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.     

Site-selective C–H nitration of N-aryl-7-azaindoles under palladium(II) catalysis

The site-selective C–H nitration reaction of 7-azaindoles with t-butyl nitrite under palladium catalysis is described. This protocol provides an efficient method for the construction of ortho-nitrated N-aryl-7-azaindoles with excellent site-selectivity and functional group compatibility. The formed 7-azaindole derivatives can be readily transformed into 7-azaindoles containing an aniline functional group under palladium-catalyzed hydrogenation conditions.     

Determination of docetaxel in rat plasma and its application in the comparative pharmacokinetics of Taxotere and SID530, a novel docetaxel formulation with hydroxypropyl‐β‐cyclodextrin

In this study, a sensitive, simple and reliable method for the quantification of docetaxel in rat plasma was developed and validated using liquid chromatography–tandem mass spectrometry (LC‐MS/MS). The plasma samples were prepared by protein precipitation, and paclitaxel was used as an internal standard (IS). Chromatographic separation was achieved using a Gemini C₁₈ column (2.0 × 150 mm, 5 µm) with a mobile phase consisting of 0.1% formic acid–acetonitrile (30:70, v/v). The precursor–product ion pairs used for multiple reaction monitoring were m/z 808.5 → 527.5 (docetaxel) and m/z 854.2 → 286.5 (IS, paclitaxel). A calibration curve for docetaxel was constructed over the range 1–1000 ng/mL. The developed method was specific, precise and accurate, and no matrix effect was observed. The validated method was applied in a comparative pharmacokinetic study in which two docetaxel formulations, SID530, a new parenteral formulation of docetaxel with hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD), and Taxotere, were administered to rats at a dose of 5 mg/kg. For SID530 and Taxotere, the mean C₀ values were 1494 and 1818 ng/mL, respectively, and the AUC_last values were 837 and 755 h ng/mL, respectively. These two formulations did not show any statistical differences with regard to the pharmacokinetic parameters, thus establishing that the SID530 and Taxotere products are pharmacokinetically comparable in male rats. Copyright © 2012 John Wiley & Sons, Ltd.     

Deposition of a Continuous and Conformal Copper Seed Layer by a Large-Area Electron Cyclotron Resonance Plasma Source with Embedded Lisitano Antenna

To deposit copper seed layer on ultra large scale integration devices, a large-area (Ø 378 mm) electron cyclotron resonance plasma has been generated by using permanent magnets-embedded Lisitano antenna. The plasma source operates in the pressure range of 0.2–1.5 mTorr with microwave power range of 500–2,000 W. By using a Langmuir probe, the electron density and temperature have been measured near the DC sputter target position. Measurements indicate argon plasmas having electron densities of ~5 × 10¹⁰/cm and electron temperatures of 5 eV with 750 W microwave power at gas pressures of 0.5 mTorr. Using this plasma source and a DC sputter, we obtained excellent conformal copper seed layer with high aspect ratios of 12:1. This is in contrast with conventional methods using magnetron sputter, which has aspect ratios of 2–3:1. Also, improvements are observed in the smoothness (root mean square roughness of 1.345 nm), uniformity (2.5 % at 300 mm wafer), and sidewall symmetricity (more than 95 %) of the copper seed layer.     

Unexpected reactivity of pyridinium salts toward alkynyl Fischer complexes to produce oxo‐heterocycles

The unprecedented reaction of ketone‐containing aromatic pyridinium salts 3a ‐ e and alkynyl Fischer complexes 1a ‐ f proceeds via a mild domino process to provide 4,6‐disubstituted pyran‐2‐ones 5a ‐ k and 2,3,5‐trisubstituted furans 6a ‐ h (45‐97%). According of the results of isotopic labeling experiments, a mechanism involving an initial Michael addition appears to be the key step, obtaining a mesomeric structure responsible for the formation of both products.     

Biomimetic pH/redox dual stimuli‐responsive zwitterionic polymer block poly(L‐histidine) micelles for intracellular delivery of doxorubicin into tumor cells

A series of pH/redox dual stimuli‐responsive poly(2‐methacryloyloxyethyl phosphorylcholine)₂₅‐block‐poly(l ‐histidine)_n (p[MPC])₂₅‐b‐p[His]_n, n = 20, 35, 50, and 75) copolymers consisting of a pH‐responsive p(His)_n block and a biocompatible phospholipid analog p(MPC) block connected by a redox‐responsive disulfide linker have been synthesized. The block copolymers are self‐assembled into uniform micelles (～100 nm) in which doxorubicin (Dox) is efficiently encapsulated. The in vitro release profile shows an enhanced release of Dox at low pH (5.0) in 10 mM glutathione (GSH). The in vitro cell viability assays performed using various cell lines show that the blank hybrid micelles have no acute or intrinsic toxicity. A pH‐dependent cytotoxicity is observed with the Dox‐loaded micelles, especially at pH 5.0. Moreover, confocal microscopy images and flow cytometry results show the pH‐dependent cellular uptake of Dox‐loaded micelles. Therefore, the Dox‐loaded micelles can be considered a good candidate for cancer therapy. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2061–2070     

Photovoltaic devices using semiconducting polymers containing head‐to‐tail‐structured bithiophene,pyrene, and benzothiadiazole derivatives

An alternating copolymer composed of heal‐to‐tail‐structured 3,4′‐dihexyl‐2,2′‐bithiophene (DHBT) and pyrene units [poly(DHBT‐alt‐PYR)] was synthesized using a Stille coupling reaction for use in photovoltaic devices as a p‐type donor. For the reduction of the bandgap energy of poly(DHBT‐alt‐PYR), 4,7‐bis(3′‐hexyl‐2,2′‐bithiophen‐5‐yl)benzo[c][1,2,5]thiadiazole (BHBTBT) units were introduced into the polymer. Poly(DHBT‐co‐PYR‐co‐BHBTBT)s were synthesized using the same polymerization reaction. The synthesized polymers were soluble in common organic solvents and formed smooth thin films after spin casting. The optical bandgap energies of the polymers were obtained from the onset absorption wavelengths. The measured optical bandgap energy of poly(DHBT‐alt‐PYR) was 2.47 eV. As the BHBTBT content in the ter‐polymers increased, the optical bandgap energies of the resulting polymers decreased. The bandgap energies of poly(50DHBT‐co‐40PYR‐co‐10BHBTBT) and poly(50DHBT‐co‐20PYR‐co‐30BHBTBT) were 1.84 and 1.73 eV, respectively. Photovoltaic devices were fabricated with a typical sandwich structure of ITO/PEDOT:PSS/active layer/LiF/Al using the polymers as electron donors and [6,6]‐phenyl C₇₁‐butyric acid methyl ester as the electron acceptor. The device using poly(50DHBT‐co‐20PYR‐co‐30BHBTBT) showed the best performance among the fabricated devices, with an open‐circuit voltage, short‐circuit current, fill factor, and maximum power conversion efficiency of 0.68 V, 5.54 mA/cm², 0.35, and 1.31%, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012