The vicinal difluoro motif : the synthesis and conformation of erythro- and threo-diastereoisomers of 1,2-difluorodiphenylethanes, 2,3-difluorosuccinic acids and their derivatives

Background: It is well established that vicinal fluorines (RCHF-CHFR) prefer to adopt a gauche rather than an anti conformation when placed along aliphatic chains. This has been particularly recognised for 1,2-difluoroethane and extends to 2,3-difluorobutane and longer alkyl chains. It follows in these latter cases that if erythro and threo vicinal difluorinated stereoisomers are compared, they will adopt different overall conformations if the fluorines prefer to be gauche in each case. This concept is explored in this paper with erythro- and threo- diastereoisomers of 2,3-difluorosuccinates. Results: A synthetic route to 2,3-difluorosuccinates has been developed through erythro- and threo- 1,2-difluoro-1,2-diphenylethane which involved the oxidation of the aryl rings to generate the corresponding 2,3- difluorosuccinic acids. Ester and amide derivatives of the erythro- and threo- 2,3-difluorosuccinic acids were then prepared. The solid and solution state conformation of these compounds was assessed by X-ray crystallography and NMR. Ab initio calculations were also carried out to model the conformation of erythro- and threo- 1,2-difluoro-1,2-diphenylethane as these differed from the 2,3-difluorosuccinates. Conclusion: In general the overall chain conformations of the 2,3-difluorosuccinates diastereoisomers were found to be influenced by the fluorine gauche effect. The study highlights the prospects of utilising the vicinal difluorine motif (RCHF-CHFR) as a tool for influencing the conformation of performance organic molecules and particularly tuning conformation by selecting specific diastereoisomers (erythro or threo).Publisher PDFPeer reviewe

CAP-reform and the provision of non-commodity outputs in Brandenburg

This paper presents an attempt to model the response of selected farms to decoupled direct payments and the associated impact on the provision of a defined set of non-commodity outputs (NCO’s) using a combined modelling approach consisting of the AgriPoliS and MODAM models. AgriPoliS focuses on the socio-economic dimension of multifunctionality at the individual farm and regional levels and explicitly models heterogeneous farms (in size, location and efficiency) within a competitive and dynamic environment. The linear-programming model MODAM allows a detailed representation of production processes and their impact on the environmental dimension of multifunctionality at the farm level. We simulate the impact of a uniform area payment and a fully decoupled single farm payment. Our case study region is the district Ostprignitz-Ruppin in Brandenburg. Results show that the decoupling schemes create a trade-off between the NCO’s and that adjustment reactions differ between farms depending on their legal form, size, and production.decoupling, multifunctionality, non-commodity outputs, modelling, simulation, policy analysis, ecological indicators, Agricultural and Food Policy, Land Economics/Use,

CJK- Improved LO Parton Distributions in the Real Photon and Their Experimental Uncertainties

A new analysis of the radiatively generated, LO quark (u,d,s,c,b) and gluon densities in the real, unpolarized photon, improved in respect to our paper [1], is presented. We perform four new global fits to the experimental data for F2^gamma, two using a standard FFNS approach and two based on ACOT(chi) scheme [2], leading to the FFNS(CJK) and CJK models. We also present the analysis of the uncertainties of the new CJK 2 parton distributions due to the experimental errors, the very first such analysis performed for the photon. This analysis is based on the Hessian method, for a comparison for chosen cross-sections we use also the Lagrange method.Comment: Prepared for Photon 2003: International Conference on the Structure and Interactions of the Photon (Including the 15th International Workshop on Photon-Photon Collisions), Frascati (Italy), 7-11 April 2003; 10 pages, Latex using espcrc2 style, 1 tex and 5 postscript figures; FORTRAN programs available at http://www.fuw.edu.pl/~pjank/param.htm

Regularization Dependence of Running Couplings in Softly Broken Supersymmetry

We discuss the dependence of running couplings on the choice of regularization method in a general softly-broken N=1 supersymmetric theory. Regularization by dimensional reduction respects supersymmetry, but standard dimensional regularization does not. We find expressions for the differences between running couplings in the modified minimal subtraction schemes of these two regularization methods, to one loop order. We also find the two-loop renormalization group equations for gaugino masses in both schemes, and discuss the application of these results to the Minimal Supersymmetric Standard Model.Comment: 11 pages. v2: Signs of equations (1.2) and (4.2) are fixe

Resolved photon and multi-component model for γ∗\gamma^*p and γ∗γ∗\gamma^* \gamma^* scattering at high energies

We generalize our previous model for $\gamma^* p$ scattering to $\gamma \gamma$ scattering. In the latter case the number of components naturally grows. When using the model parameters from our previous $\gamma^* p$ analysis the model cross section for $\gamma \gamma$ scattering is larger than the corresponding LEP2 experimental data by more than a factor of two. However, performing a new simultaneous fit to $\gamma^* p$ and $\gamma \gamma$ total cross section we can find an optimal set of parameters to describe both processes. We propose new measures of factorization breaking for $\gamma^* \gamma^*$ collisions and present results for our new model.Comment: 23 pages, 10 figure

Measuring and Assessing Urban Sprawl: What are the Remaining Options for Future Settlement Development in Switzerland for 2030?

Transformation of land use in and around European cities is proceeding as fast as never before, and urban sprawl is a reality in Europe. This process is coming along with significant landscape changes that can even lead to the loss of landscape identity. Is it possible to find indications of which regions are prone to urban sprawl in order to curtail undesired future settlement developments in time? To answer this question we used settlement development scenarios for Switzerland, and analysed their spatial implications using a set of four metrics, which allow for comparing the degree of urban sprawl in different regions. Two aspects were explored: (1) by how much settlement development could potentially increase in Switzerland, and (2) the suitability of the metrics as indicators for characterizing and assessing the development of urban sprawl. The results show that overall in Switzerland the urban permeation and dispersion of settlement areas is likely to increase (in all scenarios), but to different degrees. However, the results differ very much between the various types of settlement and between the cantons, and even a decrease in urban dispersion is possible. In combination with scenarios of settlement growth, the metrics provide useful evidence on regional characteristics such as the overall pressure of settlement development and likely transformations of the respective settlement types that should be taken into account in spatial development concepts. There is a need for calibration of the indicators on a regional level to define specific thresholds to limit urban spraw

Preclinical evaluation of NF-kappa B-triggered dendritic cells expressing the viral oncogenic driver of Merkel cell carcinoma for therapeutic vaccination

Background: Merkel cell carcinoma (MCC) is a rare but very aggressive skin tumor that develops after integration of a truncated form of the large T-antigen (truncLT) of the Merkel cell polyomavirus (MCV) into the host’s genome. Therapeutic vaccination with dendritic cells (DCs) loaded with tumor antigens is an active form of immunotherapy, which intends to direct the immune system towards tumors which express the respective vaccination antigens. Methods: Cytokine-matured monocyte-derived DCs of healthy donors and MCC patients were electroporated with mRNA encoding the truncLT. To permit major histocompatibility complex (MHC) class II next to class I presentation, we used an RNA construct in which the antigen was fused to a DCLamp sequence in addition to the unmodified antigen. To further improve their immunogenicity, the DCs were additionally activated by co-transfection with the constitutively active nuclear factor (NF)-κB activator caIKK. These DCs were used to stimulate autologous CD8 + T-cells or a mixture of CD4 + and CD8 + T-cells. Then the percentage of T-cells, specific for the truncLT, was quantified by interferon (IFN)γ ELISpot assays. Results: Both the truncLT and its DCLamp-fusion were detected within the DCs by flow cytometry, albeit the latter required blocking of the proteasome. The transfection with caIKK upregulated maturation markers and induced cytokine production. After 2–3 rounds of stimulation, the T-cells from 11 out of 13 healthy donors recognized the antigen. DCs without caIKK appeared in comparison less potent in inducing such responses. When using cells derived from MCC patients, we could induce responses for 3 out of 5 patients; however, here the caIKK-transfected DCs did not display their superiority. Conclusion: These results show that optimized DCs are able to induce MCV-antigen-specific T-cell responses. Therapeutic vaccination with such transfected DCs could direct the immune system against MCC

Electroproduction Cross Section of Large_Et Hadrons at NLO and Virtual Photon Structure Function

We calculate Higher Order corrections to the resolved component of the electroproduction cross section of large-Et hadrons. The parton distributions in the virtual photon are studied in detail and a NLO parametrization of the latter is proposed. The contribution of the resolved component to the forward production of large-Et hadrons is calculated and its connection with the BFKL cross section is discussed.Comment: Latex, 32 pages with 6 figure

Heavy Quark Photoproduction in Ultra-peripheral Heavy Ion Collisions

Heavy quarks are copiously produced in ultra-peripheral heavy ion collisions. In the strong electromagnetic fields, c c-bar and b b-bar are produced by photonuclear and two-photon interactions; hadroproduction can occur in grazing interactions. We present the total cross sections, quark transverse momentum and rapidity distributions, as well as the Q Q-bar invariant mass spectra from the three production channels. We consider AA and pA collisions at the Relativistic Heavy Ion Collider and Large Hadron Collider. We discuss techniques for separating the three processes and describe how the AA to pA production ratios might be measured accurately enough to study nuclear shadowing.Comment: Minor changes to satisfy referees and typo fixes; 52 pages including 17 figure

Integration in European Retail Banking : Evidence from savings and lending rates to non-financial corporations

The aim of this paper is to investigate the integration process in the European Union retail banking sector during the period 1995-2008, by analysing deposit and lending rates to nonfinancial corporations which represent one of the main constituents of retail banking. An important contribution of the paper is the application of the recently developed Phillips and Sul (2007a) panel convergence methodology which has not hitherto been employed in this area. This method analyses the degree as well as the speed of convergence, identifies the presence of club formation, and measures the behaviour of each country’s transition path relative to the panel average. The results obtained point to the presence of close convergence in all deposit rates and in the short-term lending rates to non-financial corporations. However, we also detect the presence of heterogeneity in the European retail banking sector with notably some diverse convergence patterns observed for the transition paths for the deposit and lending rates with longer maturities.Submitted Versio