Laser photolysis of zinc porphyrin dissolved in cyanohexylbiphenyl liquid crystal

A laser photolysis study of ZnTPP (P) oriented in nematic and isotropic cyanohexylbiphenyl (6CB) as a function of added 1.4-benzoquinone (Q) is reported. In the absence of Q, enhancement of triplet absorption below the clearing point (nematic phase) is observed. It is attributed to the improved alignment of the optical transition in the ordered matrix and also to the increase in the intersystem crossing efficiency. T−S₁. In the presence of Q in the nematic phase. An additional increase in triplet absorption is noticed. This result is interpreted in terms of a triplet radical pair [P^+√…Q^−√]^T,RP formation which is facilitated by the ordering in the liquid crystal, thus providing an additional channel for triplet formation. The triplet P^T in 6CB (nematic or isotropic) is quenched with a second-order rate of ≈10⁸ M⁻¹ s⁻¹ as compared to 2 × 10⁹ M⁻¹ s⁻¹ in toluene.     

Gamma radiation effects on physical properties of parchment documents: Assessment of Dmax

Parchments are important documents that give testimony for History; therefore these materials should be respected and preserved. Considering incremental biodeterioration problems that have to be faced daily, the Archive of the University of Coimbra (AUC) is involved in different scientific projects in order to evaluate and determine new methods for document decontamination and preservation.The aim of this study was to evaluate gamma radiation effects on the colour and texture of the AUC parchment documents. The assessment of these effects was used to estimate the maximum gamma radiation dose (D_max) that could guarantee parchment documents′ decontamination treatment, without significant alteration of their physical properties. Parchment samples were exposed to gamma radiation doses ranging from 10 to 30 kGy. The texture and colour of samples were assessed before and after the irradiation procedure, using a texture analyser and an electronic colorimeter. Hardness and springiness were determined based on texture spectra. Lightness (L?), Chroma (C), greenness vs. redness (a*) and yellowness vs. blueness (b*) values were obtained from colorimetric measures. Results indicate no significant effects of gamma radiation on the texture and colour of parchment for the studied doses.     

Development of an LC-MS/MS method for aromatase inhibitor screening

Aromatase (CYP 19A1) is a key steroidogenic enzyme that catalyzes the conversion of androgen to estrogen. In this study, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for aromatase inhibitor screening was developed and validated. The substrate androstenedione was incubated with human CYP 19A1 supersomes in the presence of NADPH for 30 min, and estrone formation was determined by LC-MS/MS analysis. Cortisone was used as internal standard. The incubation mixture was extracted using a liquid-liquid extraction method with ethyl acetate. Chromatographic separation was achieved using a C₁₈ column (3.0?×?50 mm, 2.7 μm) with a mobile phase consisting of 0.1 % formic acid/acetonitrile adopting gradient elution at a flow rate of 0.4 mL/min. The mass spectrometer was operated in positive electrospray ionization mode. The precursor-product ion pairs used for multiple reaction monitoring were m/z 287→97 (androstenedione), m/z 271?→?159 (estrone), and m/z 361?→?163 (IS, cortisone). The developed method met the required criteria for the validation of bioanalytical methods. The validated method was successfully applied to evaluate aromatase inhibitory activity of plants extracts of Simaroubaceae.

Fluorometric analysis of borohydrides based on reductive aldehyde-to-alcohol conversion of arylaldehydes

Fluorometric analysis of borohydride (BH₄^–) species by the reduction of arylaldehydes to the corresponding arylmethanols was investigated. 9-Anthracenecarboxaldehyde (9-AA) exhibited pronounced ratiometric fluorescence signaling behavior toward borohydride in alkaline aqueous media. The borohydride-selective signaling of 9-AA was unaffected by the presence of commonly encountered metal ions and anions. 1-Pyrenecarboxaldehyde (1-PA) also showed comparable borohydride signaling behavior. The detection limit was found to be 7.4?μM (0.11?ppm) for 9-AA and 15.7?μM (0.23?ppm) for 1-PA. The utility of the probe with μPAD as a convenient tool for the determination of borohydrides was demonstrated.     

Stereocontrolled conjugate additions to dihydroindolizinone systems. Synthesis of enantiopure polysubstituted tetrahydropyrrolo[2,1-a]isoquinolones

Conjugate addition reactions of various types of nucleophiles to the γ-lactam unit of dihydroindolizinone systems have been studied. The addition of cuprates, amines or stabilized carbanions requires the activation of the unsaturated bicyclic lactam with a EWG at C-2, while sulfur-stabilized carbanions are reactive enough to add to the unsubstituted lactam. The stereochemical outcome of the conjugate addition reaction depends on the nature of the substituent at the angular position, and the incoming nucleophile. Thus 1,10b-cis or 1,10b-trans diastereomers could be obtained selectively with dr>95:5. The tandem conjugate addition–alkylation also takes place in good yields. These reactions have been applied to the synthesis of enantiopure tetrahydropyrrolo[2,1-a]isoquinolines.