Polymorphism in Sr3Fe2O7−x

The compound Sr₃Fe₂O_7–x , with variable iron valence, was investigated by X-ray powder techniques, both at room and at high temperatures. If the material is examined in massive form, a single phase called -Sr₃Fe₂O_7–x appears as previously reported in the literature. This -phase is tetragonal and exhibits the lattice parameters: a=3.874 and c=40.314 Å. Two other phases, called and -Sr₃Fe₂O_7–x , respectively, can be obtained on heating the finely powdered material when laid on a flat platinum support. The form is stable up to 1275° C, while the form is revealed only above 1275° C and changes always into -Sr₃Fe₂O_7–x when quenched. Both and phases are tetragonal, with a=4.001 and c= 58.251 for the form and a=4.013, c=57.092 Å for the form. The transition involves a true phase equilibrium, while the transformation is possible only by means of a suitable mechanical treatment of the material.     

The presence of a ferrocenyl unit on an estrogenic molecule is not always sufficient to generate in vitro cytotoxicity

We recently reported the dual (antihormonal and cytotoxic) functionality of ferrocifens, which are organometallic complexes derived from hydroxytamoxifen, the standard molecule in the treatment of hormone-dependent breast cancers. To test the hypothesis that the presence of a ferrocenyl substituent on molecules with an affinity for the estrogen receptor is sufficient to give them cytotoxic properties in vitro, we prepared complexes derived from estradiol with a ferrocenyl substituent at positions 7alpha and 17alpha. The complexes thus obtained retain a satisfactory level of affinity for the estrogen receptor (RBA values higher than 12 %). At low concentrations (0.1-1 microM) the complexes show an estrogenic effect in vitro equivalent to that of estradiol on hormone-dependent (MCF-7) breast cancer cells, and no cytotoxic effect on hormone-independent (MDA-MB-231) breast cancer cells. At high concentrations (up to 50 microM) the 17alpha-ethynylferrocenyl estradiol and 7alpha-ferrocenylmethylthio estradiol become cytotoxic (IC(50)=13.2 microM and 18.8 microM, respectively) while the 17alpha-ferrocenylestradiol remains non toxic. The low toxicity of these compounds support our hypothesis that electronic communication between the ferrocenyl and phenol moieties in the hydroxyferrocifens series is a key parameter in the generation of cytotoxic effects at submicromolar concentrations.     

The 70 kDa subunit of replication protein A is required for the G1/S and intra-S DNA damage checkpoints in budding yeast

The rfa1-M2 and rfa1-M4 Saccharomyces cerevisiae mutants, which are altered in the 70 kDa subunit of replication protein A (RPA) and sensitive to UV and methyl methane sulfonate (MMS), have been analyzed for possible checkpoint defects. The G1/S and intra-S DNA damage checkpoints are defective in the rfa1-M2 mutant, since rfa1-M2 cells fail to properly delay cell cycle progression in response to UV irradiation in G1 and MMS treatment during S phase. Conversely, the G2/M DNA damage checkpoint and the S/M checkpoint are proficient in rfa1-M2 cells and all the checkpoints tested are functional in the rfa1-M4 mutant. Preventing S phase entry by alpha-factor treatment after UV irradiation in G1 does not change rfa1-M4 cell lethality, while it allows partial recovery of rfa1-M2 cell viability. Therefore, the hypersensitivity to UV and MMS treatments observed in the rfa1-M4 mutant might only be due to impairment of RPA function in DNA repair, while the rfa1-M2 mutation seems to affect both the DNA repair and checkpoint functions of Rpa70.     

Meteorological and oceanographic conditions in the northern Adriatic Sea during the period June 1999-July 2002: influence on the mucilage phenomenon

Mucilage events (formation of very large organic aggregates and gelatinous surface layers) have been documented several times during the past two centuries in the northern Adriatic Sea (NA), while their frequency has significantly increased since 1988. In this work, meteorological and oceanographic conditions in the NA during the period June 1999-July 2002 are described and their relation to the outbreak and fate of the mucilage phenomenon was investigated. Salinity and temperature data were collected during approximately monthly cruises along three transects in the NA. Relevant meteorological situations (air temperature, rainfall, wind) were selected from large-scale ECMWF analyses and from the Local Analysis and Prediction System (LAPS; Emilia Romagna Meteorological Service), while sea conditions (waves) were analysed by means of the Wave Adriatic Model (WAM). Data for air temperature, rainfall, and wind from several meteorological stations in the region were used. Average seasonal cycles of sea temperature and salinity simulated with statistical models, based on historical data collected in the NA since 1972, were used to determine thermal and haline anomalies. The monthly anomaly variability of maximum and minimum air temperatures, rainfall amount and number of rainy days did not appear to be relevant for the mucilage phenomenon outbreak. In contrast, both vertical and horizontal thermohaline gradients in the region were more developed during late spring and summer of 2000 and particularly of 2002, when the mucilage events were of greatest extent in space and time, compared to 2001 (short-lived event) and 1999 (no event). These more pronounced gradients were due to a combination of several unusual conditions: sharp heating of the sea surface in May-June, domination of eastwards transport of freshened waters formed in the Po Delta area, and intrusion of very high salinity intermediate waters originating in the eastern Mediterranean. Moreover, in winter of both 2000 and 2002 very dense and cold water formed and remained in the bottom layer until spring, contributing to increase the stratification degree of the water column. The duration of the mucilage events and their spatial distribution in the region depend strongly on meteorological changes. Recurrent anticyclonic conditions, characterized by low wind and calm sea, favour extended events in time (up 2 months in 2002). In contrast, highly perturbed weather, particularly due to strong "bora" wind, can be determined in sharp decay of the event (e.g. in July 2000).     

A 3D SMA constitutive model in the framework of finite strain

The aim of the present paper is to propose a phenomenological thermodynamically consistent 3D model for shape memory alloys (SMA) in the finite strain range. In particular, a model able to predict the main features of SMA materials, such as the superelastic and the shape‐memory effects, is proposed. The model is based on the assumption of the local multiplicative split of the deformation gradient into an elastic and a phase transformation part. The governing state and evolutive equations are written in the undeformed configuration. The material parameters of the model are characterized by a clear physical meaning so that they can be determined by simple experimental tests. The finite deformation SMA model is also reformulated in the framework of small strain, linearizing the strain and stress measures in order to obtain a consistent constitutive model preserving the nonlinear material response. A robust algorithm is adopted in order to integrate the nonlinear evolutive equations; 2D and 3D finite elements are implemented in a numerical code considering finite and small deformations. Some numerical applications are carried out showing the performances of the proposed model and the developed numerical procedure to describe the superelastic and the shape‐memory effects of SMA devices. Comparisons of different results obtained by the small and finite strain formulations are reported. Copyright © 2009 John Wiley & Sons, Ltd.     

Combining stochastic programming and optimal control to decompose multistage stochastic optimization problems

The paper suggests a possible cooperation between stochastic programming and optimal control for the solution of multistage stochastic optimization problems. We propose a decomposition approach for a class of multistage stochastic programming problems in arborescent form (i.e. formulated with implicit non-anticipativity constraints on a scenario tree). The objective function of the problem can be either linear or nonlinear, while we require that the constraints are linear and involve only variables from two adjacent periods (current and lag 1). The approach is built on the following steps. First, reformulate the stochastic programming problem into an optimal control one. Second, apply a discrete version of Pontryagin maximum principle to obtain optimality conditions. Third, discuss and rearrange these conditions to obtain a decomposition that acts both at a time stage level and at a nodal level. To obtain the solution of the original problem we aggregate the solutions of subproblems through an enhanced mean valued fixed point iterative scheme.     

Impact of different ionization methods on the molecular assignments of asphaltenes by FT-ICR mass spectrometry

Over the years, ultrahigh resolution mass spectrometry has successfully illustrated the extreme complexity of crude oil and related solubility or polarity based fractions on a molecular level. However, the applied ionization technique greatly influences the outcome and may provide misleading information. In this work, we investigate the atmospheric pressure laser ionization (APLI) technique coupled with Fourier transform ion cyclotron resonance mass spectrometer to analyze the asphaltene fraction of a crude oil. These results were compared to data obtained by using other existing atmospheric pressure ionization methods. Furthermore elemental analysis and solid state NMR were used to obtain the bulk characteristics of the asphaltene sample. The results of the different ionization techniques were compared with the bulk properties in order to describe the potential discrimination effects of the ionization techniques that were observed. The results showed that APLI expands the range of the assigned molecules, while retaining information already observed with the generally used ion sources.