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Ceramic sherds from approximately 20 samples of lead-glazed tableware, recovered from diverse archaeological sites, including three repurposed storage pits transformed into dumpsters within the medieval city of Santarém (13th–14th century), underwent a meticulous examination. This investigation utilised techniques such as micro-Raman, ground-state diffuse reflectance absorption, and X-ray fluorescence spectroscopies, in addition to X-ray diffraction and stereomicroscopy. A parallel study was conducted on contemporaneous European ceramics (glazed sherds) sourced from archaeological sites dating back to the 13th–15th centuries in Saintonge (France), Ardenne, Zomergem, and Bruges (Belgium), as well as Surrey–Hampshire, Kingston, and Cheam (England). The first premise for comparing the Santarem samples with European production locations was their frequent commercial relations with Portugal and the frequency of these productions being found in Portugal. The colour of the ceramic bodies is predominantly white or whitish, with a few exhibiting a vivid red hue. Analyses of the fabric, mineralogical, and elemental composition of the sherds suggest that the majority of Santarém's glazed ceramics were locally or regionally produced, potentially derived from a Pliocene kaolin-rich sand formation. However, this conclusion is not supported by the absence of discovered lead glaze kilns or workshops in Santarém for the late Middle Ages. [ABSTRACT FROM AUTHOR]

Nanostructured Cobalt‐Actinide (An=Th, U) bimetallic oxides were for the first time prepared by the epoxide addition method and electrospinning technique aiming the synthesis of aerogels and nanofibers, respectively. Tested as catalysts for the methanation of CO2 and regardless of the actinide element, the yield and selectivity towards CH4 are high (>40 and 95 %, respectively), which was explained by their physicochemical properties such as reducibility and basicity and the existence of a synergic effect between cobalt and actinide species. The aerogels present the best catalytic behavior, namely those with thorium and the catalytic activity increases with the Co/An molar ratio. Both aerogels and nanofibers also present a high resistance to deactivation for at least 75 h in the gaseous stream, which is an advantage for any catalytic application. Moreover, at 300 °C they are 2 to 4 times more active than two reference catalysts (5wt % Rh/Al2O3 and NiO/Al2O3) tested in the same conditions, which to our best knowledge is a significant result. [ABSTRACT FROM AUTHOR]

Squaraine dyes have recently attracted interest as potential second generation photosensitizers for photodynamic therapy. Several cationic aminosquaraine dyes bearing benzoselenazole terminal nuclei were synthezised and their cytotoxic activity was tested against four different human tumor cell lines – breast (MCF-7), non-small cell lung (NCI-H460), cervical (HeLa) and hepatocellular (HepG2) carcinomas – and against a non-tumor porcine liver primary cell line (PLP2), both in the absence of light and under irradiation. All dyes, which displayed strong absorption within the phototherapeutic window, were found to exhibit photodynamic activity and were shown to be, in most cases, more cytotoxic, both in the dark and upon irradiation, than their benzothiazole analogues. [ABSTRACT FROM AUTHOR]

This work reports the surface photochemistry study of alloxazine adsorbed within nanochannels of MFI zeolites, namely in a series of Na橷 H攣5 zeolites where the hydrophobic and hydrophilic character of the host varies systematically. Laser-induced room temperature and 77 K luminescence of air-equilibrated solid powdered samples of alloxazine adsorbed onto the two sets of zeolites, which we will name NaZSM-5 and HZSM-5, revealed the existence of a single emission of alloxazine as a broad band centred at about 450 nm in some cases, while in others an emission with a maximum at about 510 nm was detected. The decay times of the alloxazine emission vary greatly going from solution to entrapment within the nanochannels of the ZSM-5 zeolites. In the latter case a lifetime distribution analysis has shown that the longest lifetime for the alloxazine fluorescence emission exists in the case where an isoalloxazine-type emission was detected, i.e.whenever the hydrophobic character of the host increases. Alloxazine entrapped in the more acidic zeolites exists in the form of emissive monomers. However, alloxazine emits both from monomeric and aggregated emissive forms in the case of the hydrophobic zeolites. These data indicate the formation of planar dimers of alloxazine whenever the number of active sites in the zeolite decreases. These dimers have to be formed at the intersections of the zig–zag and linear nanochannels of the zeolite since there is no space available for their formation inside the zeolite channels. The isoalloxazine tautomers are formed due to the existence of alloxazine dimers which may undergo double proton transfer in the excited state, following laser excitation. Delayed fluorescence of alloxazine was also detected for the HZSM-5 and NaZSM-5 entrapment both at room temperature and at 77 K. The present study is paradigmatic as regards the host influence on the photochemistry of the guest. [ABSTRACT FROM AUTHOR]

Nanocomposites TiO2-CdS with different relative contents of CdS (molar ratios Cd/Ti = 0.02, 0.03, 0.05, 0.1, 0.2, and 0.5) were studied. The structural, photophysical, and chemical properties were investigated using XRD, Raman spectroscopy, XPS, GSDR, and LIL. XRD and Raman results confirmed the presence of TiO2 and CdS with intensities dependent on the ratio Cd/Ti. The presence of CdSO4 was detected by XPS at the surface of all TiO2-CdS composites. The relative amount of sulphate was dependent on the CdS loading. Luminescence time-resolved spectra clearly proved the existence of an excitation transfer process from CdS to TiO2 through the luminescence emission from TiO2 after excitation of CdS at λexc=410 nm, where no direct excitation of TiO2 occurs. Photodegradation of a series of aromatic carboxylic acids—benzoic, salicylic, 4-bromobenzoic, 3-phenylpropionic, and veratric acids—showed a great enhancement in the photocatalytic efficiency of the TiO2-CdS composites, which is due, mainly, to the effect of the charge carriers’ increased lifetime. In addition, it was shown that the oxidation of CdS to CdSO4 did not result in the deactivation of the photocatalytic properties and even contributed to enhance the degradation efficiency. [ABSTRACT FROM AUTHOR]

In this study, cotton fabrics decorated with Ag/AgCl and Ag/AgBr NPs were produced by a simple hydrothermal treatment using AgCl and AgBr as precursors. Their morphological features as well as, chemical composition and structural and luminescence properties were compared. Their water disinfection aptitude against E. coli and S. aureus was also investigated under solar illumination in batch as well asin dynamic conditions. The highest activity was observed for Cot-Ag/AgCl with a quasi-complete inactivation of E. coli and S. aureus(1.5 × 10 7 cfu mL -1 ) within 15 min illumination. Disinfection efficiency under continuous flow was also tested using a home-made photoreactor and the cotton fabrics with the most efficient photocatalyst (Ag/AgCl). It has shown to be efficient at least for 10 cycles revealing the robustness of the functionalization. The mechanism of photocatalytic disinfection was explained in terms of the surface plasmon resonance (SPR) induced by the presence of Ag NPs, the resulting holes, h + , being one of the most intervenient species in the disinfection mechanism. The difference in the photocatalytic efficiency between AgCl and AgBr functionalized cotton was attributed to differences in the carriers (h + and e-) lifetime. This work provides a proof of concept for the potential applicability of Cot-Ag/AgCl or Cot-Ag/AgBr for in-flow potabilization of water under solar illumination., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A simple approach to functionalize cotton fabrics with Au and TiO 2 nanostructured layer is presented. Hybrid fabrics (Cot-Au-TiO 2 ) are prepared through reduction of AuCl 4 - on cotton, followed by a non-aqueous sol-gel procedure using tetrabutyltitanate and a hydrothermal treatment at 110°C. The generation of crystalline TiO 2 is confirmed by Raman spectroscopy. The fibres morphology and their roughness are characterized by AFM and FE-SEM. XPS shows how the concentration of the NPs precursors (Au and TiO 2 ) affects the layer composition. GSDR (Ground State Diffuse Reflectance Absorption Spectroscopy) and LIL (Laser induced luminescence) reveal a strong quenching effect induced by Au NPs. Photocatalytic activity measured through the Remazol Blue (RB) degradation reveals an enhancement under visible light, which increases with Au loading. This strong enhancement is explained through the surface plasmon resonance brought by Au NPs., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Porphyrins and some of its derivatives are well known and widely used as photosensitizers (PSs) for Photodynamic Therapy of Cancer (PDT). The present study regards the characterization and evaluation of a synthesized asymmetric porphyrin dye in solution to be used as PS for PDT. This molecule was also incorporated into biopolymeric films composed by chitosan, polyethylene glycol (PEG) and gelatin in order to overtake some of the disadvantages inherent to the PS, but more important, to evaluate the potential of a system composed by the porphyrin/biopolymer to be applied as localized therapeutic agents. FTIR spectroscopy showed a strong interaction between the polymers involved in the preparation of the films under study: film 1: chitosan, film 2: chitosan/PEG and film 3: chitosan/gelatin. Photochemical studies were performed for the dye in solution and into the three different biopolymeric films. Ground state absorption showed the characteristic bands of these kinds of dyes in solution and also incorporated into the films. The films composed by porphyrin/chitosan and porphyrin into chitosan/gelatin, revealed the presence of non-emissive aggregates exhibiting a strong quenching effect in the fluorescence intensity, quantum yields and lifetimes. In this way, the system composed by the porphyrin incorporated into the chitosan/PEG film presents the best fluorescence quantum yield and lifetime. The transient absorption spectra were obtained for all the systems indicating the formation of an excited triplet state of the porphyrins following excitation, which takes special importance in the generation of phototoxic species namely singlet oxygen. Singlet oxygen quantum yields were also determined and the results obtained were very promising for the dye in solution but also for the dye into the different substrates. The release of the dye from the three different films onto a buffer solution was evaluated and we conclude that after a few days the dye was completely released by the substrates in acidic conditions. Confocal microscopy was used for the determination of the intracellular localization of the compound under study onto HeLa cells (human cervical cancer cells line). The evaluation of the PSs anticancer activity assumes special importance for PDT studies. The system should be less toxic in the dark and more active when irradiated, therefore, toxicity in the dark and phototoxicity studies onto HeLa cells were performed., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A green, safe and fast procedure is presented for in situ generation of nanoparticles (NPs) of cuprous oxide (Cu2O) onto cotton fibres at room temperature using water as a solvent. The method is based on a mild surface oxidation of cellulose fibres to generate in a controlled way carboxylic groups acting as a binding site for the adsorption of Cu(2+) via electrostatic coordination. Then, the adsorbed Cu(2+) ions were readly converted into Cu2O by dipping the treated cotton fibres into a aqueous solution of a reducing agent. Field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), as well as UV-vis absorption and emission spectroscopic methods were used to analyse the size, morphology, chemical composition and the crystalline structure of the generated nanoparticles on the fabrics. The morphology of the ensuing Cu2O nanoparticles was shown to be dependent on the reduycing agent used. Antibacterial properties of the modified fibres were also investigated., (Published by Elsevier Ltd.)

Sherds representative of the three Portuguese faience production centers of the 17th century - Lisbon, Coimbra and Vila Nova were studied with the use of mostly non-invasive spectroscopies, namely: ground state diffuse reflectance absorption (GSDR), micro-Raman, Fourier-transform infrared (FT-IR) and proton induced X-ray (PIXE) or X-ray fluorescence emission (XRF). X-ray diffraction (XRD) experiments were also performed. The obtained results evidence a clear similarity in the pastes of the pottery produced Vila Nova and some of the ceramic pastes from Lisbon, in accordance with documental sources that described the use of Lisbon clays by Vila Nova potters, at least since mid 17th century. Quartz and Gehlenite are the main components of the Lisbon's pastes, but differences between the ceramic pastes were detected pointing out to the use of several clay sources. The spectroscopic trend exhibited Coimbra's pottery is remarkably different, Quartz and Diopside being the major components of these pastes, enabling one to well define a pattern for these ceramic bodies. The blue pigment from the Lisbon samples is a cobalt oxide that exists in the silicate glassy matrix, which enables the formation of detectable cobalt silicate microcrystals in most productions of the second half of the 17th century. No micro-Raman cobalt blue signature could be detected in the Vila Nova and Coimbra blue glazes. This is in accordance with the lower kiln temperatures in these two production centers and with Co(2+) ions dispersed in the silicate matrix. In all cases the white glaze is obtained with the use of tin oxide. Hausmannite was detected as the manganese oxide mineral used to produce the purple glaze (wine color "vinoso") in Lisbon., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Two sherds representative of the Portuguese faience production of the first and second halves of the 17th century were studied carefully with the use of non-invasive spectroscopies, namely: Ground State Diffuse Reflectance Absorption (GSDR), micro-Raman, Fourier-Transform Infrared (FT-IR), Laser Induced Luminescence (LIL) and Proton Induced X-ray (PIXE). These results were compared with the ones obtained for a Chinese Ming porcelain, Wanli period (16th/beginning of the 17th centuries), which served as an influence for the initial Lisbon's faience production. By combining information of the different non-destructive spectroscopic techniques used in this work, it was possible to conclude that: Co(3)O(4) (Co II and Co III) can be found in the silicate matrix and is the blue pigment in the "Especieiro" sample (1st half of the 17th C.). Cobalt olivine silicate (Co(2)SiO(4), Co II only) was clearly identified as the blue pigment in "Aranhões" sample (2nd half of the 17th C.) - 824 cm(-1) band in the micro-Raman-spectrum. Cobalt aluminate (CoAl(2)O(4), Co II only) is the blue pigment in the Wanli plate - 203 and 512 cm(-1) bands in the micro-Raman spectrum. The blue pigment in the 1st half 17th century of Lisbon's production was obtained by addition of a cobalt ore in low concentrations, which gives no specific Raman signature, because of complete dissolution in the glass. However, in most cases of the 2nd half 17th century, the Raman signature was quite evident, from a cobalt silicate. These findings point to the use of higher temperature kilns in the second case., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The mechanism of electron-transfer from aluminium tetrasulfonated phthalocyanine triplet state to cytochrome c was investigated in this work. This reaction successfully quenches the dye triplet state due to the formation of complexes between the solute and the protein at the active site. The electron-transfer rate constant is around 3x10(7) s(-1), and is in accordance with previous results for the singlet excited state quenching [C.A.T. Laia, S.M.B. Costa, D. Phillips, A. Beeby. Electron-transfer kinetics in sulfonated aluminum phthalocyanines/cytochrome c complexes, J. Phys. Chem. B 108 (2004) 7506-7514.] in the framework of the Marcus theory, with a reorganization energy equal to 0.94 eV. The complex formation is diffusion controlled, but heterogeneities of the protein surface charge distribution lead to quenching rate constants smaller than predicted on a hard-spheres model with electrostatic interactions. Also the binding equilibrium constant is strongly affected by this phenomenon. Ionic strength plays an important role on the complex formation, but its effect on the unimolecular electron-transfer rate constant is negligible within experimental error.

This work reports the use of benzophenone, a very well characterized probe, to study new hosts: two reversed-phase silicas. Laser-induced room temperature luminescence of argon purged solid powdered samples of benzophenone adsorbed onto the two different reversed-phase silicas, RP-18 and RP-8, revealed the existence of a low energy emission band in contrast with the benzophenone adsorbed on 60 A pore silica, where only triplet benzophenone emits. This low energy emission band was identified as the fluorescence of the ketyl radical of benzophenone, which is formed as the result of a hydrogen atom abstraction reaction of the triplet excited benzophenone from the alkyl groups of the surface of the reversed silicas. Such emission does not exist for benzophenone adsorbed onto 60 A pore silica. Room temperature phosphorescence was obtained in argon purged samples for all the surfaces under use. The decay times of the benzophenone emission vary greatly with the alkylation of the silica surface when compared with "normal" silica surface. A lifetime distributions analysis has shown that the shortest lifetimes for the benzophenone emission exist in the former case. Triplet-triplet absorption of benzophenone was detected in all cases and is the predominant absorption in the case of 60 A pore silica, while benzophenone ketyl radical formation occurs in the case of the reversed silicas. Diffuse reflectance laser flash photolysis and gas chromatography-mass spectrometry techniques provided complementary information, the former about transient species and the latter regarding the final products formed after laser irradiation, both at 266 nm or 355 nm. Product analysis and identification show that the degradation photoproducts are dependent on the excitation wavelength, the photochemistry being much more rich and complex in the 266 nm excitation case, where an alpha-cleavage reaction occurs. A detailed mechanistic analysis is proposed.