Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases

The conformational properties of gaseous trichloromethyl chloroformate (or “diphosgene”), ClC(O)- OCCl3, have been studied by vibrational spectroscopy [IR (gas), IR (matrix), and Raman (liquid)] and quantum chemical calculations (MP2 and B3LYP with 6-311G* basis sets); in addition, the structure of a single crystal at low temperature has been determined by X-ray diffraction. ClC(O)OCCl3 exhibits only one conformational form having Cs symmetry with a synperiplanar orientation of the C-O single bond relative to the CdO double bond. The calculated energy difference between the syn and anti forms, 5.73 kcal mol-1 (B3LYP) or 7.06 kcal mol-1 (MP2), is consistent with the experimental findings for the gas and liquid phases. The crystalline solid at 150 K [monoclinic, P21/n, a ) 5.5578(5) Å, b ) 14.2895(12) Å, c ) 8.6246(7) Å, â ) 102.443(2)°, Z ) 4] likewise consists only of molecules in the syn form.Fil: Arce, Valeria Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Della Vedova, Carlos Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Servicios a la Industria y al Sistema Científico; ArgentinaFil: Downs, Anthony J.. University of Oxford; Reino UnidoFil: Parsons, Simon. University of Edinburgh; Reino UnidoFil: Romano, Rosana Mariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentin

Viscoelastic material properties of the peripapillary sclera in normal and early-glaucoma monkey eyes

PURPOSE. To test the hypothesis that changes in the viscoelastic material properties of peripapillary sclera are present within monkey eyes at the onset of early experimental glaucoma detected by confocal scanning laser tomography (CSLT). METHODS. Short-term (3-9 weeks), moderate (Յ44 mm Hg) intraocular pressure (IOP) elevation was induced in one eye of each of eight male monkeys by lasering the trabecular meshwork. This procedure generated early experimental glaucoma, defined as the onset of CSLT-detected optic nerve head (ONH) surface change, in the treated eye. Scleral tensile specimens from the superior and inferior quadrants of the eight earlyglaucoma eyes were subjected to uniaxial stress relaxation and tensile tests to failure and the results compared with similar data obtained in a previous study of 12 normal (nonglaucomatous) eyes. Linear viscoelastic theory was used to characterize viscoelastic material property parameters for each specimen. Differences in each parameter due to quadrant and treatment were assessed by analysis of variance (ANOVA). RESULTS. Peripapillary sclera from the early-glaucoma eyes exhibited an equilibrium modulus (7.46 Ϯ 1.58 MPa) that was significantly greater than that measured in normal eyes (4.94 Ϯ 1.22 MPa; mean Ϯ 95% confidence interval, P Ͻ 0.01, ANOVA). Quadrant differences were not significant for the viscoelastic parameters within each treatment group. CONCLUSIONS. The long-term viscoelastic material properties of monkey peripapillary sclera are altered by exposure to moderate, short-term, chronic IOP elevations and these alterations are present at the onset of CSLT-detected glaucomatous damage to the ONH. Damage to and/or remodeling of the extracellular matrix of these tissues may underlie these changes in scleral material properties. (Invest Ophthalmol Vis Sci. 2005;46: 540 -546 1 The finite element method is a computer-based engineering technique that estimates the stresses (force/cross-sectional area) and strains (local deformation under those stresses) within a complex load-bearing structure. 2 The important aspects of a finite element model are the three-dimensional geometry and material properties of the load-bearing structure and the appropriate boundary and mechanical loading conditions. 2 Within such models of the monkey ONH, scleral material properties are needed to characterize accurately the important transition between the peripapillary sclera and the peripheral laminar beams. To characterize the material properties of peripapillary sclera, we constructed a controlled-environment testing apparatus capable of performing uniaxial biomechanical testing of soft tissues in tension. The overall response of a tissue to a load is the combination of instantaneous (elastic) and time-dependent (viscous) responses, which are governed by its viscoelastic material properties. All soft tissues are viscoelastic, and the characterization of the instantaneous and time-dependent aspects of these material properties is important in understanding a tissue's behavior as a load-bearing structure and its response to short-and long-term changes in the applied load. Accurate characterization of a tissue's material properties can lead to a broader understanding of the mechanisms that underlie tissue damage, as well as determine the resultant altered load-bearing behavior of a remodeled or healed tissue. In a previous report we performed quadrant-based uniaxial tensile testing of peripapillary sclera from normal rabbit and normal monkey eyes 3 and found no differences in the viscoelastic material properties of the peripapillary sclera by quadrant (superior, inferior, nasal, and temporal to the ONH) in either species. In addition, when normal rabbit and monkey sclera were compared with one another, peripapillary sclera from monkey eyes was stiffer and showed slower stress relaxation than sclera from rabbit eyes. The present study tests the hypothesis that changes in the viscoelastic material properties of monkey peripapillary sclera are present at the earliest detectable stage of glaucomatous damage to the ONH, defined as the onset of confocal scanning laser tomography (CSLT)-detected ONH surface change. MATERIALS AND METHODS Animals, Scleral Specimens, and Study Design All animals were treated in accordance with the ARVO Statement for the Use of Animals in Ophthalmic and Vision Research. In the present study, a single scleral tensile specimen was generated from either the superior or inferior quadrant of eight eyes with experimental early glaucoma, yielding four early-glaucoma specimens for each quadrant. Each specimen underwent a multistage uniaxial tensile test. ViscoelasFrom th

14-19 education reform under New Labour : an exploration of how politics and the economy combine with educational goals to affect policy

The area of 14-19 education and training was a significant priority for the Labour Government of Tony Blair and New Labour. Reforms such as the 14-19 White Paper (Feb 2005) were seen as key to this government’s ‘third term’ agenda. This research has at its heart the desire to identify the true drivers for 14-19 education and training reform, and critically analyse the results against alternative ‘aims’ of education. Much of current policy for this phase of education mentions the economic imperative of providing young people with the skills which both they and businesses need to compete in the global economy. This research intends to question the fact that economic goals appear to be inexorably entwined with this area of education, and analyse if this is an appropriate philosophy on which to base reform of the 14-19 phase. To achieve this, document analysis was used to identify the drivers for education reform contained within five policy documents in an attempt to understand the goals of New Labour’s 14- 19 education and training reform policy between May 1997 and February 2005. The conclusions which came from this analysis point to a consistency in the 14-19 reform programme of New Labour around the theme of the economy, with much of the content of the reforms focusing on adapting the phase in order to promote economic objectives. It is argued that by accepting economic objectives as a basis for educational reform, New Labour confused the influence of the economy for an educational aim

Deletion of Neurturin Impairs Development of Cholinergic Nerves and Heart Rate Control in Postnatal Mouse Hearts

The neurotrophic factor neurturin is required for normal cholinergic innervation of adult mouse heart and bradycardic responses to vagal stimulation. Our goals were to determine effects of neurturin deletion on development of cardiac chronotropic and dromotropic functions, vagal baroreflex response, and cholinergic nerve density in nodal regions of postnatal mice. Experiments were performed on postnatal C57BL/6 wild-type (WT) and neurturin knockout (KO) mice. Serial electrocardiograms were recorded noninvasively from conscious pups using an ECGenie apparatus. Mice were treated with atenolol to evaluate and block sympathetic effects on heart rate (HR) and phenylephrine (PE) to stimulate the baroreflex. Immunohistochemistry was used to label cholinergic nerves in paraffin sections. WT and KO mice showed similar age-dependent increases in HR and decreases in PR interval between postnatal days (P) 2.5 and 21. Treatment with atenolol reduced HR significantly in WT and KO pups at P7.5. PE caused a reflex bradycardia that was significantly smaller in KO pups. Cholinergic nerve density was significantly less in nodal regions of P7.5 KO mice. We conclude that cholinergic nerves have minimal influence on developmental changes in HR and PR, QRS, and QTc intervals in mouse pups. However, cholinergic nerves mediate reflex bradycardia by 1 week postnatally. Deletion of neurturin impairs cholinergic innervation of the heart and the vagal efferent component of the baroreflex early during postnatal development

Self-interest And Public Interest: The Motivations Of Political Actors

Self-Interest and Public Interest in Western Politics showed that the public, politicians, and bureaucrats are often public spirited. But this does not invalidate public-choice theory. Public-choice theory is an ideal type, not a claim that self-interest explains all political behavior. Instead, public-choice theory is useful in creating rules and institutions that guard against the worst case, which would be universal self-interestedness in politics. In contrast, the public-interest hypothesis is neither a comprehensive explanation of political behavior nor a sound basis for institutional design

Does direct democracy hurt immigrant minorities?: evidence from naturalization decisions in Switzerland

Do minorities fare worse under direct democracy than under representative democracy? We provide new evidence by studying naturalization requests of immigrants in Switzerland that were typically decided with referendums in each municipality. Using panel data from about 1,400 municipalities for the 1991–2009 period, we exploit Federal Court rulings that forced municipalities to transfer the decisions to their elected municipality councils. We find that naturalization rates surged by about 60% once politicians rather than citizens began deciding on naturalization applications. Whereas voters in referendums face no cost of arbitrarily rejecting qualified applicants based on discriminatory preferences, politicians in the council are constrained to formally justify rejections and may be held accountable by judicial review. Consistent with this mechanism, the increase in naturalization rates caused by switching from direct to representative democracy is much stronger for more marginalized immigrant groups and in areas where voters are more xenophobic or where judicial review is more salient

The behaviour of political parties and MPs in the parliaments of the Weimar Republic

Copyright @ 2012 The Authors. This is the author's accepted manuscript. The final published article is available from the link below.Analysing the roll-call votes of the MPs of the Weimar Republic we find: (1) that party competition in the Weimar parliaments can be structured along two dimensions: an economic left–right and a pro-/anti-democratic. Remarkably, this is stable throughout the entire lifespan of the Republic and not just in the later years and despite the varying content of votes across the lifespan of the Republic, and (2) that nearly all parties were troubled by intra-party divisions, though, in particular, the national socialists and communists became homogeneous in the final years of the Republic.Zukunftskolleg, University of Konstan

Science and Ideology in Economic, Political, and Social Thought

This paper has two sources: One is my own research in three broad areas: business cycles, economic measurement and social choice. In all of these fields I attempted to apply the basic precepts of the scientific method as it is understood in the natural sciences. I found that my effort at using natural science methods in economics was met with little understanding and often considerable hostility. I found economics to be driven less by common sense and empirical evidence, then by various ideologies that exhibited either a political or a methodological bias, or both. This brings me to the second source: Several books have appeared recently that describe in historical terms the ideological forces that have shaped either the direct areas in which I worked, or a broader background. These books taught me that the ideological forces in the social sciences are even stronger than I imagined on the basis of my own experiences. The scientific method is the antipode to ideology. I feel that the scientific work that I have done on specific, long standing and fundamental problems in economics and political science have given me additional insights into the destructive role of ideology beyond the history of thought orientation of the works I will be discussing