The present work investigates the physicochemical stability of spray paints when irradiated with artificial solar light (at spectral range 300–800 nm). This research highlights the importance of understanding the materials used in street art and public murals, recognising them as a significant component of contemporary cultural heritage. By examining the stability and degradation of spray paints toward solar light exposure, the study aims to contribute to the preservation of contemporary murals, which reflect current social and cultural narratives. A physicochemical approach was employed for the study of spray paints’ physical and thermal properties, as well as the effect of specific photochemical ageing reactions/processes. The photochemical ageing results were compared with reference (unaged) samples. Specifically, a multi-technique approach was applied using stereo microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle measurement, colorimetry, glossimetry, differential scanning calorimetry (DSC), UV-Vis spectroscopy, attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and pyrolysis-GC/MS (Py-GC/MS). The photodegradation of the spray paints occurred from the first 144 h of solar light irradiation, resulting in changes in morphology, colour, gloss, roughness, and wettability. Regarding photochemical stability, ageing seems to affect the binders more than the synthetic organic pigments and the inorganic fillers. In particular, acrylic binders showed small chemical changes, whereas the alkyd, nitrocellulose, and styrene binders underwent severe chemical modification. The results suggest that simulated daylight irradiation prompts the migration of additives toward the surface of the spray paint films. In addition, the results of the analyses on the white spray paints in comparison with the coloured paints (from the same manufacturer) showed that there seems to be an active distinct photoageing mechanism involving titanium dioxide, but the whole issue needs further investigation.

In this study the chemical characterisation of 24 commercial spray-paints in different colours as used in contemporary public murals, street art, and graffiti is presented. The analyses were focused on the identification of the binding media, pigments, and additives. In addition, four spray-paint samples were analysed in the form of bi-layered paint films to explore the possibility of determining the composition of multi-layered samples. The aim of the study was to provide a useful diagnostic tool for the conservation of spray-paints and the removal of overpaintings from both commissioned murals and any other form of cultural heritage. To achieve this goal, a multi-analytical approach was developed using Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) for the identification of the main binder, pigments, and fillers/extenders, while Raman spectroscopy and Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy (SEM/EDS) were used as complementary tools for the determination of organic and inorganic pigments, and fillers. Five kinds of binders were detected in this work: (1) acrylic resins combined with nitrocellulose, (2) acrylic resins modified with styrene and combined with nitrocellulose, (3) alkyd resins modified with styrene and combined with nitrocellulose, (4) combined acrylic and alkyd resins modified with styrene and blended with nitrocellulose, and (5) combined polystyrene and acrylic resins. Also, a wide variety of organic pigments and inorganic components were detected.

Abstract This study outlines the chemical characterisation of various commercial spray-paints in different colours as used in contemporary public murals, street art, and graffiti. The analyses were focused on the identification of the binding media, pigments, and additives. The aim of the study was twofold; to establish a protocol for the diagnosis of aerosol paints and to provide useful information, which could help conservators remove overpaintings from both commissioned murals and any other form of cultural heritage. A multi-technique approach was developed using Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) for the identification of the main binder, pigments, and extenders, while Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy (SEM/EDS) and Raman spectroscopy were used as complementary tools for the determination of organic and inorganic pigments, and fillers. Three kinds of binders based on alkyd or acrylic resins modified with nitrocellulose and/or styrene, along with a variety of organic pigments and inorganic components were detected.

In this work a series of Dawson Polyoxometalates (POMs) with different cations and addenda atoms were grown as interfacial layers between indium fin oxide (ITO) and regio-regular poly(3-hexylthiophene) (rr-P3HT) in order determine the effect of different POMs films on the energy band alignment at the heterojunction rr-P3HT/ITO. The POMs/ITO and rr-P3HT/POMs/ITO interfaces were investigated by X-ray Photoelectron and Ultra-Violet Photoelectron Spectroscopies (XPS, UPS) to gain insight into their chemical morphology, the energetics of the formed interfaces and the charge carrier barriers. We show that POMs are reduced upon deposition on ITO and the extent of their reduction is controlled by their cation and addenda atom. The deposition of POMs on ITO results to the formation of interface dipoles and the work function of ITO is increased up to 5.9 eV. When, a thin layer of rr-P3HT is formed on top of POMs modified ITO, electron transfer from rr-P3HT to the substrate occurs when the work function of POM/ITO substrates is > 4.5 eV, resulting to a pinning of the highest occupied molecular orbital (HOMO) of rr-P3HT and the formation of ohmic contacts. The results were interpreted by the integer charge transfer model (ICT).

In this work a peptide nucleic acid (PNA) was covalently connected with two different chromophores, namely porphyrin and boron-dipyrromethene. To the best of our knowledge, this is the first example in the literature where a PNA unit is covalently linked to such chromophores. The self-assembly properties of the hybrids were examined through electron microscopy experiments by adopting the "good-bad" solvent self-assembly protocol. For both hybrids (PNA-TPP and PNA-BDP) we were able to observe distinctive supramolecular architectures. During these studies we investigated the influence of the solvent system, the concentration and the deposition method on the morphology of the formed nanostructures. In the case of PNA-TPP under all examined conditions well-formed nanospheres were obtained. Interestingly, in the PNA-BDP hybrid by simply altering the solvent mixture, self-assemblies of two different morphologies were formed (spherical and flake shaped). Absorption and emission studies suggested the formation of J-aggregates in all the obtained nanostructures. The nano-architectures assembled by PNA conjugates are capable of light-harvesting and producing hydrogen using Pt nanoparticles as a photocatalyst.

All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV-vis spectroscopy and AFM measurements show that this functionality stems from the films' ability to structurally tune their HOMO-LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures' plausibility for on-chip molecular electronics operative at room temperature.

Herein, we report on the study of supramolecular assemblies based on polyoxometalates (POMs) upon their modification with amino acids. Two POM-amino acid hybrids were synthesized by coupling a functionalized Keggin type polyoxoanion [PW11O39{Sn(C6H4)C[triple bond, length as m-dash]C(C6H4)COOH}]4- with carboxyl-protected (methyl-ester) phenylalanine or diphenylalanine peptides. Surprisingly, all compounds, including the initial POM, formed supramolecular nanospheres in different solvent mixtures, which were examined by scanning electron microscopy (SEM). Molecular dynamics (MD) simulations for the POM-amino acid species revealed that the hydrophobic forces are mainly responsible for the initial aggregation into incipient micelle type structures, in which the organic arms are buried inside the aggregate while POM polar heads are more exposed to the solvent with tetrabutyl-ammonium counter cations acting as linkers.

The investigation of conditions allowing multi-electron reduction and reoxidation of polyoxometalate (POM) films onto solid substrates is considered an issue of critical importance for their successful incorporation in electronic devices, different types of sensors and catalytic systems. In the present paper, the rich multi-electron redox chemistry of films of Wells-Dawson ammonium salts, namely (NH4)6P2Mo18O62 and (NH4)6P2W18O62, on top of metallic (Al), semiconducting (ITO) and dielectric (SiO2) substrates under ambient conditions is investigated. The respective Keggin heteropolyacids, H3PMo12O40 and H3PW12O40, are also investigated for comparison. On Al substrates, the Wells-Dawson ammonium salts are found to be significantly more reduced (4-6e-) compared to the respective Keggin heteropolyacids (∼2e-), in accordance with their deeper lying lowest unoccupied molecular orbital (LUMO) level. Subsequent thermal treatment in air results in reoxidation of the initially highly reduced POM films. Similar behavior is found on ITO substrates, but in initially less reduced (2-4e-) Wells-Dawson POM films. On the other hand, on SiO2 substrates, the thermal reduction of (NH4)6P2Mo18O62 film is observed and attributed to the thermal oxidation of ammonium counterions by [P2Mo18O62]6- anions. Overall, the multi-electron reduction of Wells-Dawson ammonium salts onto metallic and semiconducting substrates (Al, ITO) is determined by the relative position of the LUMO level of POMs in relation to the Fermi level of the substrate (i.e. substrate work function) and affected in a synergistic way by the presence of ammonium counterions. In contrast, on dielectric substrates (SiO2) the reduction of Wells-Dawson POMs ((NH4)6P2Mo18O62) is attributed only to the oxidation of ammonium counterions.

In this work, silicon substrates with poly(vinyl alcohol) (PVA) patterns created by a simple, low-cost and high-fidelity photolithographic procedure were evaluated with respect to cell adhesion and alignment, viability, metabolic activity, proliferation and cell cycle progression using the human glioblastoma cell-line U87MG and human skin fibroblasts. In addition, rat adrenal pheochromocytoma cells (PC-12) were employed to evaluate a modified photolithographic protocol appropriate for adhesion of cells requiring extracellular matrix components to adhere on the surface and to demonstrate that the proposed patterned substrates could provide unhindered cell differentiation. Regarding U87MG cells and skin fibroblasts, it was found that as the stripes width increased from 10 to 50 μm, the percentage of cells attached to Si versus the total area (Si + PVA) increased from 78% and 72% to 98.5% and 94.5% (p < 0.05), for U87MG cells and skin fibroblasts, respectively, with optimum cell alignment (≥95% of adherent cells with fidelity between 0.90 and 1.0; p < 0.05) for stripes width ranging between 20 and 22.5 μm. Concerning the viability, metabolic activity and proliferation of adherent cells, no statistically significant differences were observed compared to cells cultured onto non-patterned surfaces. Regarding PC-12 cells, a modification of the patterning procedure was followed involving coating of the substrate with type IV collagen prior to the photolithographic procedure, since they could not adhere on plain Si substrates. It was found that PC-12 cells adhere selectively (>95%) to collagen-coated Si stripes when the pattern width was equal to or wider than 10 μm. Following treatment with nerve growth factor, approximately 80% (p < 0.05) of the adherent cells differentiated to neuron-like cells extending neurites exclusively within the pattern. Given that the proposed patterning procedure allows highly selective cell adhesion without affecting cell proliferation, metabolic activity, and differentiation it could serve as a useful tool in various fields including tissue engineering, cell-based sensors and analytical microsystems.

Plasma treatment is an environmentally friendly solution for modifying or nanostructuring the surface of several materials including photoactive polymers. The detailed characterization of the effect of plasma treatment on chemical and optoelectronic properties of photoactive polymers is, therefore, of specific interest. Herein, the effect of the exposure of poly(3-hexylthiophene) (P3HT) thin films to plasma created in three different gases (oxygen, argon and hydrogen) was studied. A range of spectroscopic techniques, such as x-ray (XPS) and ultraviolet (UPS) photoelectron spectroscopy in conjunction with UV–vis absorption, Fourier transform infrared (FTIR) and photoluminescence (PL) spectroscopies, are employed to quantify the extent of chemical modification occurring in each particular case. It is shown that oxygen plasma treatment leads to the disruption of the π-conjugation via the direct oxidation of the sulfur atom of the thiophene ring while the aliphatic side chain remains nearly unaffected. An oxidation mechanism is proposed according to which the sulfur atom of the thiophene ring is oxidized into sulfoxides and sulfones, which subsequently degraded into sulfonates or sulfonic acids in a relatively small degree. For argon and hydrogen plasma treatments some oxidation products are detected only at the polymer surface. In all cases the polymer surface Fermi level is shifted closer to the highest occupied molecular orbital (HOMO) energy after plasma treatment indicating p-type doping arising from surface oxidation.

Synthetic resins were introduced in paintings conservation during the 1930s, as an alternative to natural resins, due to their superior resistance to degradation. Their composition usually includes a small amount of additives, such as titanium dioxide. The objective of this work is to study the effect of TiO2 additive on the durability of Paraloid B72 (acrylic resin) and Laropal A81 (urea-aldehyde condensation polymer), both used in art conservation, against photochemical degradation. A methodology involving separating particulate TiO2 from the organic fraction of the resins has been applied, followed by accelerated ageing of the resins in their commercial (C) and modified (M, i.e. after TiO2 removal) has been implemented. The morphological characteristics of resin films were examined through scanning electron microscopy (SEM). Chemical changes, colour properties and photo-chemical stability of the resins were studied with FTIR, UV-Vis absorption spectroscopy and spectro-colorimetry. The results showed a considerably different behaviour between the C and M states of both materials. In particular, C-Paraloid B72 collapses after prolonged irradiation, but within a certain time frame it appears to be relatively stable; on the other hand, C-Laropal A81 is considerably destabilized in comparison to its M state. It can be suggested that TiO2 acts as a UV-blocker for the underlying pigment layers, at the expense of resins' stability.

The monitoring of performance characteristics of resins was always an issue for the conservation community, since the stability of the art objects depends on the service life of conservation materials used. Among the resins commonly applied in the field of paintings conservation, four of the most popular ones, Paraloid B72, Primal AC33 (acrylic polymers), Ketone Resin N (cyclohexanone) and Laropal A81 (ureaaldehyde) were selected to be comparatively studied under accelerated ageing conditions. These resins have been used by the art conservators either as consolidant materials of the paint or as protecting varnishes for the painting surface.The behaviour of the coatings under thermal ageing was investigated following a methodology depositing films of all materials onto different solid substrates (silicon wafers, quartz and simple glass slides) depending on the method of analysis used. Accelerated thermal ageing tests were conducted at 100 degrees C, for up to 432 hours. The morphological characteristics of the resins films (crack formations and surface alterations, coherence of film layers, thickness and surface roughness) were examined through scanning electron microscopy (SEM). Chemical changes of the resins were studied with FTIR and UV-Vis spectroscopy, while colour properties and thermal-chemical stability were also studied with spectro-colorimetry.It was found that, although all four displayed changes concerning their colour and film thickness, the two acrylic polymers and the aldehyde resin exhibit high stability against chemical degradation compared to the cyclohexanone based resin. Complementary solubility and swelling testing were also applied and significantly aided in supporting the spectroscopy observations. Finally, microscopic examination of most resin films revealed cracking features which may sometimes render them unsuitable for application under uncontrollable conditions.

A method is developed for extracting the direct current conductivity (sigma(dc)) of ion-conducting materials from frequency- and time-domain dielectric spectroscopy measurements. This method exploits the electrode polarization effects arising from the charging of an ion-blocking capacitor and provides a useful way of obtaining sigma(dc) for ionic conductors that do not exhibit a frequency- (time-) independent conductivity plateau; the latter absence of plateau is often encountered in the case of thin-film materials. It allows, by proper design of the test cells, the estimation of sigma(dc) independently of the specimen thickness, as demonstrated herein for SiO2 blocking layers and electrolyte systems made of a polyoxometalate (POM) molecule embedded in poly(methyl methacrylate) (PMMA) polymeric matrices. For different postpreparation and measurement conditions, the sigma(dc) values obtained for thick (8 mu m) POM PMMA layers are in good agreement not only with the observed conductivity plateaus but also with the values determined in the case of thin (270 nm) POM-PMMA layers for which no plateau is detected. The proposed method allows for the probing of a possible dependence of material properties on thickness and is of substantial interest for low-dimensional systems. The applicability and accuracy of the method are discussed and assessed in relation to the main methods currently used in the field.

Hydrogenated sub-stoichiometric oxides exhibiting perovskite structure such as those of tungsten and of molybdenum (H:MOx, where M=W or Mo and x<3) were treated by microwave (MW) post-deposition annealing in air. The purpose of this treatment was to vibrate and therefore heat, the OH bonds present in them only, without heating the rest of the lattice and the substrate. It was shown that, contrary to thermal heating, MW annealing did not affect significantly the oxygen and hydrogen contents in samples, but it caused an atomic re-arrangement; more significant for H:MoOx than for H:WOx films, attributed to the layered, two-dimensional structure of the former contrary to the three-dimensional one of the latter. It was concluded that MW annealing at appropriately chosen frequencies may potentially be used to improve atomic ordering in other materials without causing alterations of their chemical composition and avoiding the heating of the substrate.

Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl) porphyrin (ZnTMPyP4+) sensitization of a series of polyoxometalate catalysts (two Dawson type, P2Mo18O626- and P2W18O626- anions, and one Keplerate {Mo-132} cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP4+ sensitization in relation to the direct photoreduction of those compounds; (b) the P2Mo18O626- anion is more efficient (TON = 65 vs. 38, respectively) for hydrogen evolution than the P2W18O626- anion; and (c) the high nuclearity Keplerate {Mo-132} cluster exhibits the highest efficiency (TON = 215) for hydrogen evolution compared with the polyoxometalates studied.

In this work we present an all solution processing scheme for the fabrication of the three primary colors, (R-G-B), emitting organic light-emitting diodes (OLEDs) via efficient color tuning of a blue organic semi-conducting (OSC) thin film, in particular the poly[9,9-di-(2'-ethylhexyl)fluorenyl-2,7-diyl] (PF), in which different color fluorescent emitters are dispersed to define the final emitting color and thus to simplify the different color device fabrication. The transmission speed of the fabricated OLEDs was also examined for possible application in interactive telecommunications. To increase the response speed of the different color devices we altered both the device geometry and the electron injection efficiency. To this end we increased the emissive layer thickness and decreased the device emissive area and we also performed engineering of the cathode interfaces through the incorporation of solution processed porphyrin interlayers in order to lower the electron injection barrier height. The final devices exhibited improved operational characteristics and, consequently, modulation speeds. (C) 2015 Elsevier B.V. All rights reserved.

The present study is aimed at investigating the solid state reduction of a representative series of Keggin and Dawson polyoxometalate (POM) films in contact with a metallic (aluminum) electrode and at introducing them as highly efficient cathode interlayers in organic optoelectronics. We show that, upon reduction, up to four electrons are transferred from the metallic electrode to the POM clusters of the Keggin series dependent on addenda substitution, whereas a six electron reduction was observed in the case of the Dawson type clusters. The high degree of their reduction by Al was found to be of vital importance in obtaining effective electron transport through the cathode interface. A large improvement in the operational characteristics of organic light emitting devices and organic photovoltaics based on a wide range of different organic semiconducting materials and incorporating reduced POM/Al cathode interfaces was achieved as a result of the large decrease of the electron injection/extraction barrier, the enhanced electron transport and the reduced recombination losses in our reduced POM modified devices.

Modifications of the ZnO electron extraction layer with low-pressure H plasma treatment increased the efficiency of inverted polymer solar cells (PSCs) based on four different photoactive blends, namely, poly(3-hexylthiophene):[6,6]-phenyl C71 butyric acid methyl ester (P3HT:PC71BM), P3HT:1',1 '',4',4 ''-tetrahydro-di[1,4]methanonaphthaleno-[5,6]ullerene-C60 (P3HT:IC(60)BA), poly[(9-(1-octylnonyl)-9H-carbazole-2,7-diyl)-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]:PC71BM (PCDTBT:PC71BM), and (poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-(2-ethylhexy)carbonyl]thieno[3,4-b]thiophenediyl]]):PC71BM (PTB7:PC71BM), irrespective of the donor:acceptor combination in the photoactive blend. The drastic improvement in device efficiency is dominantly attributable to the reduction in the work function of ZnO followed by a decreased energy barrier for electron extraction from fullerene acceptor. In addition, reduced recombination losses and improved nanomorphology of the photoactive blend in the devices with the H plasma treated ZnO layer were observed, whereas exciton dissociation also improved with hydrogen treatment. As a result, the inverted PSC consisting of the P3HT:PC71BM blend exhibited a high power conversion efficiency (PCE) of 4.4%, the one consisting of the P3HT:IC(60)BA blend exhibited a PCE of 6.6%, and our champion devices with the PCDTBT:PC71BM and PTB7:PC71BM blends reached high PCEs of 7.4 and 8.0%, respectively.

The compatibility of polyoxometalates as hole extraction layers in single-junction organic photovoltaics and as recombination layers in polymer tandem cells is demonstrated.