884 research outputs found
Comparing Mutuality and Solidarity in Its Application to Disaster Ethics
Often it has been observed that in disaster situations, people (including victims) become altruistic and are very willing to listen, obey and act in a manner that would help bring an end to the situation. In this chapter, linking disaster ethics and human rights, it is argued that this indeed is how it should be, disaster or otherwise, and that we have moral duties to oneself and to others. An individual exhibiting solidarity, comradery and altruism during a disaster is indeed behaving as a reasonable Self, and exercising ethical individualism as per Gewirthian philosophy. It is the duty of the State and society to act as a supportive State and a caring society. In order to do this, we need to be conditioned for ethical rationality before any whiff of disaster arises, i.e. in our day-to-day conduct and decision-making, at a personal, institutional and transnational level. Our ethical resilience during disasters can only be as robust as our rational moral compass during ‘peace-time’. This chapter argues that Gewirthian solidarity ethics (GSE) should play a role in European policy and action in order to provide a system that conditions ethical rationality and in order to fulfil human rights. This involves addressing our current understanding of human rights as distinct categories of civil, political, economic, social and cultural rights and to effect a shift towards a more holistic understanding of human rights, whereby the hierarchy of fulfilment does not always prioritise civil and political rights.Peer reviewe
On a clear day you can see forever : integrating values and skills in sex offender treatment
The topic of sex offender rehabilitation frequently evokes fierce reactions, ranging from strident demands for harsher sentences contrasted with calls for more imaginative and compassionate sentencing options. There seems to be a polarization of positions centred on the question of offenders\u27 moral standing: are they moral strangers or fellow travellers? This fundamental disagreement about offenders\u27 moral status is at the core of a number of independent, although related current practice and research issues confronting the field, namely: (1) risk management versus strength-based treatment approaches; (2) the utility of utilizing individually tailored versus manual-based programmes for offenders; (3) focusing on the technical aspects or therapy as opposed to relationship and therapist factors (what has been called process issues); and (4) the conflict between protecting the community versus promoting the interests of offenders. In this paper I suggest that an approach to sex offender treatment based on a combination of human rights theory (an ethical resource) and strengths-based approaches can help us navigate our way through the above dilemmas in a way that addressees both the needs of offenders and those of the community
Individual Rights, Economic Transactions, and Recognition: A Legal Approach to Social Economics
Modernity brought the idea of individual property rights as a com- plex phenomenon. However, economics adopted a simplistic view of property as a fundamental institution, understating the complex interaction of different rights and obligations that frame the legal environment of economic processes with an insufficiently elaborated tool. Here, a more elaborate view of legal elements will be propose
Harnessing Higher-Order (Meta-)Logic to Represent and Reason with Complex Ethical Theories
The computer-mechanization of an ambitious explicit ethical theory, Gewirth's
Principle of Generic Consistency, is used to showcase an approach for
representing and reasoning with ethical theories exhibiting complex logical
features like alethic and deontic modalities, indexicals, higher-order
quantification, among others. Harnessing the high expressive power of Church's
type theory as a meta-logic to semantically embed a combination of quantified
non-classical logics, our work pushes existing boundaries in knowledge
representation and reasoning. We demonstrate that intuitive encodings of
complex ethical theories and their automation on the computer are no longer
antipodes.Comment: 14 page
Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins
Bioinorganic canon states that active-site
thiolate coordination promotes rapid electron transfer (ET)
to and from type 1 copper proteins. In recent work, we have
found that copper ET sites in proteins also can be constructed
without thiolate ligation (called “type zero” sites). Here we
report multifrequency electron paramagnetic resonance
(EPR), magnetic circular dichroism (MCD), and nuclear
magnetic resonance (NMR) spectroscopic data together with
density functional theory (DFT) and spectroscopy-oriented
configuration interaction (SORCI) calculations for type zero Pseudomonas aeruginosa azurin variants. Wild-type (type 1) and type
zero copper centers experience virtually identical ligand fields. Moreover, O-donor covalency is enhanced in type zero centers
relative that in the C112D (type 2) protein. At the same time, N-donor covalency is reduced in a similar fashion to type 1
centers. QM/MM and SORCI calculations show that the electronic structures of type zero and type 2 are intimately linked to the
orientation and coordination mode of the carboxylate ligand, which in turn is influenced by outer-sphere hydrogen bonding
A new view of electrochemistry at highly oriented pyrolytic graphite
Major new insights on electrochemical processes at graphite electrodes are reported, following extensive investigations of two of the most studied redox couples, Fe(CN)64–/3– and Ru(NH3)63+/2+. Experiments have been carried out on five different grades of highly oriented pyrolytic graphite (HOPG) that vary in step-edge height and surface coverage. Significantly, the same electrochemical characteristic is observed on all surfaces, independent of surface quality: initial cyclic voltammetry (CV) is close to reversible on freshly cleaved surfaces (>400 measurements for Fe(CN)64–/3– and >100 for Ru(NH3)63+/2+), in marked contrast to previous studies that have found very slow electron transfer (ET) kinetics, with an interpretation that ET only occurs at step edges. Significantly, high spatial resolution electrochemical imaging with scanning electrochemical cell microscopy, on the highest quality mechanically cleaved HOPG, demonstrates definitively that the pristine basal surface supports fast ET, and that ET is not confined to step edges. However, the history of the HOPG surface strongly influences the electrochemical behavior. Thus, Fe(CN)64–/3– shows markedly diminished ET kinetics with either extended exposure of the HOPG surface to the ambient environment or repeated CV measurements. In situ atomic force microscopy (AFM) reveals that the deterioration in apparent ET kinetics is coupled with the deposition of material on the HOPG electrode, while conducting-AFM highlights that, after cleaving, the local surface conductivity of HOPG deteriorates significantly with time. These observations and new insights are not only important for graphite, but have significant implications for electrochemistry at related carbon materials such as graphene and carbon nanotubes
Theoretical study of the electronic spectra of small molecules that incorporate analogues of the copper-cysteine bond
The copper-sulphur bond which binds cysteinate to the metal centre is a key factor in the spectroscopy of blue copper proteins. We present theoretical calculations describing the electronically excited states of small molecules, including CuSH, CuSCH_3, (CH_3)_2SCuSH, (imidazole)-CuSH and (imidazole)_2-CuSH, derived from the active site of blue copper proteins that contain the copper-sulphur bond in order to identify small molecular systems that have electronic structure that is analogous to the active site of the proteins. Both neutral and cationic forms are studied, since these represent the reduced and oxidised forms of the protein, respectively. For CuSH and CuSH^+, excitation energies from time-dependent density functional theory with the B97-1 exchange-correlation functional agree well with the available experimental data and multireference configuration interaction calculations. For the positive ions, the singly occupied molecular orbital is formed from an antibonding combination of a 3d orbital on copper and a 3pπ orbital on sulphur, which is analogous to the protein. This leads several of the molecules to have qualitatively similar electronic spectra to the proteins. For the neutral molecules, changes in the nature of the low lying virtual orbitals leads the predicted electronic spectra to vary substantially between the different molecules. In particular, addition of a ligand bonded directly to copper results in the low-lying excited states observed in CuSH and CuSCH_33 to be absent or shifted to higher energies
Modulus variation of composite graphite electrodes in lithium-ion batteries during electrochemical cycling
Graphite is currently the most common anode material used in commercial lithium-ion batteries. During battery charging and discharging processes, lithium ions intercalate into and deintercalate from graphite, forming several distinct stages of graphite-lithium intercalation compounds (G-LICs). Each stage of G-LIC has a unique spacing between graphene layers, with the spacing increasing for increasing lithium content. In graphite-based composite electrodes (graphite particles in a porous polymer matrix), the changing layer spacing leads to stress and strain evolution on the composite length scale. In two separate experiments, we use substrate-curvature measurements to monitor stress changes in a thin electrode constrained on an inert, rigid substrate, and we use digital image correlation to track strain changes in a free-standing, unconstrained electrode. Combining the in-situ stress and strain analyses enables us to extract the change in the apparent modulus of the composite graphite electrode as a function of electrode potential and lithium content. As expected, we found that constrained electrodes develop compressive stress during lithiation (~10 MPa) and that unconstrained electrodes undergo free expansion (~1.5% linear strain). Interestingly, the apparent modulus of the electrode increases the most significantly during the formation of the dilute stage I compound, increases slightly with the formation of the stage IV, dilute stage II, and stage II compounds, and then decreases with the formation of the stage I compound (LiC 6). During delithiation, unconstrained electrodes contract, recovering nearly their original size. In constrained electrodes during delithation, however, the compressive stress is first relaxed, and then a tensile stress develops and is subsequently relaxed. The tensile stress leads to an apparent softening of the composite electrode over a broad range of electrode potential and capacity. At the end of one complete lithiation/delithiation cycle, the apparent modulus returns to approximately its original value. The evolution of stress, strain, and modulus data provides quantitative information on the coupled electro-chemo-mechanical response of battery electrodes and insight on material strategies to increase battery reliability
Elucidating Zn and Mg Electrodeposition Mechanisms in Nonaqueous Electrolytes for Next-Generation Metal Batteries
Cyclic voltammetry and linear sweep voltammetry with an ultramicroelectrode (UME) were employed to study Zn and Mg electrodeposition and the corresponding mechanistic pathways. CVs obtained at a Pt UME for Zn electroreduction from a trifluoromethylsulfonyl imide (TFSI^–) and chloride-containing electrolyte in acetonitrile exhibit current densities that are scan rate independent, as expected for a simple electron transfer at a UME. However, CVs obtained from three different Mg-containing electrolytes in THF exhibit an inverse dependence between scan rate and current density. COMSOL-based simulation suggests that Zn electrodeposition proceeds via a simple one-step, two-electron transfer (E) mechanism. Alternatively, the Mg results are best described by invoking a chemical step prior to electron transfer: a chemical–electrochemical (CE) mechanism. The chemical step exhibits an activation energy of 51 kJ/mol. This chemical step is likely the disproportionation of the chloro-bridged dimer [Mg_2(μ–Cl)_3·6THF]^+ present in active electrodeposition solutions. Our work shows that Mg deposition kinetics can be improved by way of increased temperature
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