Material and diagnostic characterization of 17th century mural paintings by spectra‐colorimetry and SEM‐EDS: An insight look at José de Escovar Workshop at the CONVENT of Na Sra da Saudação (Southern Portugal)

The early 17th century mural paintings set from the low‐choir of the extinct Dominican Convent of Nossa Senhora da Saudação in the town of Montemor‐o‐novo were analyzed by a setup comprising visible spectra‐colorimetry and scanning electron microscopy coupled with energy dispersive X‐ray spectrometry (SEM‐EDS) complemented with optical microscopy (OM), micro X‐ray diffraction, micro FTIR, and micro Raman spectroscopy. The main goals were material and diagnostic characterization of the paint layers and pictorial techniques used by Jose de Escovar workshop, one of the most active and controversial easel and mural painters of Evora Archiepiscopate between 1585 and 1622. The results show a differentiate use of red, blue, and green pigments in an alkaline environment. Stable mercury sulfide (HgS) was identified in almost all red areas in the latest scenes while, in the first ones, red ochre (Fe₂O₃) is the predominant pigment. Faded smalt (a co‐potassium silicate glass) is present pure in the sky background or mixed with red ochre in the garments at the beginning of the low‐choir but less at the end. Five kinds of copper‐based materials, with different degrees of color alteration, were found, namely malachite and azurite, copper chlorides, copper sulfates (e.g., posjnakite), and pseudomalachite. Another curious feature is the uneven use of a limewash made with slaked calcitic lime in the carnations. Lack of material, internal organization strategies, or technical differences within the team are probably the most likely causes. © 2013 Wiley Periodicals, Inc. Col Res Appl, 39, 288–306, 2014; Published Online 5 February 2013 in Wiley Online Library ( wileyonlinelibrary.com ). DOI 10.1002/col.21792     

“纸绢釉”的研制及其在宋风瓷画创作中的应用

"纸绢釉"是一种经高温烧成能呈现出陈年宣纸或绢布状的棕褐色系泛轻微点状机理的新釉料,烧成后其丰富的机理纹优于单色釉的单一色彩质感,又优于普通颜色釉无法在釉下再做绘画装饰的特性,整体色系质感十分适合表现宋画风格的陶瓷艺术作品,用纸绢釉表现的艺术作品其特点在于融合了对传统宋画的传承和创作者自身的审美素养以及当前时代背景下的文化精神,实现了一种独特的宋风美学样式,也表达了当代艺术创作者对于传统与创新的更深层次的审美理解和艺术追求。     

Study of various interventions in the façades of a historical building—Methodology proposal,chromatic and material analysis

Visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), and energy dispersive X‐ray spectroscopy (EDS) in addition to scanning electron microscopy (SEM) have been used for determining the color and chemical composition of the architectural elements of the façades of a historical building, which today is the seat of the Diputación Provincial of Cadiz. It dates from 1770 and was built as Custom Headquarters. It is near the port and is almost encircled by the walls of the city. The determination of the color and chemical composition of the materials that provoke this color and the determination of the layers found in the extracted samples from significant zones allow to define the various interventions over the façade and to localize the time in which they were made. This is possible by comparing with graphical registries and historical documentation. The objective is a study of the color of the different façades that the building has had in order to know the history of the building and to choose materials and colors that should be used in a restoration intervention of this historical building. © 2005 Wiley Periodicals, Inc. Col Res Appl, 30, 382–390, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.     

Preparation of styrene‐maleic acid copolymers and its application in encapsulated pigment red 122 dispersion

Styrene‐maleic acid copolymers were synthesized by free radical polymerization. Encapsulated pigment red 122 dispersions were prepared by sedimentation with these copolymers. Effects of copolymer structure such as molar content of maleic acid, molecular weight, and the amount of copolymers on stability and particle size of dispersion were investigated. The results showed that encapsulated pigment dispersion with higher stability, smaller particle size, and narrower particle distribution could be achieved when the molar content of maleic acid was at 0.43 and the intrinsic viscosity was at 79.65 ml/g with amount of copolymers 10%. The encapsulated layer was about 5 nm which could be observed by TEM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Characterization of a Pt-Pd combustion catalyst on an alumina washcoat,with and without prior hydrothermal treatment of the washcoat

Two Pt/Pd catalysts on cordierite monoliths were prepared by impregnating two differently treated alumina washcoats with 10 mol [Pt+Pd] per gram catalyst in the atomic ratio Pt/Pd=4.0. Both washcoats were first thermally treated, calcined, for 2 h at 550 °C in air and one of them was additionally treated, hydrothermally, in 100% steam for 2 h at 814 °C. The hydrothermally treated catalyst was more active for complete oxidation of xylene in air: its light-off temperature was 232 °C, compared to 259 °C for the sample calcined only. To explain this higher activity, both catalysts were characterized by BET surface area, pore-size distribution, hydrogen chemisorption, X-ray diffraction, TEM/STEM/EDS and low-energy ion scattering spectroscopy (LEIS). The catalyst with a hydrothermally treated washcoat had 30% lower surface area, larger alumina crystal size, higher degree of crystallization of alumina and larger average catalyst pore size (11 nm vs. 6 nm), than the one with the washcoat, treated only thermally. The LEIS results indicated a surface enrichment of Pd on both catalysts. The Pt signal in LEIS was higher for the hydrothermally treated sample.     

Modeling and biological investigations of an unusual behavior of novel synthesized acridine-based polyamine ligands in the binding of double helix and G-quadruplex DNA

Three novel 2,7-substituted acridine derivatives were designed and synthesized to investigate the effect of this functionalization on their interaction with double-stranded and G-quadruplex DNA. Detailed investigations of their ability to bind both forms of DNA were carried out by using spectrophotometric, electrophoretic, and computational approaches. The ligands in this study are characterized by an open-chain (L1) or a macrocyclic (L2, L3) framework. The aliphatic amine groups in the macrocycles are joined by ethylene (L2) or propylene chains (L3). L1 behaved similarly to the lead compound m-AMSA, efficiently intercalating into dsDNA, but stabilizing G-quadruplex structures poorly, probably due to the modest stabilization effect exerted by its protonated polyamine chains. L2 and L3, containing small polyamine macrocyclic frameworks, are known to adopt a rather bent and rigid conformation; thus they are generally expected to be sterically impeded from recognizing dsDNA according to an intercalative binding mode. This was confirmed to be true for L3. Nevertheless, we show that L2 can give rise to efficient π-π and H-bonding interactions with dsDNA. Additionally, stacking interactions allowed L2 to stabilize the G-quadruplex structure: using the human telomeric sequence, we observed the preferential induction of tetrameric G-quadruplex forms. Thus, the presence of short ethylene spacers seems to be essential for obtaining a correct match between the binding sites of L2 and the nucleobases on both DNA forms investigated. Furthermore, current modeling methodologies, including docking and MD simulations and free energy calculations, provide structural evidence of an interaction mode for L2 that is different from that of L3; this could explain the unusual stabilizing ability of the ligands (L2>L3>L1) toward G-quadruplex that was observed in this study.     

Synthesis,Structure, and Explosive Properties of a New Trinitrate Derivative of an Unexpected Condensation Product of Nitromethane with Glyoxal

In the condensation reaction of nitromethane with glyoxal carried out in an aqueous solution of sodium hydroxide, 3,6‐dinitro‐cyclohexane‐1,2,4,5‐tetraol was obtained (the expected product, described in the literature) and, unexpectedly, also tricyclic nitro‐triol (6b‐nitrohexahydro‐2H‐1,3,5‐trioxacyclopenta[cd]‐pentalene‐2,4,6‐triol), which has been unknown until now, was obtained as the main product. The structure of the compound was confirmed with ¹H NMR and ¹³C NMR spectroscopy, LR, and HR‐MS techniques and with single‐crystal X‐ray diffractometry. The tricyclic triol (formally a hemiacetal) was transformed into 6b‐nitrohexahydro‐2H‐1,3,5‐trioxacyclopenta[cd]‐pentalene‐2,4,6‐triyl trinitrate by reaction with 98 % HNO₃. Some explosive properties of this compound were determined including: friction and impact sensitivity, activation energy, detonation velocity, heat of combustion in an oxygen atmosphere and enthalpy of formation. The nitrate ester is a powerful explosive with performance close to that of pentaerythritol tetranitrate (PETN).     

Identification and characterisation of a calcium carbonate-binding protein, blue mussel shell protein (BMSP), from the nacreous layer

The nacreous layer of molluscan shells consists of a highly organised, layered structure comprising calcium carbonate aragonite crystals, each surrounded by an organic matrix. In the Japanese pearl oyster Pinctada fucata, the Pif protein from the nacreous layer functions in aragonite binding, and plays a key role in nacre formation. Here, we investigated whether the blue mussel Mytilus galloprovincialis also has a protein with similar functions in the nacreous layer. By using a calcium carbonate-binding assay, we identified the novel protein blue mussel shell protein (BMSP) 100 that can bind calcium carbonate crystals of both aragonite and calcite. When the entire sequence of a cDNA encoding BMSP 100 was determined, it was found that BMSP is a preproprotein consisting of a signal peptide and two proteins, BMSP 120 and BMSP 100. BMSP 120 contains four von Willebrand factor A (VWA) domains and one chitin-binding domain, thus suggesting that it has a role in maintaining structure within the matrix. Immunohistochemical analysis revealed that BMSP 100 is present throughout the nacreous layer with dense localisation in the myostracum. Posttranslational modification analysis indicated that BMSP 100 is phosphorylated and glycosylated. These results suggest that there is a common molecular mechanism between P. fucata and M. galloprovincialis that underlies the nacreous layer formation.     

Identification of a novel moth sex pheromone inEriocrania cicatricella (Zett.) (Lepidoptera: Eriocraniidae) and its phylogenetic implications

Extracts from different body parts of adult femaleEriocrania cicatricella (Zett.) were tested for electrophysiological activity on conspecific male antennae. Extracts from the Vth abdominal segment, containing a pair of exocrine glands, elicited the largest electroantennographic response when compared to extracts of other body parts. Female extracts were analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). The EAD active peaks were identified as (Z)-4-hepten-2-one, (2R)-heptane-2-ol, and (2R)-(Z)-4-hepten-2-ol by coinjection on a gas chromatography and by comparison of mass spectra with those of synthetic standards. In field tests, a blend of these three pheromone components was highly attractive to conspecific males, and a subtractive assay confirmed that the unsaturated alcohol is the major pheromone component, whereas no definite behavioral activity could be assigned to the ketone or the saturated alcohol. A bait containing the two alcohols withS-configuration was attractive to maleE. sparrmannella (Bosc), whereas no males ofE. cicatricella were found in these traps. The sex pheromone compounds inE. cicatricella are chemically similar to pheromones reported in Trichoptera and they are produced in homologous glands.     

Identification and Characterization of D‐Succinylase,and a Proposed Enzymatic Method for D‐Amino Acid Synthesis

Chiral amino acids are important intermediates for the pharmaceutical industry. We have developed a novel one‐pot enzymatic method for D ‐amino acid synthesis by the dynamic kinetic resolution of N‐succinyl‐dl ‐amino acids using D ‐succinylase (DSA) and N‐succinylamino acid racemase (NSAR, EC 4.2.1.113). The DSA from Cupriavidus sp. P4‐10‐C, which hydrolyzes N‐succinyl‐D ‐amino acids enantioselectively to their corresponding D ‐amino acids, was identified for the first time by screening soil microorganisms. Subsequently, the DSA gene was cloned and overexpressed in Escherichia coli. DSA was shown to comprise two subunits with molecular masses of 26 kDa and 60 kDa. Additionally, the NSAR gene from Geobacillus stearothermphilus NCA1503, which racemizes N‐succinylamino acids, was also cloned and overexpressed in E. coli. The highly purified DSA and NSAR prepared from each recombinant E. coli were characterized and used for D ‐amino acid synthesis. A one‐pot enzymatic method converted 100 mM N‐succinyl‐dl ‐phenylalanine to D ‐phenylalanine in 91.1% conversion with 86.7% ee. This novel enzymatic method may be useful for the industrial production of many D ‐amino acids.

     

Identification of the Verruculogen Prenyltransferase FtmPT3 by a Combination of Chemical,Bioinformatic and Biochemical Approaches

Previous studies showed that verruculogen is the end product of a biosynthetic gene cluster for fumitremorgin‐type alkaloids in Aspergillus fumigatus and Neosartorya fischeri. In this study, we isolated fumitremorgin A from N. fischeri. This led to the identification of the responsible gene, ftmPT3, for O‐prenylation of an aliphatic hydroxy group in verruculogen. This gene was found at a different location in the genome of N. fischeri than the identified cluster. The coding sequence of ftmPT3 was amplified by fusion PCR and overexpressed in Escherichia coli. The enzyme product of the soluble His₈‐FtmPT3 with verruculogen and dimethylallyl diphosphate (DMAPP) was identified unequivocally as fumitremorgin A by NMR and MS analyses. K_M values of FtmPT3 were determined for verruculogen and DMAPP at 5.7 and 61.5 μM , respectively. Average turnover number (k_cat) was calculated from kinetic parameters of verruculogen and DMAPP to be 0.069 s^?1. FtmPT3 also accepted biosynthetic precursors of fumitremorgin A, for example, fumitremorgin B and 12,13‐dihydroxyfumitremorgin C, as substrates and catalyses their prenylation.     

Synthesis of a hypercrosslinked,ionic, mesoporous polymer monolith and its application in deep oxidative desulfurization

In this study, we used a facile and scalable strategy to produce a hypercrosslinked, ionic, mesoporous polymer monolith (HCIMPM). On the basis of structure‐directing polymeric crosslinking, the interconnected nanonetwork was formed through the in situ crosslinking of the homopolymer poly(vinyl imidazole) via a quaternization reaction, and its textural properties could be effectively adjusted by the block copolymer poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide)(PEO₂₀PPO₇₀PEO₂₀). The maximum specific surface area and pore volume were 212 m²/g and 1.08 cm³/g, respectively. Furthermore, the synthetic framework could be functionalized via the loading of PW₁₂ through ion exchange. The obtained HCIMPM with PW₁₂O₄₀^3? (PW‐HCIMPM) was applied in the oxidative desulfurization, and approximately 100% sulfur removal could be achieved in the model oil with hydrogen peroxide (30 wt %) as an oxidant. Moreover, the solid catalyst could be recovered readily and recycled at least six times without a significant decrease in the desulfurization efficiency. As for real diesel, we also observed that almost all of the original sulfur compounds could be converted in 120 min. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46280.