Excited-State Structure, Vibrations, and Nonradiative Relaxation of Jet-Cooled 5-Fluorocytosine

The S0 → S1 vibronic spectrum and S1 state nonradiative relaxation of jet-cooled keto-amino 5-fluorocytosine (5FCyt) are investigated by two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm–1 resolution. The 000 rotational band contour is polarized in-plane, implying that the electronic transition is 1ππ*. The electronic transition dipole moment orientation and the changes of rotational constants agree closely with the SCS-CC2 calculated values for the 1ππ* (S1) transition of 5FCyt. The spectral region from 0 to 300 cm–1 is dominated by overtone and combination bands of the out-of-plane ν1′ (boat), ν2′ (butterfly), and ν3′ (HN–C6H twist) vibrations, implying that the pyrimidinone frame is distorted out-of-plane by the 1ππ* excitation, in agreement with SCS-CC2 calculations. The number of vibronic bands rises strongly around +350 cm–1; this is attributed to the 1ππ* state barrier to planarity that corresponds to the central maximum of the double-minimum out-of-plane vibrational potentials along the ν1′, ν2′, and ν3′ coordinates, which gives rise to a high density of vibronic excitations. At +1200 cm–1, rapid nonradiative relaxation (knr ≥ 1012 s–1) sets in, which we interpret as the height of the 1ππ* state barrier in front of the lowest S1/S0 conical intersection. This barrier in 5FCyt is 3 times higher than that in cytosine. The lifetimes of the ν′ = 0, 2ν1′, 2ν2′, 2ν1′ + 2ν2′, 4ν2′, and 2ν1′ + 4ν2′ levels are determined from Lorentzian widths fitted to the rotational band contours and are τ ≥ 75 ps for ν′ = 0, decreasing to τ ≥ 55 ps at the 2ν1′ + 4ν2′ level at +234 cm–1. These gas-phase lifetimes are twice those of S1 state cytosine and 10–100 times those of the other canonical nucleobases in the gas phase. On the other hand, the 5FCyt gas-phase lifetime is close to the 73 ps lifetime in room-temperature solvents. This lack of dependence on temperature and on the surrounding medium implies that the 5FCyt nonradiative relaxation from its S1 (1ππ*) state is essentially controlled by the same ∼1200 cm–1 barrier and conical intersection both in the gas phase and in solution.

Excited state interactions between the chiral Au 38 L 24 cluster and covalently attached porphyrin

A protected S-acetylthio porphyrin was synthesized and attached to the Au38(2-phenylethanethiolate)24 cluster in a ligand exchange reaction. Chiral high performance liquid chromatography of the functionalized cluster yielded enantiomeric pairs of clusters probably differing in the binding site of the porphyrin. As proven by circular dichroism, the chirality was maintained. Exciton coupling between the cluster and the chromophore is observed. Zinc can be incorporated into the porphyrin attached to the cluster, as evidenced by absorption and fluorescence spectroscopy, however, the reaction is slow. Quenching of the chromophore fluorescence is observed, which can be explained by energy transfer from the porphyrin to the cluster. Transient absorption spectra of Au38(2-phenylethanethiolate)24 and the functionalized cluster probe the bleach of the gold cluster due to ground state absorption and the characteristic excited state absorption signals. Zinc incorporation does not have a pronounced effect on the photophysical behaviour. Decay times are typical for the molecular behaviour of small monolayer protected gold clusters.

Humanitarian intervention and the issue of state sovereignty in the discourse of legal experts between the 1830s and the First World War

This article discusses the tensions between the principle of state sovereignty and the idea of a "humanitarian intervention" (or a intervention on humanitarian grounds) as they resulted from the debate of leading legal scholars in the 19th and early 20th century. While prominent scholars such as Johann Caspar Bluntschli, Gustave Rolin Jaequemyns or Aegidius Arntz spoke out in favour of a form of "humanitarian interventions", others such as August Wilhelm Heffter or Pasquale Fiore were much more critical and in many cases spoke out in favour of absolute state sovereignty.

The welfare state determinants of health: Implications of regimes and pathways

Background. Population health within and between nations is heavily influenced by political determinants, yet these determinants have received significantly less attention than socioeconomic factors in public health. It has been hypothesized that the welfare state, as a political variable, may play a particularly prominent role in affecting both health indicators and health disparities in developed countries. The research, however, provides conflicting evidence regarding the health impact of particular regimes over others and the mechanisms through which the welfare state can most significantly affect health.^ Objective. To perform a systematic review of the literature as a means of exploring what the current research indicates regarding the benefits or detriments of particular regimes styles and the pathways through which the welfare state can impact heath indicators and health disparities within developed countries.^ Methods. A thorough search of the EBSCO, Pubmed, Medline, Web of Science, and Scopus electronic databases was conducted and resulted in the identification of 15 studies that evaluated the association between welfare state regime and population health outcomes, and/or pathways through with the welfare state influences health. ^ Results. Social democratic countries tended to perform best when infant mortality rate (IMR) was the primary outcome of interest, whereas liberal countries performed strongly in relation to self perceived health. The results were mixed regarding welfare state effectiveness in mitigating health inequities, with Christian democratic countries performing as well as social democratic countries. In relation to welfare state pathways, public health spending and medical coverage were associated with positive health indicators. Redistributive impact of the welfare state was also consistently associated with better health outcomes while social security expenditures were not.^ Discussion/Conclusions. Studies consistently discovered a significant relationship between the welfare state and population health and/or health disparities, lending support to the hypothesis that the welfare state is, indeed, an important non-medical determinant of health. However, it is still fairly unclear which welfare state regime may be most protective for health, as results varied according to the measured health indicator. The research regarding welfare state pathways is particularly undeveloped, and does not provide much insight into the importance of in-kind service provision or cash transfers, or targeted or universal approaches to the welfare state. Suggestions to direct future research are provided.^

The movement toward patient safety: State action related to reporting and disclosure of healthcare-associated infections

Increasing attention has been given to the problem of medical errors over the past decade. Included within that focused attention has been a strong interest in reducing the occurrence of healthcare-associated infections (HAIs). Acting concurrently with federal initiatives, the majority of U.S. states have statutorily required reporting and public disclosure of HAI data. Although the occurrence of these state statutory enactments and other state initiatives represent a recognition of the strong concern pertaining to HAIs, vast differences in each state’s HAI reporting and public disclosure requirements creates a varied and unequal response to what has become a national problem.^ The purpose of this research was to explore the variations in state HAI legal requirements and other state mandates. State actions, including statutory enactments, regulations, and other initiatives related to state reporting and public disclosure mechanisms were compared, discussed, and analyzed in an effort to illustrate the impact of the lack of uniformity as a public health concern.^ The HAI statutes, administrative requirements, and other mandates of each state and two U.S. territories were reviewed to answer the following seven research questions: How far has the state progressed in its HAI initiative? If the state has a HAI reporting requirement, is it mandatory or voluntary? What healthcare entities are subject to the reporting requirements? What data collection system is utilized? What measures are required to be reported? What is the public disclosure mechanism? How is the underlying reported information protected from public disclosure or other legal release?^ Secondary publicly available data, including state statutes, administrative rules, and other initiatives, were utilized to examine the current HAI-related legislative and administrative activity of the study subjects. The information was reviewed and analyzed to determine variations in HAI reporting and public disclosure laws. Particular attention was given to the seven key research questions.^ The research revealed that considerable progress has been achieved in state HAI initiatives since 2004. Despite this progress, however, when reviewing the state laws and HAI programs comparatively, considerable variations were found to exist with regards to the type of reporting requirements, healthcare facilities subject to the reporting laws, data collection systems utilized, reportable measures, public disclosure requirements, and confidentiality and privilege provisions. The wide variations in state statutes, administrative rules, and other agency directives create a fragmented and inconsistent approach to addressing the nationwide occurrence of HAIs in the U.S. healthcare system. ^

Gacaca and DDR : the disputable record of state-building in Rwanda

State-building is currently considered to be an indispensable process in overcoming state fragility: a condition characterized by frequent armed conflicts as well as chronic poverty. In this process, both the capacity and the legitimacy of the state are supposed to be enhanced; such balanced development of capacity and legitimacy has also been demanded in security sector reform (SSR), which is regarded as being a crucial part of post-conflict state-building. To enhance legitimacy, the importance of democratic governance is stressed in both state-building and SSR in post-conflict countries. In reality, however, the balanced enhancement of capacity and legitimacy has rarely been realized. In particular, legitimacy enhancement tends to stagnate in countries in which one of multiple warring parties takes a strong grip on state power. This paper tries to understand why such unbalanced development of state-building and SSR has been observed in post-conflict countries, through a case study of Rwanda. Analyses of two policy initiatives in the security sector - Gacaca transitional justice and disarmament, demobilization, and reintegration (DDR) - indicate that although these programs achieved goals set by the government, their contribution to the normative objectives promoted by the international community was quite debatable. It can be understood that this is because the country has subordinated SSR to its state-building process. After the military victory of the former rebels, the Rwandan Patriotic Front (RPF), the ruling elite prioritized the establishment of political stability over the introduction of international norms such as democratic governance and the rule of law. SSR was implemented only to the extent that it contributed to, and did not threaten, Rwanda's RPF-led state-building.

Infrastructure Finance in Developing Countries by State and Multilateral Development Banks

Infrastructure concession is an alternative widely used by governments to increase investment. In the case of the road sector, the main characteristics of the concessions are: long-term projects, high investments in the early years of the contract and high risks. A viability analysis must be carried out for each concession and consider the characteristics of the project. When the infrastructure is located in a developing country, political and market growth uncertainties should be add in the concession project analysis, as well as economic instability, because they present greater risks. This paper is an analysis of state bank participation in road infrastructure finance in developing countries. For this purpose, we studied road infrastructure financing and its associated risks, and also the features of developing countries. Furthermore, we considered the issue of state banks and multilateral development banks that perform an important role by offering better credit lines than the private banks, in terms of cost, interest and grace period. Based on this study, we analyzed the Brazilian Development Bank - BNDES – and their credit supply to road infrastructure concessions. The results show that BNDES is the main financing agent for long-term investment in the sector, offering loans with low interest rates in Brazilian currency. From this research we argue that a single state bank should not alone support the increasing demand for finance in Brazil. Therefore, we conclude that there is a need to expand the supply of credit in Brazil, by strengthening private banks in the long-term lending market.

Partial molar volume, surface area, and hydration changes for equilibrium unfolding and formation of aggregation transition state: High-pressure and cosolute studies on recombinant human IFN-γ

The equilibrium dissociation of recombinant human IFN-γ was monitored as a function of pressure and sucrose concentration. The partial molar volume change for dissociation was −209 ± 13 ml/mol of dimer. The specific molar surface area change for dissociation was 12.7 ± 1.6 nm2/molecule of dimer. The first-order aggregation rate of recombinant human IFN-γ in 0.45 M guanidine hydrochloride was studied as a function of sucrose concentration and pressure. Aggregation proceeded through a transition-state species, N*. Sucrose reduced aggregation rate by shifting the equilibrium between native state (N) and N* toward the more compact N. Pressure increased aggregation rate through increased solvation of the protein, which exposes more surface area, thus shifting the equilibrium away from N toward N*. The changes in partial molar volume and specific molar surface area between the N* and N were −41 ± 9 ml/mol of dimer and 3.5 ± 0.2 nm2/molecule, respectively. Thus, the structural change required for the formation of the transition state for aggregation is small relative to the difference between N and the dissociated state. Changes in waters of hydration were estimated from both specific molar surface area and partial molar volume data. From partial molar volume data, estimates were 25 and 128 mol H2O/mol dimer for formation of the aggregation transition state and for dissociation, respectively. From surface area data, estimates were 27 and 98 mol H2O/mol dimer. Osmotic stress theory yielded values ≈4-fold larger for both transitions.

The Economics of State Aid for the Rescue and Restructuring of Firms in Difficulty: Theoretical Considerations, Empirical Analysis and Proposals for Reform. Bruges European Economic Research (BEER) Papers 27/September 2013

State aid for rescue and restructuring (R&R) of companies in difficulty causes a significant distortion of competition. It prevents the market from eliminating inefficient companies. Because of this, the European Commission has to be specially strict when it assesses rescue or restructuring aid. This paper examines recent cases of corporate restructuring partly funded with public money. It explains the main aspects of the current guidelines which are applicable to R&R State Aid and establishes a theoretical framework for the economic assessment of R&R aid. It then analyses decisions adopted by the European Commission concerning R&R state aid during the period 2000-2013. It finds that there is little economic rationale in the granting of R&R aid. The paper concludes by applying the lessons drawn from the empirical analysis to the anticipated revision of the R&R guidelines in the context of the State Aid Modernisation process.

The Emergence of a Network of ‘European Embassies’: Increasing Cooperation between EU Delegations and Member State Diplomatic Missions. EU Diplomacy Paper No. 10, December 2014

Five years after the entry into force of the Treaty of Lisbon and at the end of the first mandate of the High Representative of the Union for Foreign Affairs and Security Policy/Vice-President of the European Commission (HR/VP), this analysis provides an in-depth view of the on-going institutional socialisation between Member State Embassies and EU Delegations. Specifically, it focuses on the Member States’ perceptions of the role of EU Delegations. These perceptions can back up or restrain the EU Delegations in fulfilling their mandate. More precisely, the paper examines to what extent the socialisation between EU Delegations and EU Member State Embassies helps the Delegations to fulfil their mandate in bilateral diplomacy. It argues that EU Delegations are still under dynamic processes of institutional socialisation with the Member States’ Embassies which increasingly accept and expect EU Delegations’ actions. The post-Lisbon context of EU Diplomacy is consolidating a primus inter pares role of Delegations being central hubs coordinating and implementing EU policies on the spot.

Syria and Lebanon: Diverging paths of state unsustainability. MEDPRO Technical Report No. 6/June 2011

Any analysis of the prospects for stability and sustainability in the states of Syria and Lebanon reveals the strong ties that exist between these two countries and the impact of external influences on their overall development. Their trajectories, while starkly divergent in terms of the challenges confronting them at present, converge on a path of long-term unsustainability. Lebanon is in the midst of yet another transition phase, triggered by the collapse of Hariri’s government in January 2011. The current situation might be described as one of deteriorating status quo; the state is performing poorly in terms of its delivery of fundamental public services and its institutional legitimacy is tenuous in the face of emerging para-state structures and latent (occasionally active) violence. In Syria, challenges to the sustainability of the state have evolved dramatically since the beginning of 2011, and are now nearing a tipping point. In view of the mounting unrest and violence in the country, the future prospects for its economic and political development are dim. More ominously, the risk of widespread conflict, with sectarian overtones, cannot be discounted.

Social Investment and State Capacity. CEPS Working Document No. 419/February 2016

This paper looks at the difference between the levels and nature of social policy expenditure in northern and northwest European countries and the countries of southern, central, and eastern Europe, and examines the relationship between social investment and state capacity in these country groupings. The authors show that southern and eastern countries have a much greater preference for ‘compensating’ rather than ‘capacitating’ social policy spending. Furthermore, the state capacity in these countries is lower, which generates less state revenue. Based on these observations they conclude that low state capacity and low state revenue go hand in hand with the preference for capacitating social policies, as these policies involve less delegation and discretion than social investment policies. This paper shows that high state capacity is probably a necessary precondition for effective social investment policies, although some limited alternative paths do exist.

The university and the state. An address before the University of Tennessee, June 14, 1898.

Mode of access: Internet.

Church and state : a historical handbook /

Includes index.