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111.
Annemarie Huijser Dr. Alessandro Pezzella Dr. Jonas K. Hannestad Lucia Panzella Dr. Alessandra Napolitano Prof. Marco d'Ischia Prof. Villy Sundström Prof. 《Chemphyschem》2010,11(11):2424-2431
The UV‐dissipative mechanisms of the eumelanin building block 5,6‐dihydroxyindole‐2‐carboxylic acid (DHICA) and the 4,7‐dideutero derivative (DHICA‐d2) in buffered H2O or D2O have been characterized by using ultrafast time‐resolved fluorescence spectroscopy. Excitation of the carboxylate anion form, the dominating state at neutral pH, leads to dual fluorescence. The band peaking at λ=378 nm is caused by emission from the excited initial geometry. The second band around λ=450 nm is owed to a complex formed between the mono‐anion and specific buffer components. In the absence of complex formation, the mono‐anion solely decays non‐radiatively or by emission with a lifetime of about 2.1 ns. Excitation of the neutral carboxylic acid state, which dominates at acidic pH, leads to a weak emission around λ=427 nm with a short lifetime of 240 ps. This emission originates from the zwitterionic state, formed upon excitation of the neutral state by sub‐ps excited‐state intramolecular proton transfer (ESIPT) between the carboxylic acid group and the indole nitrogen. Future studies will unravel whether this also occurs in larger building blocks and ESIPT is a built‐in photoprotective mechanism in epidermal eumelanin. 相似文献
112.
Qasim Chaudhry Nadège Piclin Jane Cotterill Marco Pintore Nick R Price Jacques R Chrétien Alessandra Roncaglioni 《Chemistry Central journal》2010,4(Z1):S5
Background
The new European Regulation on chemical safety, REACH, (Registration, Evaluation, Authorisation and Restriction of CHemical substances), is in the process of being implemented. Many chemicals used in industry require additional testing to comply with the REACH regulations. At the same time EU member states are attempting to reduce the number of animals used in experiments under the 3 Rs policy, (refining, reducing, and replacing the use of animals in laboratory procedures). Computational techniques such as QSAR have the potential to offer an alternative for generating REACH data. The FP6 project CAESAR was aimed at developing QSAR models for 5 key toxicological endpoints of which skin sensitisation was one.Results
This paper reports the development of two global QSAR models using two different computational approaches, which contribute to the hybrid model freely available online.Conclusions
The QSAR models for assessing skin sensitisation have been developed and tested under stringent quality criteria to fulfil the principles laid down by the OECD. The final models, accessible from CAESAR website, offer a robust and reliable method of assessing skin sensitisation for regulatory use.113.
Duquesnoy E Marongiu B Castola V Piras A Porcedda S Casanova J 《Natural product communications》2010,5(12):1995-1998
Two samples (leaves and twigs) of Abies alba Miller from Corsica were extracted using supercritical CO2 and their chemical compositions were compared with those of the essential oils obtained from the same batch of plant material. In total 45 components were identified using combined analysis by GC (RI), GC-MS and 13C NMR. It was observed that the contents of monoterpenes (mainly represented by limonene, alpha-pinene and camphene) were significantly lower in the supercritical fluid extract (SFE) than in the essential oil (EO). Conversely, the proportions of sesquiterpenes were much higher in CO2 extracts than in essential oils (around 30% vs 4%). Cis-abienol, a diterpene alcohol, was identified only in SFE, and the proportions of this constituent (7.5% and 17.3%) were determined using quantitative 13C NMR since it was under estimated using the standard conditions of GC. 相似文献
114.
Peruzzo D Zanderigo F Bertoldo A Pillonetto G Cosottini M Cobelli C 《Magnetic resonance imaging》2011,29(7):927-936
Dynamic susceptibility contrast magnetic resonance imaging (DSC-MRI) allows the noninvasive assessment of brain hemodynamics alterations by quantifying, via deconvolution, the cerebral blood flow (CBF) and mean transit time (MTT). Singular value decomposition (SVD) and block-circulant SVD (cSVD) are the most widely adopted deconvolution method, although they bear some limitations, including unphysiological oscillations in the residue function and bias in the presence of delay and dispersion between the tissue and the arterial input function. A nonlinear stochastic regularization (NSR) has been proposed, which performs better than SVD and cSVD on simulated data both in the presence and absence of dispersion. Moreover, NSR allows to quantify the dispersion level. Here, cSVD and NSR are compared for the first time on a group of nine patients with severe atherosclerotic unilateral stenosis of internal carotid artery before and after carotid stenting to investigate the effect of arterial dispersion. According to region of interest-based analysis, NSR characterizes the pathologic tissue more accurately than cSVD, thus improving the quality of the information provided to physicians for diagnosis. In fact, in 7 (78%) of the 9 subjects, CBF and MTT maps provided by NSR allow to correctly identify the pathologic hemisphere to the physician. Moreover, by emphasizing the difference between pathologic and healthy tissues, NSR may be successfully used to monitor the subject's recovery after the treatment and/or surgery. NSR also generates dispersion level and non-dispersed CBF and MTT maps. The dispersion level provides information on CBF and MTT estimates reliability and may also be used as a clinical indicator of pathological tissue state complementary to CBF and MTT, thus increasing the clinical information provided by DSC-MRI analysis. 相似文献
115.
In the present paper, we start studying epistemic updates using the standard toolkit of duality theory. We focus on public announcements, which are the simplest epistemic actions, and hence on Public Announcement Logic (PAL) without the common knowledge operator. As is well known, the epistemic action of publicly announcing a given proposition is semantically represented as a transformation of the model encoding the current epistemic setup of the given agents; the given current model being replaced with its submodel relativized to the announced proposition. We dually characterize the associated submodel-injection map as a certain pseudo-quotient map between the complex algebras respectively associated with the given model and with its relativized submodel. As is well known, these complex algebras are complete atomic BAOs (Boolean algebras with operators). The dual characterization we provide naturally generalizes to much wider classes of algebras, which include, but are not limited to, arbitrary BAOs and arbitrary modal expansions of Heyting algebras (HAOs). Thanks to this construction, the benefits and the wider scope of applications given by a point-free, intuitionistic theory of epistemic updates are made available. As an application of this dual characterization, we axiomatize the intuitionistic analogue of PAL, which we refer to as IPAL, prove soundness and completeness of IPAL w.r.t. both algebraic and relational models, and show that the well known Muddy Children Puzzle can be formalized in IPAL. 相似文献
116.
117.
We study the dynamics of the space debris in the 1:1 and 2:1 resonances, where geosynchronous and GPS satellites are located. By using Hamiltonian formalism, we consider a model including the geopotential contribution for which we compute the secular and resonant expansions of the Hamiltonian. Within such model we are able to detect the equilibria and to study the main features of the resonances in a very effective way. In particular, we analyze the regular and chaotic behavior of the 1:1 and 2:1 resonant regions by analytical methods and by computing the Fast Lyapunov Indicators, which provide a cartography of the resonances. This approach allows us to detect easily the location of the equilibria, the amplitudes of the libration islands and the main dynamical stability features of the resonances, thus providing an overview of the 1:1 and 2:1 resonant domains under the effect of Earth’s oblateness. The results are validated by a comparison with a model developed in Cartesian coordinates, including the geopotential, the gravitational attraction of Sun and Moon and the solar radiation pressure. 相似文献
118.
Samuel Boissière Marc Nieper-Wißkirchen Alessandra Sarti 《Journal de Mathématiques Pures et Appliquées》2011,95(5):553-563
We define Enriques varieties as a higher dimensional generalization of Enriques surfaces and construct examples by using fixed point free automorphisms on generalized Kummer varieties. We also classify all automorphisms of generalized Kummer varieties that come from an automorphism of the underlying abelian surface. 相似文献
119.
In this note we describe explicitly those linear spaces of nilpotent matrices, which are stable under conjugation by diagonal matrices. As an application, we deduce a generalized version of a result of Valcher and Fornasini on pairs of nonnegative nilpotent matrices. 相似文献
120.