Abstract: Recent studies in which X-ray beams of macroscopic to (sub) microscopic dimensions were used for non-destructive analysis and characterization of pigments, paint micro samples and/or entire paintings by Vincent van Gogh are concisely reviewed. The overview presented encompasses the use of laboratory and synchrotron radiation-based instrumentation and deals with the use of several variants of X-ray fluorescence (XRF) as a method of elemental analysis and imaging as well as with the combined use of X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Microscopic and macroscopic XRF are variants of the method that are well suited to visualize the elemental distribution of key elements, mostly metals, present in paint multi layers, either on the length scale from 1–100 μm inside micro samples taken from paintings or on the 1–100 cm length scale when the (subsurface) distribution of specific pigments in entire paintings is concerned. In the context of the characterization of van Gogh's pigments subject to natural degradation, the use of methods limited to elemental analysis or imaging usually is not sufficient to elucidate the chemical transformations that have taken place. However, at synchrotron facilities, combinations of μ-XRF with related methods such as μ-XAS and μ-XRD have proven themselves to be very suitable for such studies. Their use is often combined with microscopic Fourier transform infra-red (μ-FTIR) spectroscopy since this method delivers complementary information at more or less the same length scale as the X-ray microprobe techniques. Also in the context of macroscopic imaging of works of art, the complementary use of X-ray based and infra-red based imaging appears very promising; some recent developments are discussed.

Abstract: This chapter lays out a conservation timeline, from past to future, for the Amsterdam version of Van Gogh's Sunflowers. It starts by considering the restoration history of the painting in order to assess its current physical state, and looks ahead to formulate an appropriate strategy for future conservation treatment and display. Due attention is paid to the two recorded episodes of restoration performed in 1927 and 1961 by the Dutch restorer, Jan Cornelis Traas. Based on physical and chemical investigation of Sunflowers we attempt to reconstruct what these former treatments (which are barely documented) entailed and consider the repercussions for the present condition of the painting. The former interventions by Traas also serve as a benchmark to reflect on current choices made, highlighting the extent to which ideas and methodologies have continued to evolve over the past century as conservation has moved further away from being a singularly craft-based activity to become an established historical and scientific discipline underpinned by ethical guidelines. Jan Cornelis Traas (1898–1984) As mentioned, the two main recorded interventions to the Amsterdam Sunflowers may be associated with the Dutch restorer, Jan Cornelis Traas, who treated the picture in 1927, close to the start of his career, and again in 1961, shortly before he retired. Traas was the first restorer to be appointed at the Mauritshuis in The Hague where he worked from 1931 to 1962 and treated hundreds of paintings, including iconic masterpieces such as Girl with a Pearl Earring by Johannes Vermeer. Yet despite the magnitude and importance of his restoration oeuvre, J.C. Traas (as he is usually referred to in surviving documents), has remained somewhat obscure. He is shown here in the only known surviving photograph of him at work, shortly before he retired (fig. 7.1). Unlike his illustrious contemporaries, A. Martin de Wild (1899–1969) and Helmut Ruhemann (1891–1973), for example, Traas did not publish anything, he appears to have kept no records of his work and no personal archive is known. However, the study of some newly discovered historical documents, combined with physical examination of Sunflowers and a large number of other works he treated, allows us to recover an idea of his working practices and approaches viewed within the context of his day.

Abstract: During the conservation treatment of Memling’s Christ with Singing and Music-making Angels, three panel paintings that are among the most monumental works in early Netherlandish art, the conservators came across insoluble surface layers containing calcium oxalates. A very thin and irregular layer of this type, hardly visible to the naked eye, was spread across the surface of all three panels. A much thicker layer forming an opaque and highly disfiguring crust that obscured the composition (Figs. 15.1 and 15.7) was locally present on areas of dark copper-containing paint, where multiple layers of old discolored coatings and accretions remained in place before the most recent cleaning. This article describes the application of a wide range of analytical techniques in order to fully understand the stratigraphy and composition of the crusts on the Memling paintings. FTIR spectroscopy in transmission and reflection mode, micro-ATR-FTIR imaging and macro-rFTIR scanning, SEM-EDX, mobile XRD, and SR-μXRD showed that the crusts contained two related Ca-based oxalate salts, whewellite and weddellite, and were separated from the original paint surface by varnish, indicating that they did not originate from degradation of the original paint but from a combination of microbial action and a thick accumulation of dirt. Supported by the results from these different analytical techniques, which when used together proved to be very effective in providing complementary information that addressed this specific conservation problem, and aided by the presence of the intermediate varnish layer(s), the conservators were able to remove most of the crusts with spectacular results.

Abstract: Heterogeneous catalysts are often & ldquo;black boxes & rdquo; due to the insufficient understanding of the detailed mechanisms at the catalytic sites. An atomic-level elucidation of the processes taking place in those regions is, thus, mandatory to produce robust and selective heterogeneous catalysts. We have improved the description of the whole reactive scenario for polymeric carbon nitrides (PCN) by combining atomic-level characterizations with magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectroscopy, classical reactive molecular dynamics (RMD) simulations, and quantum chemistry (QC) calculations. We disclose the structure & minus;property relationships of an ad hoc modified PCN by inserting an aryl amino group that turned out to be very efficient for the production of H2O2. The main advancement of this work is the development of a difluoromethylene-substituted aryl amino PCN to generate H2O2 at a rate of 2.0 mM & middot;h & minus;1 under the irradiation of household blue LEDs and the identification of possible active catalytic sites with the aid of 15N and 19F MAS solid-state NMR without using any expensive labeling reagent. RMD simulations and QC calculations confirm and further extend the experimental descriptions by revealing the role and locations of the identified functionalities, namely, NH linkers, & minus;NH2 terminal groups, and difluoromethylene units, reactants, and products. <comment>Superscript/Subscript Available</comment

Abstract: The electrochemical behavior of some of the most relevant endocrine-disrupting phenols using unmodified carbon screen-printed electrodes (SPEs) is described for the first time. Experiments were made to assess the electrochemical behavior of phenol (PHOH), pentachlorophenol (PCP), 4-tert octylphenol (OP) and bisphenol A (BPA) and their determination in the most favorable conditions, using voltammetric methods such as cyclic voltammetry (CV), linear sweep voltammetry (LSV) and square wave voltammetry (SWV) in Britton Robinson (BR) buffer. Further, the usefulness of the electrochemical approach was validated with real samples from a local river and was compared to commercial phenols test kit, which is commonly used for on-site screening in industrial streams and wastewaters. Finally, the approach was compared with a lab-bench standard method using real samples, i.e., high-performance liquid chromatography with a photodiode array detector (HPLC-DAD).

Abstract: The use of a Pt electrode coated with a layer of Nafion has been described in previous works as an attractive way to perform the potentiometric detection of hydrogen peroxide. Despite of the attractive features of this approach, the nature of the non-Nernstian response of this system was not properly addressed. In this work, using a mixed potential model, the open circuit potential of the Pt electrode is shown to be under kinetic control of the oxygen reduction reaction (ORR). It is proposed that hydrogen peroxide acts as an oxygenated species that blocks free sites on the Pt surface, interfering with the ORR. Therefore, the effect of the polyelectrolyte coating can be understood in terms of the modulation of the factors that affects the kinetics of the ORR, such as an increase of the H+ concentration, minimization of the effect of the spectator species, etc. Because of the complexity and the lack of models that accurately describe systems with practical applications, this work is not intended to provide a mechanistic but rather a phenomenological view on problem. A general framework to understand the factors that affect the potentiometric response is provided. Experimental evidence showing that the use of polyelectrolyte coatings are a powerful way to control the mixed potential open new ways for the development of robust and simple potentiometric sensors.

Abstract: Herein, an isothermal padlock probe-based assay for the simple and portable detection of pathogens coupled with a glucose oxidase (GOx)-based electrochemical readout is reported. Infectious diseases remain a constant threat on a global scale, as in recurring pandemics. Rapid and portable diagnostics hold the promise to tackle the spreading of diseases and decentralising healthcare to point-of-care needs. Ebola, a hypervariable RNA virus causing fatalities of up to 90% for recent outbreaks in Africa, demands immediate attention for bedside diagnostics. The design of the demonstrated assay consists of a rolling circle amplification (RCA) technique, responsible for the generation of nucleic acid amplicons as RCA products (RCPs). The RCPs are generated on magnetic beads (MB) and subsequently, connected via streptavidin-biotin bonds to GOx. The enzymatic catalysis of glucose by the bound GOx allows for an indirect electrochemical measurement of the DNA target. The RCPs generated on the surface of the MB were confirmed by scanning electron microscopy, and among other experimental conditions such as the type of buffer, temperature, concentration of GOx, sampling and measurement time were evaluated for the optimum electrochemical detection. Accordingly, 125 μg mL−1 of GOx with 5 mM glucose using phosphate buffer saline (PBS), monitored for 1 min were selected as the ideal conditions. Finally, we assessed the analytical performance of the biosensing strategy by using clinical samples of Ebola virus from patients. Overall, this work provides a proof-of-concept bioassay for simple and portable molecular diagnostics of emerging pathogens using electrochemical detection, especially in resource-limited settings.

Abstract: This work reports the use of modified screen-printed carbon electrodes (SPCEs) for the identification of three drugs of abuse and two habitual cutting agents, caffeine and paracetamol, combining voltammetric sensing and chemometrics. In order to achieve this goal, codeine, heroin and morphine were subjected to Square Wave Voltammetry (SWV) at pH 7, in order to elucidate their electrochemical fingerprints. The optimized SPCEs electrode array, which have a differentiated response for the three oxidizable compounds, was derived from Carbon, Prussian blue, Cobalt (II) phthalocyanine, Copper (II) oxide, Polypyrrole and Palladium nanoparticles ink-modified carbon electrodes. Finally, Principal Component Analysis (PCA) coupled with Silhouette parameter assessment was used to select the most suitable combination of sensors for identification of drugs of abuse in presence of cutting agents.