Combined Monte Carlo and quantum mechanics study of the solvatochromism of phenol in water. The origin of the blue shift of the lowest pi-pi* transition

A combined and sequential use of Monte Carlo simulations and quantum mechanical calculations is made to analyze the spectral shift of the lowest pi-pi* transition of phenol in water. The solute polarization is included using electrostatic embedded calculations at the MP2/aug-cc-pVDZ level giving a dipole moment of 2.25 D, corresponding to an increase of 76% compared to the calculated gas-phase value. Using statistically uncorrelated configurations sampled from the MC simulation,first-principle size-extensive calculations are performed to obtain the solvatochromic shift. Analysis is then made of the origin of the blue shift. Results both at the optimized geometry and in room-temperature liquid water show that hydrogen bonds of water with phenol promote a red shift when phenol is the proton-donor and a blue shift when phenol is the proton-acceptor. In the case of the optimized clusters the calculated shifts are in very good agreement with results obtained from mass-selected free jet expansion experiments. In the liquid case the contribution of the solute-solvent hydrogen bonds partially cancels and the total shift obtained is dominated by the contribution of the outer solvent water molecules. Our best result, including both inner and outer water molecules, is 570 +/- 35 cm(-1), in very good agreement with the small experimental shift of 460 cm(-1) for the absorption maximum.

Contribution of the second Landau level to the exchange energy of the three-dimensional electron gas in a high magnetic field

We derive a closed analytical expression for the exchange energy of the three-dimensional interacting electron gas in strong magnetic fields, which goes beyond the quantum limit (L=0) by explicitly including the effect of the second, L=1, Landau level and arbitrary spin polarization. The inclusion of the L=1 level brings the fields to which the formula applies closer to the laboratory range, as compared to previous expressions, valid only for L=0 and complete spin polarization. We identify and explain two distinct regimes separated by a critical density n(c). Below n(c), the per particle exchange energy is lowered by the contribution of L=1, whereas above n(c) it is increased. As special cases of our general equation we recover various known more limited results for higher fields, and we identify and correct a few inconsistencies in some of these earlier expressions.

The origin of the metazoan biphasic life cycle: New insights from an ancient phylum

The biphasic life cycle, characterised by metamorphosis from a pelagic larva to a benthic adult, is found throughout the Metazoa. So is sexual reproduction via eggs and sperm. Amidst a tangled web of hypotheses on the origin of metazoan biphasy, current weight of opinion lies with a simple, larva-like holopelagic ancestor that independently settled multiple times to incorporate a benthic phase into the life cycle. This school of thought derives from Haeckel's interpretation of the gastrula as the recapitulation of a gastrean ancestor that evolved via selection on a simple, planktonic hollow ball-of-cells to develop the capacity to feed. We suggest that a paradigm shift is required to accomodate accumulating evidence of the genomic and developmental complexity of the metazoan last common ancestor, which was likely to have already possessed a biphasic lifecycle. Here we incorporate recent evidence from basal metazoans, in particular poriferans, to argue that a more parsimonious theory of the origin of biphasy is as a direct consequence of sexual reproduction in an ancestral benthic adult form. The metazoan embryo can itself be considered the precursor to a biphasic life cycle, wherein the embryo represents one phase and the adult another. Embryos in the water column are subject to natural selection for longeveity and dispersal, which sets them on the evolutionary trajectory towards the crown metazoan planktonic larvae. This alternate view considers the conserved use of regulatory genes in disparate metazoans as a reflection of both the complexity of the LCA and the antiquity of the biphasic life cycle. It does not require that extant embryogenesis, including gastrulation, recapitulates evolution.

The neural histogenetic origin of the oral granular cell tumor: An immunohistochemical evidence

Aims: Granular cell tumor (GCT) is a rare neoplasm that can appear in any site of the body, but most are located intraorally. Its histogenetic origin remains unclear. This report analyzes the immunoprofile of 15 cases of granular cell tumors, occurring in 13 women and 2 men and the lesions were located on the tongue or upper lip. Patient age ranged from 7 to 52. Methods: The patients demographic data and the cytological and architectural features of the lesions were analyzed in oral GCTs (n = 15). The lesions were also submitted to a panel of immunohistochemical stains with antibodies against S-100, p75, NSE, CD-68, Ki-67, Synaptofisin, HHF-35, SMA, EMA, Chromogranin, Progesterone, Androgen and Estrogen. Results: Among the fifteen cases analyzed, the most common location was the tongue (84.6%). Histologically, the tumors exhibited cellular proliferation composed mainly by polygonal cells presenting an abundant granular eosinophilic cytoplasm. The nuclei were central, and the cell membranes were moderately clear. No mitotic figures were observed. The immunohistochemical analysis showed positivity in all cases for S-100, p75, NSE and CD-68, and no immunoreactivity for Ki-67, Synaptofisin, HHF-35, SMA, EMA, Chromogranin, Progesterone, Androgen and Estrogen. Conclusion: The immunoprofile of granular cell tumors showed nerve sheath differentiation - lending support to their neural origin - and helping to establish a differential diagnosis between this lesion and other oral granular cell tumors, whether benign or malignant.

On the permutation behaviour of Dickson polynomials of the second kind

The known permutation behaviour of the Dickson polynomials of the second kind in characteristic 3 is expanded and simplified. (C) 2002 Elsevier Science (USA).

Reshaping European Union development policy: collective choices and the new global order

Abstract The European Union (EU) is one of the world´s leading donors in official development assistance (ODA) to give a strong weight in the relationship with recipient partner countries, in particular with those that are more dependent on it. Besides the material weight of its funding, the EU has retained historical ties and influence in diplomatic, political and economic terms in many of its ODA recipient partner countries (particular in Sub-Saharan Africa). Since the 2000s, the EU development policy has not only undergone major structural changes in its institutional framework but also has started to face a new international aid scenario. This paper explores why a normative-based EU development policy is being challenged by reformed EU institutions and a new global order, and how the EU is attempting to respond to this context in face of the deepest recession since the end of the Second World War.

On the origin of the electrical response of vapor grown carbon nanofiber + epoxy composites

The origin of the electrical response of vapor grown carbon nanofiber (VGCNF) + epoxy composites is investigated by studying the electrical behavior of VGCNF with resin, VGCNF with hardener and cured composites, separately. It is demonstrated that the onset of the conductivity is associated to the emergence of a weak disorder regime. It is also shown that the weak disorder regime is related to a hopping depending on the physical properties of the polymer matrix.

A cellulose liquid crystal motor: a steam engine of the second kind

The salient feature of liquid crystal elastomers and networks is strong coupling between orientational order and mechanical strain. Orientational order can be changed by a wide variety of stimuli, including the presence of moisture. Changes in the orientation of constituents give rise to stresses and strains, which result in changes in sample shape. We have utilized this effect to build soft cellulose-based motor driven by humidity. The motor consists of a circular loop of cellulose film, which passes over two wheels. When humid air is present near one of the wheels on one side of the film, with drier air elsewhere, rotation of the wheels results. As the wheels rotate, the humid film dries. The motor runs so long as the difference in humidity is maintained. Our cellulose liquid crystal motor thus extracts mechanical work from a difference in humidity.

The detrital origin of the Moncorvo ordovician ironstones

The Moncorvo Ordovician ironstones in northeastern Portugal consist of iron ore sedimentary horizons frequently interbanded with psamites and quartzites. Ore reserves may probably exceed 1 000 million tonnes and this makes Moncorvo the largest iron ore deposit in the European Union. Compact poorly banded massive layers may exceed 90 meters in thickness which is quite an extraordinary feature for a Phanerozoic deposit. If the thickness of Precambrian deposits may reach a few hundred meters, the thickness of Phanerozoic deposits never exceed a maximum of 15 meters generally forming a number of comparatively thin layers confined to a particular member of a sedimentary sequence. A detailed microscopic analysis of the ores revealed that initially a compact magnetite/quartzite layer, detrital in character (the magnetite occasionally showing chromite cores), was deposited by entrapment in near shore lagoons where rivers debouched, rather than in the open sea. This stage was followed by oscilating and transgressive shore lines which gave rise to breaks in sedimentation in combined river delta and shallow water marine environment where detrital material and fine iron oxide and clay suspensions were deposited in fluctuating environments. These events gave rise to layers of both magnetite (martite) and specularite intergrown with quartz, silicates and phosphates. Textural and mineralogical studies show that the deposits consist of ferruginous clastic sediments and are not chemically deposited cherts. Field, geological and palaeontological evidence also supports a detrital origin, the facies being typical of zones rich in oxygen and close to the feeding continent. The uncommon huge development of Moncorvo was due to the fact that the deposits occur in restricted basins on a continental platform were clastic sediments were predominantly deposited. Not only morphologically but also chemically the deposits are more similar to Precambrian iron formations than to Phanerozoic ironstones.