a single L1 receiver with a high data rate, as long as the direction of the displacement is pointing to a particular satellite. Within this scenario, the carrier phase will be modulated by antenna displacement. During a period of a few dozen seconds, the relative displacement to the satellite, the satellite clock, and the atmospheric phase delays can be assumed as a polynomial time function. The residuals from a polynomial adjustment contain the phase modulation owing to small displacements, random noise, receiver clock short time instabilities, and multipath. The results showed that it is possible to detect displacements of centimeters in the phase data of a single satellite and millimeters in the difference between the phases of two satellites. After applying a periodic nonsinusoidal displacement of 10 m to the antenna, it is clearly recovered in the difference of the residuals. The time domain spectrum obtained by the fast Fourier transform (FFT) exhibited a defined peak of the third harmonic much more than the random noise using the proposed third-degree polynomial model. DOI: 10.1061/(ASCE)SU.1943-5428.0000070. (C) 2012 American Society of Civil Engineers.

Electron collisions with the HCOOH...(H2O)n (n=1, 2 and 3) complexes in liquid phase: the influence on the π* shape resonance of formic acid

In this conference we report cross sections for elastic collisions of low-energy electrons with the HCOOH…(H2O)n complexes, with n = 1, 2 and 3. The scattering cross sections were computed with the Schwinger multichannel method [K. Takatsuka and V. McKoy, Phys. Rev. A 24 , 2473 (1981); Phys. Rev. A 30 , 1734 (1984)] with pseudopotentials [M. H. F. Bettega, L. G. Ferreira, and M. A. P. Lima, Phys. Rev. A 47, 1111 (1993)] in the static-exchange and static-exchange plus polarization approximations, for energies from 0.5 eV to 6 eV. We considered some diÆerent hydrogen-bonded structures for the complexes that were generated with classical Monte Carlo simulations [K. Coutinho and S. Canuto, J. Chem. Phys. 113, 9132, (2000)]. The aim of this work is to investigate the effect of the surrounding water molecules on the π* shape resonance of the solute. Previous theoretical and experimental studies carried out in the gas phase reported a π* state for HCOOH at around 1.9 eV. For the n = 1 case and for all complexes, the stabilization of the resonance was observed (it appears at lower energy compared to the value obtained in the gas phase), as reported previously for the CH2O…H2O complexes [T. C. Freitas, M. A. P. Lima, S. Canuto, and M. H. F. Bettega, Phys. Rev. A 80, 062710 (2009)]. This result indicates that the presence of the solvent may affect the processes related to the π* state, such as the molecular dissociation by electron impact. For the n = 2 case we have observed both stabilization and destabilization of the π* resonance, that is associated with the hydrogen bond donor or acceptor role of the water molecules in the complexes. For the n = 3 case, preliminary static-exchange results show the stabilization of the π* state. We propose an explanation of the stabilization/destabilization of the π* state in terms of the polarization of the solute due to the surrounding water molecules and the net charge in the solute.

Annealed Ising model on hierarchical structures: a transfer matrix approach.

Spin systems in the presence of disorder are described by two sets of degrees of freedom, associated with orientational (spin) and disorder variables, which may be characterized by two distinct relaxation times. Disordered spin models have been mostly investigated in the quenched regime, which is the usual situation in solid state physics, and in which the relaxation time of the disorder variables is much larger than the typical measurement times. In this quenched regime, disorder variables are fixed, and only the orientational variables are duly thermalized. Recent studies in the context of lattice statistical models for the phase diagrams of nematic liquid-crystalline systems have stimulated the interest of going beyond the quenched regime. The phase diagrams predicted by these calculations for a simple Maier-Saupe model turn out to be qualitative different from the quenched case if the two sets of degrees of freedom are allowed to reach thermal equilibrium during the experimental time, which is known as the fully annealed regime. In this work, we develop a transfer matrix formalism to investigate annealed disordered Ising models on two hierarchical structures, the diamond hierarchical lattice (DHL) and the Apollonian network (AN). The calculations follow the same steps used for the analysis of simple uniform systems, which amounts to deriving proper recurrence maps for the thermodynamic and magnetic variables in terms of the generations of the construction of the hierarchical structures. In this context, we may consider different kinds of disorder, and different types of ferromagnetic and anti-ferromagnetic interactions. In the present work, we analyze the effects of dilution, which are produced by the removal of some magnetic ions. The system is treated in a “grand canonical" ensemble. The introduction of two extra fields, related to the concentration of two different types of particles, leads to higher-rank transfer matrices as compared with the formalism for the usual uniform models. Preliminary calculations on a DHL indicate that there is a phase transition for a wide range of dilution concentrations. Ising spin systems on the AN are known to be ferromagnetically ordered at all temperatures; in the presence of dilution, however, there are indications of a disordered (paramagnetic) phase at low concentrations of magnetic ions.