62 research outputs found

    Theoretical models of nonlinear effects in two-component cooperative supramolecular copolymerizations

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    The understanding of multi-component mixtures of self-assembling molecules under thermodynamic equilibrium can only be advanced by a combined experimental and theoretical approach. In such systems, small differences in association energy between the various components can be significantly amplified at the supramolecular level via intricate nonlinear effects. Here we report a theoretical investigation of two-component, self-assembling systems in order to rationalize chiral amplification in cooperative supramolecular copolymerizations. Unlike previous models based on theories developed for covalent polymers, the models presented here take into account the equilibrium between the monomer pool and supramolecular polymers, and the cooperative growth of the latter. Using two distinct methodologies, that is, solving mass-balance equations and stochastic simulation, we show that monomer exchange accounts for numerous unexplained observations in chiral amplification in supramolecular copolymerization. In analogy with asymmetric catalysis, amplification of chirality in supramolecular polymers results in an asymmetric depletion of the enantiomerically related monomer pool

    Changing patterns in diagnostic strategies and the treatment of blunt injury to solid abdominal organs

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    Background: In recent years there has been increasing interest shown in the nonoperative management (NOM) of blunt traumatic injury. The growing use of NOM for blunt abdominal organ injury has been made possible because of the progress made in the quality and availability of the multidetector computed tomography (MDCT) scan and the development of minimally invasive intervention options such as angioembolization. Aim: The purpose of this review is to describe the changes that have been made over the past decades in the management of blunt trauma to the liver, spleen and kidney. Results: The management of blunt abdominal injury has changed considerably. Focused assessment with sonography for trauma (FAST) examination has replaced diagnostic peritoneal lavage as diagnostic modality in the primary survey. MDCT scanning with intravenous contrast is now the gold standard diagnostic modality in hemodynamically stable patients with intra-abdominal fluid detected with FAST. One of the current discussions in the l erature is whether a whole body MDCT survey should be implemented in the primary survey. Conclusions The progress in imaging techniques has contributed to NOM being currently the treatment of choice for hemodynamically stable patients. Angioembolization can be used as an adjunct to NOM and has increased the succe

    Anion-templated assembly of [2]rotaxanes.

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    Anion templation is used to develop a general method for rotaxane synthesis. The anion-templated synthesis of three new [2]rotaxanes containing positively charged pyridinium axles and neutral isophthalamide macrocyclic components is described. The incorporation of electron withdrawing substituents, such as the nitro group, into the 5-position of an isophthalamide bis-vinyl acyclic precursor results in a significant improvement in [2]rotaxane assembly yields. Rotaxane anion binding strengths are also enhanced whilst the rotaxane's unique interlocked binding domain ensures selectivity for chloride--the templating anion--is maintained

    Systems Chemistry

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    Self-Organization

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    Uneven Power and the Pursuit of Peace: How Regional Power Transitions Motivate Integration. CES Working Paper, no. 150, 2007

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    This paper addresses two related puzzles confronting students of regional and international integration: Why do states willingly pool and delegate sovereignty within international institutions? What accounts for the timing and content of regional integration agreements? Most theories of integration suggest that states integrate in order to solve problems of incomplete information and reduce transaction costs and other barriers to economic growth. In contrast I argue that integration can serve to establish a credible commitment that rules out the risk of future conflict among states of unequal power. Specifically, I suggest that integration presents an alternative to preventive war as a means to preclude a rising revisionist power from establishing a regional hegemony. The implication is that it is not countries enjoying stable and peaceful relations that are most likely to pursue integration, but rather countries that find themselves caught in a regional security dilemma, which they hope to break out of by means of institutionalized cooperation. I evaluate this proposition against evidence from two historical cases of regional integration: the German Zollverein and the European Communities
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