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261.
Unraveling the Degradation Mechanism of Purine Nucleotides Photosensitized by Pterins: The Role of Charge‐Transfer Steps
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Mariana P. Serrano Dr. Carolina Lorente Dr. Claudio D. Borsarelli Dr. Andrés H. Thomas 《Chemphyschem》2015,16(10):2244-2252
Photosensitized reactions contribute to the development of skin cancer and are used in many applications. Photosensitizers can act through different mechanisms. It is currently accepted that if the photosensitizer generates singlet molecular oxygen (1O2) upon irradiation, the target molecule can undergo oxidation by this reactive oxygen species and the reaction needs dissolved O2 to proceed, therefore the reaction is classified as 1O2‐mediated oxidation (type II mechanism). However, this assumption is not always correct, and as an example, a study on the degradation of 2′‐deoxyguanosine 5′‐monophosphate photosensitized by pterin is presented. A general mechanism is proposed to explain how the degradation of biological targets, such as nucleotides, photosensitized by pterins, naturally occurring 1O2 photosensitizers, takes place through an electron‐transfer‐initiated process (type I mechanism), whereas the contribution of the 1O2‐mediated oxidation is almost negligible. 相似文献
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Generating and analyzing spatial social networks 总被引:1,自引:0,他引:1
Meysam Alizadeh Claudio Cioffi-Revilla Andrew Crooks 《Computational & Mathematical Organization Theory》2017,23(3):362-390
In this paper, we propose a class of models for generating spatial versions of three classic networks: Erdös-Rényi (ER), Watts-Strogatz (WS), and Barabási-Albert (BA). We assume that nodes have geographical coordinates, are uniformly distributed over an m × m Cartesian space, and long-distance connections are penalized. Our computational results show higher clustering coefficient, assortativity, and transitivity in all three spatial networks, and imperfect power law degree distribution in the BA network. Furthermore, we analyze a special case with geographically clustered coordinates, resembling real human communities, in which points are clustered over k centers. Comparison between the uniformly and geographically clustered versions of the proposed spatial networks show an increase in values of the clustering coefficient, assortativity, and transitivity, and a lognormal degree distribution for spatially clustered ER, taller degree distribution and higher average path length for spatially clustered WS, and higher clustering coefficient and transitivity for the spatially clustered BA networks. 相似文献
266.
Pseudo–almost‐periodic solutions for delayed differential equations with integrable dichotomies and bi–almost‐periodic Green functions
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Using the existence of integrable bi–almost‐periodic Green functions of linear homogeneous differential equations and the contraction fixed point, we are able to prove the existence of almost and pseudo–almost‐periodic mild solutions under quite general hypotheses for the differential equation with constant delay in a Banach space X, where τ>0 is a fixed constant. The results extend the corresponding ones in the case of exponential dichotomy. Some examples illustrate the importance of the concepts. 相似文献
267.
Summary An algorithm for the transformation of generalized Companion forms for multivariable linear systems to Jordan form is considered.The procedure is based on a preliminary transformation to the corresponding maximum length chains canonical form (MLCGCF) and on knowledge of the eigenvalues and their multiplicity.
This work was supported by CNR (Italian Council of Researches). 相似文献
Sommario Viene presentato un algoritmo per la trasformazione della matrice dinamica di sistemi lineari a più variabili di ingresso-uscita da forma companion generalizzata in forma di Jordan.Il procedimento è basato su una trasformazione preliminare in forma canonica a catene di massima lunghezza (MLCGCF) e sulla conoscenza degli autovalori e della loro multeplicità.
This work was supported by CNR (Italian Council of Researches). 相似文献
268.
Luca Bertini Claudio Greco Piercarlo Fantucci Luca De Gioia 《International journal of quantum chemistry》2014,114(13):851-861
Upon irradiation with ultraviolet wavelengths, Fe2(S2C3H6)(CO)6, a simple model of the [FeFe]‐hydrogenase active site, undergoes CO dissociation to form the unsaturated Fe2(S2C3H6)(CO)5 species and successively a solvent adduct at the vacant coordination site. In the present work, the CO‐photolysis of Fe2(S2C3H6)(CO)6 was investigated by density functional theory (DFT) and time‐dependent DFT (TDDFT). Trans Fe2(S2C3H6)(CO)5 form and the corresponding trans heptane or acetonitrile solvent adducts are the lowest energy ground state forms. CO dissociation barriers computed for the lowest triplet state are roughly halved with respect to those for the ground state suggesting that some low‐lying excited potential energy surface (PES) could be loosely bound with respect to Fe? C bond cleavage. The TDDFT excited state PESs and geometry optimizations for the excited states likely involved in the CO‐photolysis suggest that the Fe? S bond elongation and the partial isomerization toward the rotated form could take place simultaneously, favoring the trans CO photodissociation. © 2014 Wiley Periodicals, Inc. 相似文献
269.
Maria-Beatrice Coltelli Claudio ToncelliFrancesco Ciardelli Simona Bronco 《Polymer Degradation and Stability》2011,96(5):982-990
The transesterification during the melt blending of polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) was investigated in presence of Ti(OBu)4 as a catalyst. Both the effect of catalyst concentration and reaction duration was considered. The process was studied by analyzing the molecular weight of the polyesters by size exclusion chromatography (SEC). The rheological, thermal and morphological properties of the blends were investigated by melt flow rate, DSC and SEM analyses, respectively. Evidences about the formation of PBAT-PLA copolymers were obtained and discussed. The tensile properties of compression moulded films were also determined and correlated to the structure and phase morphology development of the blends. In particular, the use of Ti(OBu)4 resulted in the improvement of compatibility. Moreover, the decrease in stiffness and the increase in elongation at break with the increase of mixing time was observed, in good agreement with the improved compatibility of the modified blend. 相似文献
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