Rates of electronic energy transfer in conformationally flexible bichromophoric macrocyclic complexes: a combined experimental and molecular modeling study

Electronic energy transfer (EET) rate constants between a naphthalene donor and anthracene acceptor in [ZnL4a](ClO4)(2) and [ZnL4b](ClO4)(2) were determined by time-resolved fluorescence where L-4a and L-4b are the trans and cis isomers of 6-((anthracen-9-yl-methyl)amino)-6,13-dimethyl-13-((naphthalen-1-yl-methyl)amino)-1,4,8,11-tetraazacyclotetradecane, respectively. These isomers differ in the relative disposition of the appended chromophores with respect to the macrocyclic plane. The trans isomer has an energy transfer rate constant (k(EET)) of 8.7 x 10(8) s(-1), whereas that of the cis isomer is significantly faster (2.3 x 10(9) s(-1)). Molecular modeling was used to determine the likely distribution of conformations in CH3CN solution for these complexes in an attempt to identify any distance or orientation dependency that may account for the differing rate constants observed. The calculated conformational distributions together with analysis by H-1 NMR for the [ZnL4a](2+) trans complex in the common trans-III N-based isomer gave a calculated Forster rate constant close to that observed experimentally. For the [ZnL4b](2+) cis complex, the experimentally determined rate constant may be attributed to a combination of trans-Ill and trans-I N-based isomeric forms of the complex in solution.

Structural definition of the low-temperature phase transition of tris(ethane-1,2-diamine)zinc(II) dinitrate

The 93 K X-ray crystal structure of tris(ethane-1,2-diamine)zinc(II) dinitrate is reported. As predicted by the spectroscopic studies of other workers, there is a reversible phase transition of the structure at low temperature. We have determined this temperature to be 143 K. The structure at this temperature and below resembles that of the room temperature structure, except the crystallographic D-3 symmetry of the complex cation (296 K) is lowered to C-2 ( below 144 K) by subtle changes in cation-anion hydrogen bonding. No change in the conformation of the cation or its bond lengths and angles was found.

Dietary influences on survival after ovarian cancer

We evaluated the effects of various food groups and micronutrients in the diet on survival among women who originally participated in a population-based case-control study of ovarian cancer conducted across 3 Australian states between 1990 and 1993. This analysis included 609 women with invasive epithelial ovarian cancer, primarily because there was negligible mortality in women with borderline tumors. The women's usual diet was assessed using a validated food frequency questionnaire. Deaths in the cohort were identified using state-based cancer registries and the Australian National Death Index (NDI). Crude 5-year survival probabilities were estimated using the Kaplan-Meier technique, and adjusted hazard ratios (HRs) and 95% confidence intervals (CIs) were obtained from Cox regression models. After adjusting for important confounding factors, a survival advantage was observed for those who reported higher intake of vegetables in general (HR = 0.75, 95% CI = 0.57-0.99, p-value trend 0.01 for the highest third, compared to the lowest third), and cruciferous vegetables in particular (HR = 0.75, 95% CI = 0.57-0.98, p-value trend 0.03), and among women in the upper third of intake of vitamin E (HR = 0.76, 95% CI = 0.58-1.01, p-value trend 0.04). Inverse associations were also seen with protein (p-value trend 0.09), red meat (p-value trend 0.06) and white meat (p-value trend 0.07), and modest positive trends (maximum 30% excess) with lactose (p-value trend 0.04), calcium and dairy products. Although much remains to be learned about the influence of nutritional factors after a diagnosis of ovarian cancer, our study suggests the possibility that a diet high in vegetable intake may help improve survival. (C) 2003 Wiley-Liss, Inc.

The tale of a Trojan horse or the quest for market access? China and the World Trade Organization

In 2001, China finally joined the WTO. The accession of China was looked forward to by many WTO members and China itself. However, observers had some fears that the Chinese accession would prove to be a Trojan horse, disrupting the working of the WTO. This paper looks into the Chinese accession and its involvement in the WTO Dispute Settlement and argues that these fears seem so far to be unfounded.

On differentiability and analyticity of positive definite functions

We derive a set of differential inequalities for positive definite functions based on previous results derived for positive definite kernels by purely algebraic methods. Our main results show that the global behavior of a smooth positive definite function is, to a large extent, determined solely by the sequence of even-order derivatives at the origin: if a single one of these vanishes then the function is constant; if they are all non-zero and satisfy a natural growth condition, the function is real-analytic and consequently extends holomorphically to a maximal horizontal strip of the complex plane.

Studies on mosquitoes (Diptera: Culicidae) and anthropic environment: 7- Behaviour of adults Nyssorhynchus anophelines with special reference to Anopheles albitarsis s.l. in South-Eastern Brazil

Results obtained with catches performed at several sites of the Ribeira Valley, SP (Brazil) are reported. Collections with Shannon type traps showed a concentration of An.albitarsis s.l. in the Experimental Farm of Pariquera-Açu County, associated with the development of irrigated rice cultivation. Two species of the complex, named A and B, were recognized. Species B predominated in the samples. Indoor and outdoor crepuscular human bait captures were performed a the domiciliary environment. The two species showed a generally low William's media valve of 0.2, the highest value obtained was 1.6. No differences were found between indoor and outdoor behaviours between the two species of the complex.

Impact of a 1755-like tsunami in Huelva, Spain

Coastal areas are highly exposed to natural hazards associated with the sea. In all cases where there is historical evidence for devastating tsunamis, as is the case of the southern coasts of the Iberian Peninsula, there is a need for quantitative hazard tsunami assessment to support spatial planning. Also, local authorities must be able to act towards the population protection in a preemptive way, to inform 'what to do' and 'where to go' and in an alarm, to make people aware of the incoming danger. With this in mind, we investigated the inundation extent, run-up and water depths, of a 1755-like event on the region of Huelva, located on the Spanish southwestern coast, one of the regions that was affected in the past by several high energy events, as proved by historical documents and sedimentological data. Modelling was made with a slightly modified version of the COMCOT (Cornell Multi-grid Coupled Tsunami Model) code. Sensitivity tests were performed for a single source in order to understand the relevance and influence of the source parameters in the inundation extent and the fundamental impact parameters. We show that a 1755-like event will have a dramatic impact in a large area close to Huelva inundating an area between 82 and 92 km(2) and reaching maximum run-up around 5 m. In this sense our results show that small variations on the characteristics of the tsunami source are not too significant for the impact assessment. We show that the maximum flow depth and the maximum run-up increase with the average slip on the source, while the strike of the fault is not a critical factor as Huelva is significantly far away from the potential sources identified up to now. We also show that the maximum flow depth within the inundated area is very dependent on the tidal level, while maximum run-up is less affected, as a consequence of the complex morphology of the area.

Studies on mosquitoes (Diptera: Culicidae) and anthropic environment. 12- Host-seeking behaviour of Anopheles albitarsis s.l. in South-Eastern Brazil

Results obtained with Anopheles albitarsis s.l. catches mainly performed through human bait at the Ribeira Valley region, SP (Brazil), are reported. Two species of the complex were recognized, namely An. albitarsis s.s. and species B. This latter predominated both in the rice fields and in the dwelling environments. The crepuscular rhythms showed an unimodal sunset pattern with most blood-seeking females caught during dusk. The absence of differences between indoor and outdoor behavior was confirmed for both species of the complex.

Electrical transport properties of CuS single crystals

Electrical resistivity, transverse magnetoresistance and thermoelectric power measurements were performed on CuS high quality single crystals in the range 1.2-300 K and under fields of up to 16 T. The zero field resistivity data are well described below 55 K by a quasi-2D model, consistent with a carrier confinement at lower temperatures, before the transition to the superconducting state. The transverse magnetoresistance develops mainly below 30 K and attains values as large as 470% for a 16 T field at 5 K, this behaviour being ascribed to a band effect mechanism, with a possible magnetic field induced DOS change at the Fermi level. The transverse magnetoresistance shows no signs of saturation, following a power law with field Delta rho/rho(0) proportional to H(1.4), suggesting the existence of open orbits for carriers at the Fermi surface. The thermoelectric power shows an unusual temperature dependence, probably as a result of the complex band structure of CuS.

Complex market integration in MASCEM electricity market simulator

The restructuring that the energy sector has suffered in industrialized countries originated a greater complexity in market players’ interactions, and thus new problems and issues to be addressed. Decision support tools that facilitate the study and understanding of these markets become extremely useful to provide players with competitive advantage. In this context arises MASCEM, a multi-agent system for simulating competitive electricity markets. To provide MASCEM with the capacity to recreate the electricity markets reality in the fullest possible extent, it is essential to make it able to simulate as many market models and player types as possible. This paper presents the development of the Complex Market in MASCEM. This module is fundamental to study competitive electricity markets, as it exhibits different characteristics from the already implemented market types.

Hierarchical cluster analysis of groups of individuals : application to business data

3rd SMTDA Conference Proceedings, 11-14 June 2014, Lisbon Portugal.

Rapid determination of tartaric acid in wines

A flow-spectrophotometric method is proposed for the routine determination of tartaric acid in wines. The reaction between tartaric acid and vanadate in acetic media is carried out in flowing conditions and the subsequent colored complex is monitored at 475 nm. The stability of the complex and the corresponding formation constant are presented. The effect of wavelength and pH was evaluated by batch experiments. The selected conditions were transposed to a flowinjection analytical system. Optimization of several flow parameters such as reactor lengths, flow-rate and injection volume was carried out. Using optimized conditions, a linear behavior was observed up to 1000 µg mL-1 tartaric acid, with a molar extinction coefficient of 450 L mg-1 cm-1 and ± 1 % repeatability. Sample throughput was 25 samples per hour. The flow-spectrophotometric method was satisfactorily applied to the quantification of tartaric acid (TA) in wines from different sources. Its accuracy was confirmed by statistical comparison to the conventional Rebelein procedure and to a certified analytical method carried out in a routine laboratory.

Analysis and visualization of seismic data using mutual information

Seismic data is difficult to analyze and classical mathematical tools reveal strong limitations in exposing hidden relationships between earthquakes. In this paper, we study earthquake phenomena in the perspective of complex systems. Global seismic data, covering the period from 1962 up to 2011 is analyzed. The events, characterized by their magnitude, geographic location and time of occurrence, are divided into groups, either according to the Flinn-Engdahl (F-E) seismic regions of Earth or using a rectangular grid based in latitude and longitude coordinates. Two methods of analysis are considered and compared in this study. In a first method, the distributions of magnitudes are approximated by Gutenberg-Richter (G-R) distributions and the parameters used to reveal the relationships among regions. In the second method, the mutual information is calculated and adopted as a measure of similarity between regions. In both cases, using clustering analysis, visualization maps are generated, providing an intuitive and useful representation of the complex relationships that are present among seismic data. Such relationships might not be perceived on classical geographic maps. Therefore, the generated charts are a valid alternative to other visualization tools, for understanding the global behavior of earthquakes.

Fractional dynamics and MDS visualization of earthquake phenomena

This paper analyses earthquake data in the perspective of dynamical systems and fractional calculus (FC). This new standpoint uses Multidimensional Scaling (MDS) as a powerful clustering and visualization tool. FC extends the concepts of integrals and derivatives to non-integer and complex orders. MDS is a technique that produces spatial or geometric representations of complex objects, such that those objects that are perceived to be similar in some sense are placed on the MDS maps forming clusters. In this study, over three million seismic occurrences, covering the period from January 1, 1904 up to March 14, 2012 are analysed. The events are characterized by their magnitude and spatiotemporal distributions and are divided into fifty groups, according to the Flinn–Engdahl (F–E) seismic regions of Earth. Several correlation indices are proposed to quantify the similarities among regions. MDS maps are proven as an intuitive and useful visual representation of the complex relationships that are present among seismic events, which may not be perceived on traditional geographic maps. Therefore, MDS constitutes a valid alternative to classic visualization tools for understanding the global behaviour of earthquakes.

Legal and political regulation of higher education in Portugal: an evolutionary perspective on the current policy issues and the problem of order

The higher education system in Europe is currently under stress and the debates over its reform and future are gaining momentum. Now that, for most countries, we are in a time for change, in the overall society and the whole education system, the legal and political dimensions have gained prominence, which has not been followed by a more integrative approach of the problem of order, its reform and the issue of regulation, beyond the typical static and classical cost-benefit analyses. The two classical approaches for studying (and for designing the policy measures of) the problem of the reform of the higher education system - the cost-benefit analysis and the legal scholarship description - have to be integrated. This is the argument of our paper that the very integration of economic and legal approaches, what Warren Samuels called the legal-economic nexus, is meaningful and necessary, especially if we want to address the problem of order (as formulated by Joseph Spengler) and the overall regulation of the system. On the one hand, and without neglecting the interest and insights gained from the cost-benefit analysis, or other approaches of value for money assessment, we will focus our study on the legal, social and political aspects of the regulation of the higher education system and its reform in Portugal. On the other hand, the economic and financial problems have to be taken into account, but in a more inclusive way with regard to the indirect and other socio-economic costs not contemplated in traditional or standard assessments of policies for the tertiary education sector. In the first section of the paper, we will discuss the theoretical and conceptual underpinning of our analysis, focusing on the evolutionary approach, the role of critical institutions, the legal-economic nexus and the problem of order. All these elements are related to the institutional tradition, from Veblen and Commons to Spengler and Samuels. The second section states the problem of regulation in the higher education system and the issue of policy formulation for tackling the problem. The current situation is clearly one of crisis with the expansion of the cohorts of young students coming to an end and the recurrent scandals in private institutions. In the last decade, after a protracted period of extension or expansion of the system, i. e., the continuous growth of students, universities and other institutions are competing harder to gain students and have seen their financial situation at risk. It seems that we are entering a period of radical uncertainty, higher competition and a new configuration that is slowly building up is the growth in intensity, which means upgrading the quality of the higher learning and getting more involvement in vocational training and life-long learning. With this change, and along with other deep ones in the Portuguese society and economy, the current regulation has shown signs of maladjustment. The third section consists of our conclusions on the current issue of regulation and policy challenge. First, we underline the importance of an evolutionary approach to a process of change that is essentially dynamic. A special attention will be given to the issues related to an evolutionary construe of policy analysis and formulation. Second, the integration of law and economics, through the notion of legal economic nexus, allows us to better define the issues of regulation and the concrete problems that the universities are facing. One aspect is the instability of the political measures regarding the public administration and on which the higher education system depends financially, legally and institutionally, to say the least. A corollary is the lack of clear strategy in the policy reforms. Third, our research criticizes several studies, such as the one made by the OECD in late 2006 for the Ministry of Science, Technology and Higher Education, for being too static and neglecting fundamental aspects of regulation such as the logic of actors, groups and organizations who are major players in the system. Finally, simply changing the legal rules will not necessary per se change the behaviors that the authorities want to change. By this, we mean that it is not only remiss of the policy maker to ignore some of the critical issues of regulation, namely the continuous non-respect by academic management and administrative bodies of universities of the legal rules that were once promulgated. Changing the rules does not change the problem, especially without the necessary debates form the different relevant quarters that make up the higher education system. The issues of social interaction remain as intact. Our treatment of the matter will be organized in the following way. In the first section, the theoretical principles are developed in order to be able to study more adequately the higher education transformation with a modest evolutionary theory and a legal and economic nexus of the interactions of the system and the policy challenges. After describing, in the second section, the recent evolution and current working of the higher education in Portugal, we will analyze the legal framework and the current regulatory practices and problems in light of the theoretical framework adopted. We will end with some conclusions on the current problems of regulation and the policy measures that are discusses in recent years.