Theory of electron transfer reactions in blue-copper proteins

The rates of electron transfer reactions in azurin and plastocyanin are calculated with the Intersecting-State Model and compared with experimental data. The calculated distance, free-energy and temperature dependencies of the intraprotein rates in Ru-modified azurins are in good agreement with the experiment. These calculations do not require the fitting of any parameters. Significant tunneling contributions to the room temperature rate are found in some systems. In some cases the symmetry or the orientation of the donor and acceptor orbitals are not favorable and the ET rates are reduced by factors exceeding 4 orders of magnitude.     

Rapid method for radiostrontium determination in milk in emergency situations using PS resin

This study describes a new and rapid procedure for radiostrontium determination in milk samples based on the use of plastic scintillation resins (PS resins). The proposed method reduces the time of analysis by at least 2 h by combining separation and measurement preparation into a single step and optimizing the pre-treatment steps. The method is robust and reproducible, with good total recoveries (65% on average) and a relative bias for total radiostrontium activity (⁸⁹Sr + ⁹⁰Sr) below 7%. The minimum detectable activity for 100 mL of milk sample measured for 60 min is about 0.34 Bq L^?1. The proposed method can quantify radiostrontium content in 5 h, which makes it suitable for use in emergency situations.     

Pressure dependence of triplet formation in acridine and phenazine vapours

The pressure dependence of T₁ formation in acridine and phenazine vapours was studied between 0.05 torr and 40 torr of an added buffer gas, by microsecond flash photolysis. In contrast to the pressure dependence of anthracene triplet formation, in the heterocyclic compounds the triplet absorption increases slightly with pressure up to 1 torr and then decreases strongly with an increase in pressure up to 30–40 torr. These effects were confirmed by the slight increase followed by a decrease with time of the integrated areas of the T₁ acridine spectra observed at much shorter times by means of nanosecond flash photolysis. The absorption of the lowest triplet was found to have an induction period more than one order of magnitude longer than the laser pulse or the singlet lifetimes revealing that the T₁ state is not populated directly from S₁ but via other electronic triplet states. The pressure effects on triplet formation are interpreted in terms of a reversible intersystem crossing S₁ ? T₁ associated with vibrational relaxation in the triplet states.     

Synthesis and photochemical behavior of phosphorus dendrimers containing azobenzene units within the branches and/or on the surface

We describe the synthesis of three series of phosphorus-containing dendrimers having azobenzene derivatives specifically placed at some generations in the interior and/or on the surface. The largest compound obtained possesses 48 azobenzene groups on the surface. Irradiation at 350 nm induces isomerization of the azobenzene groups from the E form to the Z form, whatever their location. The thermal back-isomerization to the E form in the dark at room temperature was observed in all cases. The kinetics of this Z-->E back-isomerization was studied in several cases; the rate is not dependent on the number of azobenzene units or of the generation, when the azobenzene groups are linked to the surface of the dendrimer. A different behavior was observed when the azobenzene groups were located within the framework of the dendrimer.     

Theoretical models to predict the inhibitory effect of ligands of sphingosine kinase 1 using QTAIM calculations and hydrogen bond dynamic propensity analysis

We report here the results of two theoretical models to predict the inhibitory effect of inhibitors of sphingosine kinase 1 that stand on different computational basis. The active site of SphK1 is a complex system and the ligands under the study possess a significant conformational flexibility; therefore for our study we performed extended simulations and proper clusterization process. The two theoretical approaches used here, hydrogen bond dynamics propensity analysis and Quantum Theory of Atoms in Molecules (QTAIM) calculations, exhibit excellent correlations with the experimental data. In the case of the hydrogen bond dynamics propensity analysis, it is remarkable that a rather simple methodology with low computational requirements yields results in excellent accord with experimental data. In turn QTAIM calculations are much more computational demanding and are also more complex and tedious for data analysis than the hydrogen bond dynamic propensity analysis. However, this greater computational effort is justified because the QTAIM study, in addition to giving an excellent correlation with the experimental data, also gives us valuable information about which parts or functional groups of the different ligands are those that should be replaced in order to improve the interactions and thereby to increase the affinity for SphK1. Our results indicate that both approaches can be very useful in order to predict the inhibiting effect of new compounds before they are synthesized.     

Crystallization in PHB/DGEBA blends

Real‐time experiments using small‐angle X‐ray scattering and differential scanning calorimetry on blends of the semicrystalline polyester poly(3‐hydroxybutyrate) (PHB) and amorphous monomer epoxy DGEBA (diglycidyl ether of bisphenol A) were performed. Differences in the processes of melting and re‐crystallization were observed in blends relative to pure PHB. The results obtained in this study indicated that re‐crystallization is more important in blends with 50% DGEBA than in pure PHB. Moreover, segregation toward the interfibrillar region would facilitate re‐crystallization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 882–886