Equilibrium polymerization of cyclic carbonate oligomers. III. Chain branching and the gel transition

Ring-opening polymerization of cyclic polycarbonate oligomers, where monofunctional active sites act on difunctional monomers to produce an equilibrium distribution of rings and chains, leads to a "living polymer." Monte Carlo simulations [two-dimensional (2D) and three-dimensional (3D)] of the effects of single [J. Chem. Phys. 115, 3895 (2001)] and multiple active sites [J. Chem. Phys. 116, 7724 (2002)] are extended here to trifunctional active sites that lead to branching. Low concentrations of trifunctional particles c(3) reduce the degree of polymerization significantly in 2D, and higher concentrations (up to 32%) lead to further large changes in the phase diagram. Gel formation is observed at high total density and sizable c(3) as a continuous transition similar to percolation. Polymer and gel are much more stable in 3D than in 2D, and both the total density and the value of c(3) required to produce high molecular weight aggregates are reduced significantly. The degree of polymerization in high-density 3D systems is increased by the addition of trifunctional monomers and reduced slightly at low densities and low c(3). The presence of branching makes equilibrium states more sensitive (in 2D and 3D) to changes in temperature T. The stabilities of polymer and gel are enhanced by increasing T, and-for sufficiently high values of c(3)-there is a reversible polymer-gel transformation at a density-dependent floor temperature. (C) 2002 American Institute of Physics.

Alien gosd in the new epics: Noah remythologised through the ancient astronaut hypothesis in Abel's Montagut's "La gesta d'Utnoa"

Modern scientific world-view has undermined traditional myths, the functional survival of which seems to depend today in the West on a positivist justification. This would place them in the field of real History, through their study and revitalization by pseudoscientific disciplines such as the Atlantis and the ancient astronaut hypotheses. These have inspired new epic poems in (regular) verse that combine classic and/or biblical myths with a (pseudo)scientific modern world-view. For example, the critical rewriting of Noah’s myth by using the ancient astronaut hypothesis as a fictional device to produce a contemporary kind of plausibility allowed Abel Montagut to renew epic poetry, updating it also by adopting science fiction chronotopes in order to structure his fictional construction and to generate a high ethical sense for our time. Thus, his Poemo de Utnoa (1993) / La gesta d’Utnoa (1996), which has become a major classic of the literature in Esperanto thanks to its original version in this language, is a landmark of both science fiction and neo-biblical epics. This poem is written from a secular and purely literary perspective.

William Herschel Telescope observations of distant comets

We present results from broad-band V- and R-filter observations obtained at the 4.2-m William Herschel Telescope on La Palma on 2002 July 12-14. A total of six comets were imaged, and their heliocentric distances ranged from 2.8 to 6.1 au. The comets observed were 43P/Wolf-Harrington, 129P/Shoemaker-Levy 3, 133P/Elst-Pizarro, 143P/Kowal-Mrkos, P/1998 U4 (Spahr) and P/2001 H5 (NEAT). A detailed surface brightness profile analysis indicates that three of the targeted comets (43P/Wolf-Harrington, 129P/Shoemaker-Levy 3 and P/1998 U4) were visibly active, and the remaining three comets were stellar in appearance. Further analysis shows that for the three `stellar-like' comets the possible coma contribution to the observed flux does not exceed 12.2 per cent, and in the case of comet 143P/Kowal-Mrkos the coma contribution is expected to be as low as 1 per cent, and so the resulting photometry most likely represents that of the projected nucleus surface. Effective radii for the inactive comets range from 1.02 to 4.56 km, and the effective radius upper limits for the active comets range from 1.94 to 4.15 km. We assume an albedo and phase coefficient of 0.04 and 0.035 mag deg-1, respectively, with the exception of comets 133P/Elst-Pizarro and 143P/Kowal-Mrkos for which phase coefficients were previously measured. These values are compared with previous measurements, and for comet 43P/Wolf-Harrington we find that the nucleus axial ratio a/b could be as large as 2.44. For the active comets we measured dust production levels in terms of the Af? quantity. Spectral gradients were extracted for two of the inactive comets from their measured broad-band colour indices, and compared with the rest of the comet population for which (V-R) colour and spectral gradient values exist. We find a spectral gradient for 143P/Kowal-Mrkos of 9.9 +/- 8.1 per cent/100 nm, which is very typical of Jupiter-family comets, the majority of which have reflectivity gradients in the range 0-13 per cent (100 nm)-1. The spectral gradient for comet 133P/Elst-Pizarro is amongst the bluest yet measured. We measure a (V-R) colour index value of 0.14 +/- 0.11 for the nucleus of 133P/Elst-Pizarro which is considerably lower than previous measurements. A possible explanation for this difference is considered.

Inscribir el declive en el tiempo. Detroit: Auge y crisis de la ciudad industrial

A comienzos del siglo XX, Detroit era una ciudad dinámica en pleno desarrollo. Pronto se convirtió en la cuarta ciudad de Estados Unidos, la capital de la naciente industria automovilística. El crecimiento se prolongó hasta finales de los años 50, cuando, a pesar del auge económico de Estados Unidos y de su área metropolitana, Detroit comenzó a mostrar los primeros signos de estancamiento. La crisis se ha prolongado hasta hoy, cuando Detroit constituye el paradigma de la ciudad industrial en declive. Estas dos imágenes contrapuestas, el auge y la crisis, no parecen explicar por sí mismas las causas de la intensidad y persistencia del declive de Detroit. Analizar las interacciones entre crecimiento económico, políticas públicas locales y desarrollo urbano a lo largo del tiempo permitirá subrayar las continuidades y comprender en qué medida el declive de Detroit ancla sus raíces en el modelo planteado durante la etapa de auge.

Reduced-size polarized basis sets for calculations of molecular electric properties. III. Second-row atoms

Reduced-size polarized (ZmPolX) basis sets are developed for the second-row atoms X = Si, P, S, and Cl. The generation of these basis sets follows from a simple physical model of the polarization effect of the external electric field which leads to highly compact polarization functions to be added to the chosen initial basis set. The performance of the ZmPolX sets has been investigated in calculations of molecular dipole moments and polarizabilities. Only a small deterioration of the quality of the calculated molecular electric properties has been found. Simultaneously the size of the present reduced-size ZmPolX basis sets is about one-third smaller than that of the usual polarized (PolX) sets. This reduction considerably widens the range of applications of the ZmPolX sets in calculations of molecular dipole moments, dipole polarizabilities, and related properties.

Dogs in the paradise: The influence of the cynical philosophy in the construction of the myth of the good savage

This paper studies the influence of cynic philosophy in the construction of the myth of the good savage. In the first part it studies the importance of cynicism in the XVI century and how the cynic influence of Erasmus, More and Montaigne was fundamental to the way that Europe approached the American indigenous. In the second part it studies the cynic motives that could have influenced in the construction of the myth of the good savage.

Tris(1-ethyl-3-methylimidazolium) hexabromidoeuropate(III)

The crystal structure of the title compound, (C6H11N2)(3-)[EuBr6], consists of 1-ethyl-3-methylimidazolium cations and centrosymmetric octahedral hexabromidoeuropate anions. The [EuBr6](3-) anions are located at the corners and face-centres of the monoclinic unit cell. Characteristic hydrogen-bonding interactions can be observed between the bromide anions and the acidic H atoms of the imidazolium cations.

Visible and Near-Infrared Emission by Samarium(III)-Containing Ionic Liquid Mixtures

Highly luminescent anionic samarium(III) beta-diketonate and dipicolinate complexes were dissolved in the imidazolium ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. The solubility of the complexes in the ionic liquid was ensured by a careful choice of the countercation of the samarium(III) complex. The samarium(III) complexes that were considered are [C(6)mim][SM(tta)(4)], where tta is 2-thenoyltrifluoroacetonate; [C(6)mim][Sm(nta)(4)], where nta is 2-naphthoyltrifluoroacetonate; [C(6)mim][Sm(hfa)(4)], where hfa is hexafluoroacetylacetonate; and [choline](3)-[Sm(dpa)(3)], where dpa is pyridine-2,6-dicarboxylate (dipicolinate) and [choline](+) is (2-hydroxyethyl)trimethyl ammonium. The crystal structures of the tetrakis samarium(III) P-diketonate complexes revealed a distorted square antiprismatic coordination for the samarium(III) ion in all three cases. Luminescence spectra were recorded for the samarium(III) complexes dissolved in the imidazolium ionic liquid as well as in a conventional solvent, that is, acetonitrile or water for the beta-diketonate and dipicolinate complexes, respectively. These experiments demonstrate that [C(6)mim][Tf2N] is a suitable spectroscopic solvent for studying samarium(III) luminescence. High-luminescence quantum yields were observed for the samarium(III) beta-diketonate complexes in solution.

La música práctica en san Agustín: "vestigium" y "signum"

En distintos momentos de su producción intelectual, Agustín se refirió al asunto de la música. En este artículo mostraremos que Agustín uso dos esquemas conceptuales distintos para describir el fenómeno de la música práctica en su relación con el mundo espiritual, el esquema de las Artes Liberales y el de la teoría del signo, y que en virtud de ello la música sería concebida de dos modos diferentes: como vestigium y como signum del mundo espiritual, respectivamente. Al final del artículo analizaremos la diferencia entre las dos concepciones considerando tres elementos: la naturaleza de la relación entre mundo material y espiritual, el contenido espiritual al que remite y la noción de belleza que implica.

Psychological status of patients referred for orthognathic correction of skeletal II and III discrepancies

Objective: To establish the extent of psychological problems among patients who require orthognathic treatment. Materials and Methods: Five aspects of psychological functioning were assessed for 162 patients who required orthognathic treatment and compared with 157 control subjects.

Results: Analysis of variance did not detect any significant difference in the five psychological scores recorded for the skeletal II, skeletal III, and control groups. The proportion of subjects with one or more psychological measure beyond the normal range was 27% for skeletal II subjects, 25% for skeletal III subjects, and 26% for control subjects. One skeletal II subject (1.5%), three skeletal III subjects (3%), and five control subjects (3%) required referral for psychological counseling.

Conclusions: The orthognathic patients did not differ significantly from the control subjects in their psychological status. © 2010 by The EH Angle Education and Research Foundation, Inc.

Selective Imaging of Damaged Bone Structure (Microcracks) Using a Targeting Supramolecular Eu(III) Complex As a Lanthanide Luminescent Contrast Agent

The synthesis and photophysical evaluation of a new supramolecular lanthanide complex is described which was developed as a luminescent contrast agent for bone structure analysis. We show that the Eu(III) emission of this complex is not pH dependent within the physiological pH range, and that its steady state emission is not significantly modulated by a series of group I and II as well as d-metal ions, and that this agent can be successfully employed to image mechanically formed cracks (scratches) in bone samples after 4 or 24 hours, using confocal laser-scanning microscopy.

Ionic liquid as plasticizer for europium(III)-doped luminescent poly(methyl methacrylate) films

Flexible luminescent polymer films were obtained by doping europium(III) complexes in blends of poly(methyl methacrylate) (PMMA) and the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. Different europium(III) complexes have been incorporated in the polymer/ionic liquid matrix: [C(6)mim][Eu(nta)(4)], [C(6)mim][Eu(tta)(4)], [Eu(tta)(3)(phen)] and [choline](3)[Eu(dpa)(3)], where nta is 2-naphthoyltrifluoroacetonate, tta is 2-thenoyltrifluoroacetonate, phen is 1,10-phenanthroline, dpa is 2,6-pyridinedicarboxylate ( dipicolinate) and choline is the 2-hydroxyethyltrimethyl ammonium cation. Bright red photoluminescence was observed for all the films upon irradiation with ultraviolet radiation. The luminescent films have been investigated by high-resolution steady-state luminescence spectroscopy and by time-resolved measurements. The polymer films doped with beta-diketonate complexes are characterized by a very intense D-5(0) -> F-7(2) transition ( up to 15 times more intense than the D-5(0) -> F-7(1)) transition, whereas a marked feature of the PMMA films doped with [choline](3)[Eu(dpa)(3)] is the long lifetime of the D-5(0) excited state (1.8 ms).

Mandelohydroxamic acid as ligand for copper(II) 15-metallacrown-5 lanthanide(III) and copper(II) 15-metallacrown-5 uranyl complexes

The formation of pentanuclear copper(ii) complexes with the mandelohydroxamic ligand was studied in solution by electrospray ionization mass spectrometry (ESI-MS), absorption spectrophotometry, circular dichroism and H-1 NMR spectroscopy. The presence of lanthanide(iii) or uranyl ions is essential for the self-assembly of the 15-metallacrown-5 compounds. The negative mode ESI-MS spectra of solutions containing copper(II), mandelohydroxamic acid and lanthanide(iii) ions (Ln = La, Ce, Nd, Eu, Gd, Dy, Er, Tm, Lu, Y) or uranyl in the ratio 5:5:1 showed only the peaks that could be unambiguously assigned to the following intact molecular ions: {Ln(NO3)(2)[15-MCuIIN(MHA)-5](2-)}(-) and {Ln(NO3)[15-MCCuIIN(MHA)-5](3-)}(-), where MHA represents doubly deprotonated mandelohydroxamic acid. The NMR spectra of the pentanuclear species revealed only one set of peaks indicating a fivefold symmetry of the complex. The pentanuclear complexes synthesized with the enantiomerically pure R- or S-forms of mandelohydroxamic acid ligand, showed circular dichroism spectra which were mirror images of each other. The pentanuclear complex made from the racemic form of the ligand showed no signals in the CD spectrum. The UV/ Vis titration experiments revealed that the order in which the metal salts are added to the solution of the mandelohydroxamic acid ligand is crucial for the formation of metallacrown complexes. The addition of copper(ii) to the solutions containing mandelohydroxamic acid and neodymium(iii) in a 5:1 ratio lead to the formation of a pentanuclear complex in solution. In contrary, titration of lanthanide(iii) salt to the solution containing copper(ii) and mandelohydroxamic acid did not show any evidence for the formation of pentanuclear species. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Study of the luminescence of tris(2-thenoyltrifluoroacetonato)lanthanide(III) complexes covalently linked to 1,10-phenanthroline-functionalized hybrid sol-gel glasses

The solubility and uniform distribution of lanthanide complexes in sol-get glasses can be improved by covalently linking the complexes to the sol-gel matrix. In this study, several lanthanide beta-diketonate complexes (Ln = Nd, Sm, Eu, Tb, Er, Yb) were immobilized on a 1,10-phenanthroline functionalized sol-gel glass. For the europium(Ill) complex, a sol-gel material of diethoxydimethylsilane (DEDMS) with polymer-like properties was derived. For the other lanthanide complexes, the sol-gel glass was prepared by using a matrix of tetramethoxysilane (TMOS) and DEDMS. Both systems were prepared under neutral reaction conditions. High-resolution emission and excitation spectra were recorded. The luminescence lifetimes were measured. (c) 2004 Elsevier B.V. All rights reserved.