Resonance Raman and DFT studies of tetra-tert-butyl porphine: Assignment of strongly enhanced distortion modes in a ruffled porphyrin

The free-base form of tetra-tert-butyl porphine (TtBP), which has extremely bulky meso substituents, is severely distorted from planarity, with a ruffling angle of 65.5degrees. The resonance Raman spectrum of TtBP (lambda(ex) = 457.9 nm) and its d(2), d(8), and d(10) isotopomers have been recorded, and while the spectra show high-frequency bands similar to those observed for planar meso-substituted porphyrins, there are several additional intense bands in the low-frequency region. Density functional calculations at the B3-LYP/6-31G(d) level were carried out for all four isotopomers, and calculated frequencies were scaled using a single factor of 0.98. The single factor scaling approach was validated on free base porphine where the RMS error was found to be 14.9 cm(-1). All the assigned bands in the high-frequency (> 1000 cm(-1)) region of TtBP were found to be due to vibrations similar in character to the in-plane skeletal modes of conventional planar porphyrins. In the low-frequency region, two of the bands, assigned as nu(8) (ca. 330 cm(-1)) and nu(16) (ca. 540 cm(-1)), are also found in planar porphyrins such as tetra-phenyl porphine (TPP) and tetra-iso-propyl porphine (IPP). Of the remaining three very strong bands, the lowest frequency band was assigned as gamma(12) (pyr swivel, obsd 415 cm(-1), calcd 407 cm(-1) in do). The next band, observed at 589 cm-1 in the do compound (calcd 583 cm(-1)), was assigned as a mode whose composition is a mixture of modes that were previously labeled gamma(13) (gamma(CmCaHmCa)) andy gamma(11) (pyr fold(asym)) in NiOEP. The final strong band, observed at 744 cm(-1) (calcd 746 cm(-1)), was assigned to a mode whose composition is again a mixture of gamma(11) and gamma(13), although here it is gamma(11) rather than gamma(13) which predominates. These bands have characters and positions similar to those of three of the four porphyrin ring-based, weak bands that have previously been observed for NiTPP. In addition there are several weaker bands in the TtBP spectra that are also

The Contours of the Right to Self-defence: Is the Requirement of Imminence Merely a Translator for the Concept of Necessity?

The right to self-defence has lately been subjected to intense academic controversy, both at the domestic and international level. The debate is focused on the question of whether or not the requirement of imminence is merely a translator for the notion of necessity. At the domestic level, the debate has mainly been kindled by feminist scholars, who, in the context of the 'battered woman', argue that the requirement of imminence should be discarded from the contours of the self-defence doctrine. The purpose of this article is to prove the necessity of the imminence requirement as a litmus test to detect possible abuses of the self-defence doctrine.

Considering the impact of the 'Right to Bargain' Legislation in Ireland: A Review

Ireland is rare among advanced economies in not having statutory trade union recognition legislation for collective bargaining purposes. The matter has been a source of policy contention over the years with attempts to resolve it encapsulated in the so-called ‘Right to Bargain’ legislation, introduced in 2001. This legislation has sought to circumvent statutory recognition in Ireland by putting in place an alternative mechanism for unions to represent members in non-union firms where collective bargaining is not practiced. This review, based on a mixture of empirical and documentary evidence, demonstrates that this legislation was moderately successful for a short period in generating pay rises, improved employment conditions and better access to procedures for union members in non-unionised firms. Indeed, in some respects, it was a superior institutional mechanism to a statutory recognition regime.

On the Origin of the Right to Copy: Charting the Movement of Copyright Law in Eighteenth Century Britain (1695-1775)

Taking as its point of departure the lapse of the 1662 Licensing Act in 1695, this book examines the lead up to the passage of the Statute of Anne 1710 and charts the movement of copyright law throughout the eighteenth century, culminating in the House of Lords decision in Donaldson v Becket (1774). The established reading of copyright's development throughout this period, from the 1710 Act to the pronouncement in Donaldson, is that it was transformed from a publisher's right to an author's right; that is, legislation initially designed to regulate the marketplace of the bookseller and publisher evolved into an instrument that functioned to recognise the proprietary inevitability of an author's intellectual labour. The historical narrative which unfolds within this book presents a challenge to that accepted orthodoxy. The traditional analysis of the development of copyright in eighteenth-century Britain is revealed to exhibit the character of long-standing myth, and the centrality of the modern proprietary author as the raison d'etre of the modern copyright regime is displaced.

Measuring children’s experience of their right to participate in school and community: a rights-based approach

This paper discusses the development of a children’s rights-based measure of participation and the findings from its use in a survey of 10 to 11 year old children (n= 3773). The measure, which was developed in collaboration with a group of children, had a high reliability (Cronbach’s alpha = .89). Findings suggest that children’s positive experience of their participation rights is higher in school than in community, and higher for girls compared to boys. It is argued that involving children in the ‘measurement’ of their own lives has the potential to generate more authentic data on children’s lived experiences.

What is an absolute right? Deciphering absoluteness in the context of Article 3 of the European Convention on Human Rights

The answer to the question of what it means to say that a right is absolute is often taken for granted, yet still sparks doubt and scepticism. This article investigates absoluteness further, bringing rights theory and the judicial approach on an absolute right together. A theoretical framework is set up that addresses two distinct but potentially related parameters of investigation: the first is what I have labelled the ‘applicability’ criterion, which looks at whether and when the applicability of the standard referred to as absolute can be displaced, in other words whether other considerations can justify its infringement; the second parameter, which I have labelled the ‘specification’ criterion, explores the degree to which and bases on which the content of the standard characterised as absolute is specified. This theoretical framework is then used to assess key principles and issues that arise in the Strasbourg Court’s approach to Article 3. It is suggested that this analysis allows us to explore both the distinction and the interplay between the two parameters in the judicial interpretation of the right and that appreciating the significance of this is fundamental to the understanding of and discourse on the concept of an absolute right.

Right-Wing Violence in Germany: Assessing the Objectives, Personalities and Terror Trail of the National Socialist Underground and the State's Response to It

In the last five years the forces of organised right-wing extremism have made electoral advances across many states in contemporary Europe. Germany has not been immune and the extreme right party, the National Democratic Party of Germany won its first seat in the European Parliament since 1989. The recent successes of the extreme right pose issues for European society about tolerance and immigration policy, but this scene has also been associated with an upsurge in racially motivated political violence and acts of right-wing terrorism. Much of this violence is perpetrated by small neo-Nazi styled groups. This paper looks at the most notorious and recent of such groups to emerge in Germany, the National Socialist Underground. The paper explores the origins and personalities behind this terror cell, provides derails of its criminal activities and murder spree, and questions why it took so long for the authorities to identify the NSU.

A Density Functional Theory Study on the Active Center of Fe-Only Hydrogenase: Characterization and Electronic Structure of the Redox States

We have carried out extensive density functional theory (DFT) calculations for possible redox states of the active center in Fe-only hydrogenases. The active center is modeled by [(H(CH(3))S)(CO)(CN(-))Fe(p)(mu-DTN)(mu-CO)Fe(d)(CO)(CN(-))(L)](z) (z is the net charge in the complex; Fe(p)= the proximal Fe, Fe(d) = the distal Fe, DTN = (-SCH(2)NHCH(2)S-), L is the ligand that bonds with the Fed at the trans position to the bridging CO). Structures of possible redox states are optimized, and CO stretching frequencies are calculated. By a detailed comparison of all the calculated structures and the vibrational frequencies with the available experimental data, we find that (i) the fully oxidized, inactive state is an Fe(II)-Fe(II) state with a hydroxyl (OH(-)) group bonded at the Fe(d), (ii) the oxidized, active state is an Fe(II)-Fe(l) complex which is consistent with the assignment of Cao and Hall (J. Am. Chem. Soc. 2001, 123, 3734), and (iii) the fully reduced state is a mixture with the major component being a protonated Fe(l)-Fe(l) complex and the other component being its self-arranged form, Fe(II)-Fe(II) hydride, Our calculations also show that the exogenous CO can strongly bond with the Fe(II)-Fe(l) species, but cannot bond with the Fe(l)-Fe(l) complex. This result is consistent with experiments that CO tends to inhibit the oxidized, active state, but not the fully reduced state. The electronic structures of all the redox states have been analyzed. It is found that a frontier orbital which is a mixing state between the e(g) of Fe and the 2pi of the bridging CO plays a key role concerning the reactivity of Fe-only hydrogenases: (1) it is unoccupied in the fully oxidized, inactive state, half-occupied in the oxidized, active state, and fully occupied in the fully reduced state; (ii) the e(g)-2pi orbital is a bonding state, and this is the key reason for stability of the low oxidation states, such as Fe(l)-Fe(l) complexes; and (iii) in the e(g)-2pi orbital more charge accumulates between the bridging CO and the Fe(d) than between the bridging CO and the Fe(p), and the occupation increase in this orbital will enhance the bonding between the bridging CO and the Fe(d), leading to the bridging-CO shift toward the Fe(d).

Tenant Right and Agrarian Society in Ulster 1600-1870

The book has been described by various Irish historians as "the definitive treatment of that most peculiar institution--the Ulster Custom--and its tangled relationship with irish land and politics" (Liam Kennedy), "a brilliantly reconceptualised sketch of the Irish land question" (David Miller). "All previous discussion," according to another reviewer, "must take second place to Dowling's exhaustive survey, which draws on the whole range of surviving estate records to examine the theory and practice of tenant right across three centuries" (Sean Connolly).

Consociationalism and the evolution of political cleavages in Northern Ireland, 1989-2004

Political cleavages are often understood as deriving from either deep-rooted social divisions or institutional incentives. Contemporary Northern Ireland provides a test of the mutability of apparently entrenched cleavages to institutional change. Research undertaken before the ceasefire in the 1990s found noticeable asymmetries in the patterns of cleavage within the unionist and nationalist blocs. Within the unionist bloc, economic 'left-right' issues formed the main ideological division between the two major unionist parties. This contrasted with an ethno-national source of ideological division between the two nationalist parties. The emergence of a consociational form of government structure since then has demonstrated the ability of institutional incentives to swiftly reform some aspects of party competition however. As evidence of this, we show that between 1989 and 2004 there was little change in the sources of support for Sinn F�©in relative to the SDLP, but the influence of left-right ideology within the unionist bloc was negated as the influence of ethno-nationalism dramatically increased.

Analysis of DNA processing reactions in bacterial conjugation by using suicide oligonucleotides

Protein TrwC is the conjugative relaxase responsible for DNA processing in plasmid R388 bacterial conjugation. TrwC has two catalytic tyrosines, Y18 and Y26, both able to carry out cleavage reactions using unmodified oligonucleotide substrates. Suicide substrates containing a 30-Sphosphorothiolate linkage at the cleavage site displaced TrwC reaction towards covalent adducts and thereby enabled intermediate steps in relaxase reactions to be investigated. Two distinct covalent TrwC–oligonucleotide complexes could be separated from noncovalently bound protein by SDS–PAGE. As observed by mass spectrometry, one complex contained a single, cleaved oligonucleotide bound to Y18, whereas the other contained two cleaved oligonucleotides, bound to Y18 and Y26. Analysis of the cleavage reaction using suicide substrates and Y18F or Y26F mutants showed that efficient Y26 cleavage only occurs after Y18 cleavage. Strand-transfer reactions carried out with the isolated Y18–DNA complex allowed the assignment of specific roles to each tyrosine. Thus, only Y18 was used for initiation. Y26 was specifically used in the second transesterification that leads to strand transfer, thus catalyzing the termination reaction that occurs in the recipient cell.