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.

Density functional/Monte Carlo study of ring-opening polymerization

Density functional calculations of the structure, potential energy surface and reactivity for organic systems closely related to bisphenol-A-polycarbonate (BPA-PC) provide the basis for a model describing the ring-opening polymerization of its cyclic oligomers by nucleophilic molecules. Monte Carlo simulations using this model show a strong tendency to polymerize that is increased by increasing density and temperature, and is greater in 3D than in 2D. Entropy in the distribution of inter-particle bonds is the driving force for chain formation. (C) 2002 Elsevier Science B.V. All rights reserved.

The regulation and role of osteopontin in malignant transformation and cancer.

Osteopontin (OPN) is a predominantly secreted extracellular matrix glycophosphoprotein which binds to alpha v-containing integrins and has an important role in malignant cell attachment and invasion. High OPN expression in the primary tumor is associated with early metastasis and poor outcome in human breast and other cancers. Forced OPN overexpression in benign cells may induce neoplastic-like cell behaviour including increased attachment and invasion in vitro as well as the ability to metastasize in vivo. Conversely, OPN inhibition by antisense cDNA impedes cell growth and tumor forming capacity. OPN is not mutationally activated in cancer but its expression is regulated by Wnt/Tcf signaling, steroid receptors, growth factors, ras, Ets and AP-1 transcription factors. Presumably these factors are implicated in induction of OPN overexpression in cancer. Greater understanding of the role of OPN in neoplastic change and its transcriptional regulation may enable development of novel cancer treatment strategies

Non-agrocultural co-peratives and economy transformation in Cuba: politic processes and strategies

Contribution of co-operatives has been demonstrated since the 1970s as the main development line in agricultural production in Cuba. In contrast, there has been a late recognition of urban co-operatives, even if the need of transformations based on the realization of property in different territorial scenarios had been identified. The article analyses the reform processes launched since the first decade of the 21st century focusing on the nature of the initiatives fostering formation and promotion of nonagricultural co-operatives including follow up of their performance. The potential and limitations of the recent experiences are examined in order to reflect on the organizational processes and transformations from the point of view of their members. To conclude, some questions are posed about whether these co-operatives are capable of avoiding the impact of earlier employment circumstances and of developing strategies aimed at reinforcing voluntary membership and autonomy on which they are founded.

From the transformation to the bancarization of the spanishsaving banks: an analysis of the results pursued

This research arises due to the current restructuring process in which is immersed the Spanish banking sector. The above mentioned process is carried out to try to reduce the doubts on the viability of the bank companies to average and long term and to be able to return again the confidence in the sector. Though the economic and financial crisis has concerned the whole banking sector, the subsector of the Spanish savings banks is the one that has experienced a major number of integrations (articulated by means of mergers, absorptions and across Institutional Protection Schemes -IPSs-), and the one that has met submitted to the bancarization process. Considering what has been said, the present paper analyses Spanish saving banks to try to discern whether thanks to that process the objectives pursued by the bank rearrangement have been fulfilled. To do this, the evolution of some important financial variables will be studied over a long period of time (1999-2012). The results suggest that not all the savings banks have seen improved their ratios of efficiency, solvency, financial gap and social work, which indicates that there is still much to be done in order to rectify the problems affecting the studied sector.

Chemical Sensing Using a Polymer Coated Long-Period Fiber Grating Interrogated by Ring-Down Spectroscopy

An etched long-period grating was used as a refractive index sensor for vapours of four volatile organic compounds, i.e. m-xylene, cyclohexane, trichloroethylene and commercial gasoline. The sensitivity to the vapours was further increased by solid-phase microextraction into a coating made of polydimethylsiloxane (PDMS)/polymethyl-octylsiloxane (PMOS) co-polymer. By further amplification of the optical loss in an optical cavity made of two identical fiber-Bragg gratings and interrogation by phase-shift cavity ring-down spectroscopy we could detect and distinguish xylene (detection limit: 134ppm) from trichloroethylene (3300ppm), cyclohexane (1850ppm) and gasoline (10,500ppm).