Abstract: Almost seventy years after artists such as Frank Stella (1936), Andy Warhol (1928-1987), James Rosenquist (1933-2017), Herb Aach (1923-1985) and Richard Bowman (1918-2001) started to incorporate Daylight Fluorescent Pigments (DFPs) in their artworks, the extent of the conservation problems that are associated with these pigments has increased progressively. Since their first appearance on the market, their composition has constantly been improved in terms of permanency. However, conservation practices on the artworks that are used in, are complicated by the fact that the composition of DFPs is proprietary and the information provided by the manufactures is limited. To be able to propose adequate conservation strategies for artworks containing DFPs, a thorough understanding of the DFPs composition must be acquired. In contrast with previous research that concentrated on identification of the coloring dye, this paper focuses on the characterization of the resin, used as the carrier for the dye. The proposed approach, involving ATR-FTIR, SPME-GC-MS and XRF analysis, provided additional insights on the organic and inorganic components of the resin. Using this approach, we investigated historical DFPs and new formulations, as well as different series from the main manufacturing companies (DayGlo, Swada, Radiant Color and Kremer) in order to obtain a full characterization of DFPs used by the artists along the years. First, the initial PCA-assisted ATR-FTIR spectroscopy allowed for an efficient classification of the main monomers in the resin polymer. Next, a further distinction was made by mass spectrometry and XRF which were optimized to allow a more specific classification of the resin and for detection of additives. In this paper we show the potential of SPME-GC-MS, never applied for the characterization of artistic materials, at present undervalued for heritage science purposes. We anticipate that this information will be highly relevant in the future stability studies and for defining (preventive) conservation strategies of fluorescent artworks.

Abstract: During the recultivation of the uranium mining area of Kõvágószõlõs (Hungary), the tailings were covered with clay and loess soil layers having a thickness of 30 cm and 100 cm, respectively. In the loess covering layer, acacia (Robinia pseudoacacia), poplars (Populus × albus, Populus × canescens), oak (Quercus pubescens), silver tree (Eleagnus angustifolia) were planted between 1996 and 2004. In order to establish the extent of the uranium and thorium transport from the sludge to the leaves by uptake and translocation processes through roots with a length higher than 1.3 m results in a remarkable redistribution of these pollutants, a gray poplar tree, growing spontaneously in the last uncovered tailing, being selected as reference tree. The U and Th concentrations in the leaves of the above-mentioned trees, in the covering layers as well as in the original sludge were determined by inductively coupled plasma sector field mass spectrometry (ICP-SF-MS). Generally, the Th concentration of the soils was about 4 times higher than that of uranium, while uranium concentration was about 10130 times higher than that of thorium in the leaf samples and its concentration ranged from 28 to 1045 ng g− 1, the last value belonging to the poplar tree growing on the last uncovered tailing. In order to assume the mobility and bioavailability of uranium if the dry leaves fall down, the uranium species in the leaves of the poplar tree growing in the uncovered reservoir were determined applying ultrasound-assisted extraction with distilled water and ammonium acetate as well as high performance liquid chromatographic (HPLC)-ICP-SF-MS technique. About 20% of total uranium could be extracted in form of uranyl cations and a presumably negatively charged uranium compound. Estimations revealed that the annual increment of U in the soil surface layer due to the dead fallen leaves in case of the investigated gray poplar (Populus × canescens) is about 1.2%.

Abstract: The identification of volatile organic compounds (VOCs) emitted by a complex museum object, composed of materials of different nature, has been optimized by solid-phase microextraction coupled to gas chromatography-mass spectrometry (SPME-GC–MS). The performance of two fiber coatings and four sampling times were tested and compared in order to define the best sampling conditions. The method allowed a fair extraction of volatile and semivolatile compounds emitted naturally by the object, without any type of accelerating aging. In addition, on-fiber derivatization was applied to improve the extraction efficiency and reduce the sampling time of harmful carboxylic acids emitted by the object. The results obtained are of prime importance to show the off-gassing activity of a valuable museum object in order to take further decisions related with its storage and display conditions.

Abstract: Illicit drug consumption constitutes a great concern worldwide due to its increased spread and abuse, and the negative consequences exerted on society. For instance, 3,4-methylenedioxymethamphetamine (MDMA), a synthetic amphetamine-type substance, was abused by 20 million people worldwide in 2020. This psychoactive substance exerts a myriad of effects on the human body being dangerous for the consumer’s health. Besides, MDMA has been used in the treatment of some psychiatric conditions. Therefore, the development of wearable devices for MDMA sensing in biological fluids is of great importance for forensic toxicology (e.g., monitoring of patients with suspected or known MDMA consumption) as well as for therapeutic management of patients. Herein, we report the development of a wearable electrochemical platform based on a hollow microneedle (MN) array sensor for the monitoring of MDMA in the interstitial fluid by square-wave voltammetry. First, the holes of the MN array were modified with conductive pastes to devise a MN patch with a three-electrode system. Subsequently, the functionalization of the working electrode with nanomaterials enhanced MDMA detection. Thereafter, analytical parameters were evaluated exhibiting a slope of 0.05 µA µM−1 within a linear range from 1 to 50 µM and a limit of detection of 0.75 µM in artificial interstitial fluid. Importantly, critical parameters such as selectivity, piercing capability, temperature, reversibility and stability were assessed. Overall, the obtained MN sensor exhibited excellent analytical performance, making it a promising tool for MDMA tracking in interstitial fluid for individuals on probation or under therapeutic treatment.

Abstract: Phenols are considered as toxic pollutants and their discharge into the environment by industries is regulated by a concentration limit. As these limits are in the low mg L−1 to µg L−1-range, sensitive methods are necessary to detect these phenols. Here, aqueous industrial phenolic samples throughout a cleaning process were analyzed by two novel electrochemical sensors. Both the photoelectrochemical (PEC) sensor and the square wave voltammetric (SWV) sensor could successfully follow the decrease of the concentration of phenols along the industrial cleaning process. The discharge sample (μg L−1) could only be analyzed by the PEC sensor and not by the SWV sensor, as the phenolic concentration was close to the LOD of the latter. With HPLC-diode array detector (DAD) measurements, classical phenols such as phenol (PHOH), hydroquinone, resorcinol and o-cresol could be identified in the industrial samples, and their presence could be linked to the electrochemical responses. At last, the performance of the PEC and SWV sensors were compared with commercial colorimetric and chemical oxygen demand (COD) test kits. This comparison demonstrated the high sensitivity of the PEC sensor in the μg L−1 concentrated phenolic samples. Together with the identification of the redox peaks through HPLC-DAD analysis, the SWV sensor can be a powerful tool in the qualitative analysis of mg L−1 concentrated phenolic samples due to its speed, simplicity and absence of laborious sample pre-treatment steps.

Abstract: Identifying and quantifying 3,4-methyl​enedioxy​methamphetamine (MDMA) on-site in suspected illicit drug samples, whether it be at recreational settings or manufacturing sites, is a major challenge for law enforcement agencies (LEAs). Various analytical techniques exist to fulfil this goal, e.g. colourimetry and portable spectroscopic techniques, each having its specific limitations (e.g. low accuracy, fluorescence, no quantification) and strengths (e.g. fast, easy to use). In this work, for the first time, an electrochemical MDMA sensor is presented to become a detection tool that can realistically be used on-site. More specifically, the use of a single buffer solution and an unmodified screen-printed electrode, along with the integration of a data analysis algorithm and mobile application permits the straightforward on-site identification and quantification of MDMA in suspicious samples. Multiple studies investigating different parameters, including pH, concentration, reproducibility, temperature and binary mixture analyses, were executed. To fully understand all the occurring redox processes, liquid chromatography coupled with high-resolution mass spectrometry analysis of partially electrolyzed MDMA samples was performed unravelling oxidation of the methylenedioxy group. Validation of the methodology was executed on 15 MDMA street samples analysed by gas chromatography coupled with mass spectrometry and compared with the performance of a commercial portable Raman and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) device. The novel methodology outperformed the spectroscopic techniques, correctly identifying all 15 street samples. Additionally, the electrochemical sensor predicted the purity of the tablets with a mean absolute error of 2.3%. Overall, this new, electrochemical detection strategy provides LEAs the rapid, low-cost, on-site detection and quantification of MDMA in suspicious samples, without requiring specialized training.

Abstract: We investigate the adsorption process of small molecules on graphene through first-principles calculations and show the presence of two main charge transfer mechanisms. Which mechanism is the dominant one depends on the magnetic properties of the adsorbing molecules. We explain these mechanisms through the density of states of the system and the molecular orbitals of the adsorbates, and demonstrate the possible difficulties in calculating the charge transfer from first principles between a graphene sheet and a molecule. Our results are in good agreement with experiment.

Abstract: The effect of a metallic gate on the bound states of a shallow donor located near the gate is studied. We calculate the energy spectrum as a function of the distance between the metallic gate and the donor and find an anti-crossing behavior in the energy levels for certain distances. We show how a transverse electric field can tune the average position of the electron with respect to the metallic gate and the impurity.

Abstract: A flow injection hydride generation graphite furnace atomic absorption spectrometric (FI-HG-GFAAS) method was applied to the determination of Se in Se-doped and undoped cereals and bakery products. For the purpose of doping, the soils used for the cultivation of the cereals were dosed with Se- doped foliar fertilizers. The samples were dissolved in a mixture of HNO(3) and H(2)O(2) solutions using micro-waveassisted digestion. The decomposition of H(2)Se generated from the sample solutions and the trapping of elemental Se were performed at a temperature of 300 degrees C on an Ir-pretreated integrated graphite platform of a transversally heated graphite atomizer(THGA). For release of the trapped Se within a fairly short atomization time (5s), an atomization temperature of 2200 degrees C was observed to be optimal. The overall efficiency of hydride generation, transport and trapping was similar to 86%. The upper limit of the linear dynamic range of calibration was 10 mu gL(-1), which corresponds to 0.5 mu g g(-1) for solid samples. Recovery of the samples spiked with Se(VI) solutions was found to be 93 +/- 6% on average. The relative standard deviation of the determinations was less than 8%. The limit of detection was found to be 0.06 mu gL(-1), corresponding to 3 ng g(-1) for solid samples. The accuracy of the method was verified with the use of IAEA-155 ( whey powder) certified reference material. End-capped THGA tubes resulted in an extension of the linear calibration range compared to that of standard THGAs. The Se content in bakery products made of undoped cereals ranged from 7.7 to 68 ng g(-1) ( wet weight) in 18 samples, whereas the Se content of the corresponding cereals was found to be below 100 ng g(-1) ( wet weight). The Se level of cereals grown on soils treated with Se- doped fertilizers ranged from 128 to 1046 ng g(-1) ( wet weight), and it depended linearly on the Se concentration of the corresponding foliar fertilizer.