New Radicals and new applications of Dynamic Nuclear Polarization of biological systems

Dynamic Nuclear Polarization (DNP) is an emerging technique that could revolutionize the NMR study of small molecules at very low concentrations by the increase in sensitivity that results from transfer of polarization between electronic and nuclear spins. Although the underlying physics has been known for a long time, in the last few years there has been a lot of excitement on the chemistry and biology NMR community caused by the demonstration that the highly polarized nuclei that are prepared in solid state at very low temperatures (1-2 K) could be rapidly transferred to liquid samples at room temperature and studied in solution by conventional NMR techniques. In favorable cases several order of magnitude increases in sensitivity have been achieved. The technique is now mature enough that a commercial instrument is available. The efficiency of DNP depends on two crucial aspects: i) the efficiency of the nuclear polarization process and ii) the efficiency of the transfer from the initial solid state to the fluid state in which NMR is measured. The preferred areas of application (iii) will be dictated by situations in which the low concentration of the sample or its intrinsic low receptivity are the limiting factors .

Cation distribution and magnetization of BaFe12-2xCoxSnxO19 (x=0.9,1.28) single crystals

The distribution of Sn4+ cations within the five crystallographic sites of the magnetoplumbite (M) ‐like compound BaFe12−2xCoxSnxO19 has been analyzed using single‐crystal x‐ray‐diffraction data. The species Fe3+ and Co2+ cannot be distinguished using x rays because of their very similar atomic numbers; however, the calculation of the apparent valencies for the different sites allows an insight into the Co2+ cation segregation. The use of previous data from neutron powder diffraction allows a precise picture of the cation distribution, which indicates a pronounced site selectivity for both Sn4+ and Co2+ cations. The Sn4+ cations prefer the 4f2 sites and to a much lower extent the 12k sites, while they do not enter the octahedral 2a sites at all. Co2+ cations are distributed among tetrahedral and octahedral sites displaying a clear preference for the tetrahedral 4f1 sites. Magnetic measurements indicate that the compound still exhibits uniaxial anisotropy with the easy direction parallel to the c axis. Nevertheless, the magnetic structure shows a considerable degree of noncolinearity. A strong reduction of the magnetic anisotropy regarding that of the undoped compound is also detected.

Cation distribution and high field magnetization studies on SrFe12-xCrxO19

With the aim of a better understanding of both cationic distribution and magnetic properties of the uniaxial SrFe12-xCrxO19hexagonal ferrites, Mössbauer spectroscopy, neutron diffraction and high field magnetization measurements have been carried out. The Cr3+ions occupy the octahedral sites of the M structure with a preference hierarchy within them. The magnetic measurements, together with the deduced cationic distribution, indicate that some sublattices have a random spin canting around the c-axis.

Cation distribution and magnetization of BaFe12-2xCoxSnxO19 (x=0.9,1.28) single crystals

The distribution of Sn4+ cations within the five crystallographic sites of the magnetoplumbite (M) ‐like compound BaFe12−2xCoxSnxO19 has been analyzed using single‐crystal x‐ray‐diffraction data. The species Fe3+ and Co2+ cannot be distinguished using x rays because of their very similar atomic numbers; however, the calculation of the apparent valencies for the different sites allows an insight into the Co2+ cation segregation. The use of previous data from neutron powder diffraction allows a precise picture of the cation distribution, which indicates a pronounced site selectivity for both Sn4+ and Co2+ cations. The Sn4+ cations prefer the 4f2 sites and to a much lower extent the 12k sites, while they do not enter the octahedral 2a sites at all. Co2+ cations are distributed among tetrahedral and octahedral sites displaying a clear preference for the tetrahedral 4f1 sites. Magnetic measurements indicate that the compound still exhibits uniaxial anisotropy with the easy direction parallel to the c axis. Nevertheless, the magnetic structure shows a considerable degree of noncolinearity. A strong reduction of the magnetic anisotropy regarding that of the undoped compound is also detected.

Polychlorinated trityl radicals for dynamic nuclear polarization: the role of chlorine nuclei

Polychlorinated trityl radicals bearing carboxylate substituents are water soluble persistent radicals that can be used for dynamic nuclear polarization. In contrast to other trityl radicals, the polarization mechanism differs from the classical solid effect. DFT calculations performed to rationalize this behaviour support the hypothesis that polarization is transferred from the unpaired electron to chlorine nuclei and from these to carbon by spin diffusion. The marked differences observed between neutral and anionic forms of the radical will be discussed.

TGF-β dependent regulation of oxygen radicals during transdifferentiation of activated hepatic stellate cells to myofibroblastoid cells

Background: The activation of hepatic stellate cells (HSCs) plays a pivotal role during liver injury because the resulting myofibroblasts (MFBs) are mainly responsible for connective tissue re-assembly. MFBs represent therefore cellular targets for anti-fibrotic therapy. In this study, we employed activated HSCs, termed M1-4HSCs, whose transdifferentiation to myofibroblastoid cells (named M-HTs) depends on transforming growth factor (TGF)-β. We analyzed the oxidative stress induced by TGF-β and examined cellular defense mechanisms upon transdifferentiation of HSCs to M-HTs. Results: We found reactive oxygen species (ROS) significantly upregulated in M1-4HSCs within 72 hours of TGF-β administration. In contrast, M-HTs harbored lower intracellular ROS content than M1-4HSCs, despite of elevated NADPH oxidase activity. These observations indicated an upregulation of cellular defense mechanisms in order to protect cells from harmful consequences caused by oxidative stress. In line with this hypothesis, superoxide dismutase activation provided the resistance to augmented radical production in M-HTs, and glutathione rather than catalase was responsible for intracellular hydrogen peroxide removal. Finally, the TGF-β/NADPH oxidase mediated ROS production correlated with the upregulation of AP-1 as well as platelet-derived growth factor receptor subunits, which points to important contributions in establishing antioxidant defense. Conclusion: The data provide evidence that TGF-β induces NADPH oxidase activity which causes radical production upon the transdifferentiation of activated HSCs to M-HTs. Myofibroblastoid cells are equipped with high levels of superoxide dismutase activity as well as glutathione to counterbalance NADPH oxidase dependent oxidative stress and to avoid cellular damage.

When do central banks prefer to intervene secretly?

Central banks often intervene secretly in the foreign exchange market. This secrecy seems to be at odds with the signalling channel. In this article we will analyse when a central bank intervening in the foreign exchange rate market purely through the signalling channel would prefer to act secretly or publicly. By using a microstructure model, we will show that the consistency of the intervention with fundamentals, the volume of noise trading, the weight given to the effectiveness of intervention and the degree of superior information held by the central bank will influence the decision to intervene secretly or publicly. Keywords: foreign exchange intervention, market microstructure. JEL Classifi…cation: D82, E58, F31, G14.

Transferència d’electrò i protó als intermediaris de reacció de les hemo-catalases

Projecte de recerca elaborat a partir d’una estada a l’University of Pennsylvania, EUA, entre els mesos d’agosta a desembre del 2006. Les hemo-catalases són enzims que protegeixen les cèl•lules dels efectes tòxics del peròxid d'hidrogen. Aquesta reacció té lloc en dues etapes, via l'intermediari Compost I (Cpd I). Tanmateix, el Compost I pot seguir una reacció secundària, a través de l'intermediari Compost II. Hi ha dos tipus d'hemo-catalases: les hemo-b (com la d'Helicobacter pylori, HPC) i les hemo-d catalases (com la de Penicillium vitale, PVC). Experimentalment s'observa que les hemo-b catalases formen Cpd II més fàcilment que les hemo-d. La formació del Cpd II consta de dos processos: la reducció del catió radical porfirínic i la protonació del grup oxoferril. Durant l'estada, es va estudiar el procès de transferència electrònica a la porfirina utilitzant una metodologia desenvolupada recentment. Els resultats mostren que per PVC la reducció és més fàcil que per HPC. Posteriorment hem realitzat una sèrie de optimitzacions de geometria CPMD QM/MM al llarg del camí per la transferència de protó (PT) de la histidina distal a l'oxoferril. Mentre que per HPC aquesta PT és espontània, per PVC l'isòmer hidroxoferrílic és menys estable que el catió imidazoli.

Decentralization and the Gains from Monitoring

This paper analyzes the delegation of contracting capacity in a moral hazard environment with sequential production in a project which involves a principal and two agents. The agent in charge of the …nal production can obtain soft information about the other agent's effort choice by investing in monitoring. I investigate the circumstances under which it is optimal for the principal to use a centralized organization in which she designs the contracts with both agents or to use a decentralized organization in which she contracts only one agent, and delegates the power to contract the other agent. It is shown that in this setting a decentralized organization can be superior to a centralized organization. This is because the principal is better off under monitoring and the incentives for an agent to invest in monitoring can be higher in a decentralized organization. The circumstances under which this is true are related to the monitoring costs and the importance of each agent for production. The results explain the recent application of the design-build method in public procurement. Journal of Economic Literature Classi…cation Numbers: D23, D82, L14, L22. Keywords: Decentralization of Contracting, Monitoring, Moral Hazard.

Information Dispersion and Equilibrium Multiplicity

This paper studies the implications of correlation of private signals about the liquidation value of a risky asset in a variation of a standard noisy rational expectations model in which traders receive endowment shocks which are private information and have a common component. We …nd that a necessary condition to generate multiple linear partially revealing rational expectations equilibria is the existence of several sources of information dispersion. In this context equilibrium multiplicity tends to occur when information is more dispersed. A necessary condition to have strategic complementarity in information acquisition is to have mul- tiple equilibria. When the equilibrium is unique there is strategic substi- tutability in information acquisition, corroborating the result obtained in Grossman and Stiglitz (1980). JEL Classi…cation: D82, D83, G14 Keywords: Multiplicity of equilibria, strategic complementarity, asym- metric information.

Nacionalismo e identidad nacional en Corea, 1876-1945

Este trabajo de investigación tiene como objetivo el análisis de las circunstancias sociopolíticas que propiciaron la aparición y consolidación del nacionalismo como paradigma dominante en la creación de una nueva identidad colectiva coreana. El nacionalismo ha sido, en las últimas décadas, el discurso dominante dentro de la sociedad y la política coreana. De la derecha a la izquierda, pasando por los conservadores y los radicales, el pueblo coreano ha acogido de manera análoga el discurso nacionalista, siendo un instrumento utilizado abiertamente por las diferentes fuerzas gubernamentales para su propia legitimación política y moral tanto en el norte como en el sur.

Sincere Lobby Formation

This paper analyzes endogenous lobbying over a unidimensional policy issue. Individuals differ in policy preferences and decide either to join one of two opposite interest lobbies or not to take part in lobbying activities. Once formed, lobbies make contributions to the incumbent government in exchange for a policy favor as in a common-agency model. A "sincere-lobby-formation" condition for equilibrium is introduced: an individual joins a lobby if their gain from the policy change that this lobby might achieve exceeds a contribution fee. Thus, an equilibrium occurs only if no lobby member would prefer their lobby to cease to exist. I show the existence of an equilibrium with two organized lobbies. Individuals with more extreme preferences are more likely to join lobbying activities. I fi…nd that lobbying somewhat moderates the government's preferences, i.e., it shifts the …final policy in favor of individuals who are initially disadvantaged by the government's pro- or anti-policy preferred position. Under a utilitarian government, however, lobbying does not affect the fi…nal policy, and political competition results in a socially optimal outcome. JEL classi…cation: D72. Keywords: Sincere lobby formation; common agency; endogenous lobbying.

A Political Agency Model of Coattail Voting

In this paper, I provide a formal justi…cation for a well-established coattail effect, when a popular candidate at one branch of government attracts votes to candidates from the same political party for other branches of government. A political agency frame- work with moral hazard is applied to analyze coattails in simultaneous presidential and congressional elections. I show that coattail voting is a natural outcome of the optimal reelection scheme adopted by a representative voter to motivate politicians' efforts in a retrospective voting environment. I assume that an office-motivated politician (executive or congressman) prefers her counterpart to be affiliated with the same political party. This correlation of incentives leads the voter to adopt a joint performance evaluation rule, which is conditioned on the politicians belonging to the same party or different parties. The two-sided coattail effects then arise. On the one hand, the executive's suc- cess/failure props up/drags down her partisan ally in congressional election, which implies presidential coattails. On the other hand, the executive's reelection itself is affected by the congressman's performance, which results in reverse coattails. JEL classi…fication: D72, D86. Keywords: Coattail voting; Presidential coattails; Reverse coattails; Simultaneous elections; Political Agency; Retrospective voting.

A Model of Party Discipline in a Congress

This paper studies party discipline in a congress within a political agency framework with retrospective voting. Party discipline serves as an incentive device to induce office- motivated congress members to perform in line with the party leadership's objective of controlling both the executive and the legislative branches of government. I show fi…rst that the same party is more likely to control both branches of government (i.e., uni…ed government) the stronger the party discipline in the congress is. Second, the leader of the governing party imposes more party discipline under uni…ed government than does the opposition leader under divided government. Moreover, the incumbents' aggregate performance increases with party discipline, so a representative voter becomes better off. JEL classi…cation: D72. Keywords: Party discipline; Political agency; Retrospective voting; Office-motivated politicians.

Cronyism in Business, Public Sector and Politics

This paper contrasts the incentives for cronyism in business, the public sector and politics within an agency problem model with moral hazard. The analysis is focused on the institutional differences between private, public and political organizations. In business, when facing a residual claimant contract, a chief manager ends up with a relatively moderate …rst-best level of cronyism within a …firm. The institutional framework of the public sector does not allow explicit contracting, which leads to a more severe cronyism problem within public organizations. Finally, it is shown that the nature of political appointments (such that the subordinate's reappointment is conditioned on the chief's re-election) together with implicit contracting makes political cronyism the most extreme case. JEL classifi…cation: D72, D73, D86. Keywords: Cronyism; Meritocracy; Manager; Bureaucrat; Politician.