This paper presents the results of the first X-ray fluorescence (XRF) investigation conducted on three late medieval chalices associated with Ireland: the Ó Learghusa chalice, auctioned as medieval Irish in 2021, does not have a confirmed provenance; the de Burgo-O'Malley chalice, dated 1494, and the TP-IEP chalice, dated 1589, both of Irish provenance. This study effectively addressed the knowledge gap concerning Irish medieval silver chalices composition. The analysis revealed that both the Ó Learghusa and de Burgo-O'Malley chalices were crafted from a silver-copper alloy and adorned using a fire-gilding technique. The blue and green enamels on the de Burgo-O'Malley chalice were found to be constituted by cobalt and iron/copper glasses, respectively. In contrast, the TP-IEP chalice exhibited a more intricate structure, being a composite object with partial silver gilt and with the bowl and base possibly made of a ternary silver-copper-gold alloy. The TP-IEP chalice's knop displayed glass, simulating gems with transparent, blue, and purple colorations. XRF analysis allowed identification of lead-potash glass, while the red glass displayed a rich iron content and was identified as soda-lime glass. The analysis allowed concluding that the de Burgo-O'Malley chalice had retained its original condition, including its original gilding and enamels, while the Ó Learghusa and TP-IEP chalices appeared to have undergone refurbishment. These significant discoveries contribute to a deeper understanding of the historical context and artistic craftsmanship behind these late medieval chalices, shedding light on their unique stories within Irish art and history. Supplementary Information: The online version contains supplementary material available at 10.1186/s40494-024-01240-2.
Direct pen writing offers versatile opportunities for development of low-cost tests for point-of-care applications. In this work a lateral flow immunoassay (LFIA) test was fabricated by hand "writing" immunoprobes onto hand-cut nitrocellulose strips with a commercial fountain pen. The qualitative capabilities of the test were extended by addition of a Raman reporter and consequent design and fabrication of a Surface Enhanced Resonant Raman Scattering (SERRS)-LFIA test. As proof-of-concept, dual detection of penicillin G was achieved in milk with a visual LOD of 20 ppm and a dynamic range of 0.03-97.5 ppm. Evaluation against equivalent tests performed with conventionally prepared LFIA strips showed comparable results, thus demonstrating the validity of the test. These results demonstrate the potential for further decrease in cost and consequent broader use of LFIA tests in remote regions and resource-limited environments.
This work presents the results of a transdisciplinary analysis performed on Harward's Almanac (Dublin, 1666), an extremely rare volume currently housed in the National Library of Ireland. The uniqueness and historical value of the Almanac is related to the presence of nineteen handwritten poems, entered by an anonymous scribe. These record textually important English clandestine satire circulating anonymously in Dublin in the late seventeenth and early eighteenth century. Following a comprehensive historical assessment, it appeared evident that the current order of leaves was incorrect. To reconstruct the correct order of the leaves, and hence the likely sequence in which the manuscript poems were inscribed, this study employed a codicological/paleographic analysis complemented by analytical (X-ray fluorescence, XRF) and statistical (Self Organizing Map, SOM) investigation. Specifically, point XRF analysis was carried out for each handwritten page of the Almanac, allowing identification of ink elemental compositions (iron-based ink) and successfully supporting the validity of historical hypotheses on the poems' order of inscription. The statistical organization of XRF data by SOMs allowed easy bi-dimensional visualization of the data set (54 points) and identification of ink similarities, once more validating the historical assessment. Supplementary Information: The online version contains supplementary material available at 10.1186/s40494-023-01107-y.
In this study, the laser-induced graphitization process of sustainable chitosan-based formulations was investigated. In particular, optimal lasing conditions were investigated alongside the effect of borax concentration in the chitosan matrix. In all cases, it was found that the obtained formulations were graphitizable with a CO2 laser. This process gave rise to the formation of high surface area, porous, and electrically conductive laser-induced graphene (LIG) structures. It was found that borax, as a cross-linker of chitosan, enabled the graphitization process when its content was ≥30 wt % in the chitosan matrix, allowing the formation of an LIG phase with a significant content of graphite-like structures. The graphitization process was investigated by thermogravimetric analysis (TGA), Raman, X-ray photoemission (XPS), and Fourier transform infrared (FTIR) spectroscopies. LIG electrodes obtained from CS/40B formulations displayed a sheet resistance as low as 110 Ω/sq. Electrochemical characterization was performed after a 10 min electrode activation by cycling in 1 M KCl. A heterogeneous electron transfer rate, k0, of 4 × 10-3 cm s-1 was determined, indicating rapid electron transfer rates at the electrode surface. These results show promise for the introduction of a new class of sustainable composites for LIG electrochemical sensing platforms.
This paper presents a novel approach for the fabrication of low cost Electrochemical-Surface Enhanced Raman Scattering (EC-SERS) sensing platforms. Laser Induced Graphene (LIG) electrodes were readily fabricated by direct laser writing of polyimide tapes and functionalized with silver nanoparticles (Ag NPs) to obtain hybrid Ag NPs - LIG electrodes suitable for EC-SERS analysis. Detection was achieved by coupling a handheld potentiostat with a Raman spectrograph, enabling measurement of SERS spectra of target analytes generated during voltage sweeps in the 0.0 to -1.0 V interval range. The sensing capabilities of the fabricated system were first tested with model molecule 4-aminobenzenethiol (4-ABT). Following sensitive detection of 4-ABT, EC-SERS analysis of food contaminant melamine in milk and antibiotic difloxacin hydrochloride (DIF) in river water was demonstrated, achieving sensitive detection of both analytes without pre-treatment steps. The easiness of fabrication, versatility of design, rapid analysis time and potential miniaturization of the system make Ag NPs - LIG electrodes suitable for a large range of in situ applications in the field of food monitoring and for environmental analysis.
Ultra-sensitive and responsive humidity sensors were fabricated by deposition of graphene oxide (GO) on laser-induced graphene (LIG) electrodes fabricated by a low-cost visible laser scribing tool. The effects of GO layer thickness and electrode geometry were investigated. Sensors comprising 0.33 mg/mL GO drop-deposited on spiral LIG electrodes exhibited high sensitivity up to 1800 pF/% RH at 22 °C, which is higher than previously reported LIG/GO sensors. The high performance was ascribed to the high density of the hydroxyl groups of GO, promoted by post-synthesis sonication treatment, resulting in high water physisorption rates. As a result, the sensors also displayed good stability and short response/recovery times across a wide tested range of 0-97% RH. The fabricated sensors were benchmarked against commercial humidity sensors and displayed comparable performance and stability. Finally, the sensors were integrated with a near-field communication tag to function as a wireless, battery-less humidity sensor platform for easy read-out of environmental humidity values using smartphones.
We report a simple, scalable two-step method for direct-write laser fabrication of 3D, porous graphene-like carbon electrodes from polyimide films with integrated contact plugs to underlying metal layers (Au or Ni). Irradiation at high average CO2laser power (30 W) and low scan speed (â¼18 mm s)-1leads to formation of 'keyhole' contact plugs through local ablation of polyimide (initial thickness 17µm) and graphitization of the plug perimeter wall. Top-surface laser-induced graphene (LIG) electrodes are then formed and connected to the plug by raster patterning at lower laser power (3.7 W) and higher scan speed (200 mm s)-1. Sheet resistance data (71 ± 15 Ω sq.)-1indicates formation of high-quality surface LIG, consistent with Raman data which yield sharp first- and second-order peaks. We have also demonstrated that high-quality LIG requires a minimum initial polyimide thickness. Capacitance data measured between surface LIG electrodes and the buried metal film indicate a polyimide layer of thickness â¼7µm remaining following laser processing. By contrast, laser graphitization of polyimide of initial thickness â¼8µm yielded devices with large sheet resistance (>1 kΩ sq.)-1. Raman data also indicated significant disorder. Plug contact resistance values were calculated from analysis of transfer line measurement data for single- and multi-plug test structures. Contacts to buried nickel layers yielded lower plug resistances (1-plug: 158 ± 7 Ω , 4-plug: 31 ± 14 Ω) compared to contacts to buried gold (1-plug: 346 ± 37 Ω , 4-plug: 52 ± 3 Ω). Further reductions are expected for multi-plug structures with increased areal density. Proof-of-concept mm-scale LIG electrochemical devices with local contact plugs yielded rapid electron transfer kinetics (rate constantk0 â¼ 0.017 cm s-1), comparable to values measured for exposed Au films (k0 â¼0.023 cm s)-1. Our results highlight the potential for integration of LIG-based sensor electrodes with semiconductor or roll-to-roll manufacturing.
We developed a flexible laser scribed graphitic carbon based lactate biosensor fabricated using a low cost 450 nm laser. We demonstrated a facile fabrication method involving electrodeposition of platinum followed by two casting steps for modification with chitosan and lactate oxidase. The biosensor demonstrated chronoamperometric lactate detection within a linear range from 0.2 mM to 3 mM, (R2 > 0.99), with a limit of detection of 0.11 mM and a sensitivity of 35.8 µA/mM/cm2. The biosensor was successful in performing up to 10 consecutive measurements (one after the other) indicating good working stability (RSD <5%). Concerning storage stability, there was no decrease in signal response after 30 days of storage at 4 °C. Additionally, we demonstrate enzymatic lactate detection whilst the flexible polyimide substrates were fixed at a curvature (K) of 0.14 mm-1. No noticeable change in signal response was observed in comparison to calibrations obtained at a curvature of 0 mm-1, signifying potential opportunities for sensor attachment or integration with oral-care products such as mouth swabs. Both laser scribed graphitic carbon and Ag/AgCl modified-laser scribed graphitic carbon were successful as reference electrodes for chronoamperometric lactate measurements. Furthermore, using a three-electrode configuration on polyimide, lactate detection in both artificial saliva and sterile human serum samples was achieved for two spiked concentrations (0.5 mM and 1 mM).
Biosensing Techniques , Chitosan , Graphite , Biosensing Techniques/methods , Carbon , Electrochemical Techniques/methods , Electrodes , Humans , Lactic Acid , Lasers , Mixed Function Oxygenases , Platinum
Interleukin-6 (IL-6) is an important immuno-modulating cytokine playing a pivotal role in inflammatory processes in disease induction and progression. As IL-6 serves as an important indicator of disease state, it is of paramount importance to develop low cost, fast and sensitive improved methods of detection. Here we present an electrochemical immunosensor platform based on the use of highly porous graphitic carbon electrodes fabricated by direct laser writing of commercial polyimide tapes and chemically modified with capture IL-6 antibodies. The unique porous and 3D morphology, as well as the high density of edge planes of the graphitic carbon electrodes, resulted in a fast heterogeneous electron transfer (HET) rate, k0 = 0.13 cm/s. The resulting immunosensor showed a linear response to log of concentration in the working range of 10 to 500 pg/mL, and low limit of detection (LOD) of 5.1 pg/mL IL-6 in phosphate buffer saline. The total test time was approximately 90 min, faster than the time required for ELISA testing. Moreover, the assay did not require additional sample pre-concentration or labelling steps. The immunosensor shelf-life was long, with stable results obtained after 6 weeks of storage at 4 °C, and the selectivity was high, as no response was obtained in the presence of another inflammatory cytokine, Interlukin-4. These results show that laser-fabricated graphitic carbon electrodes can be used as selective and sensitive electrochemical immunosensors and offer a viable option for rapid and low-cost biomarker detection for point-of-care analysis.
Realization of graphene-based sensors and electronic devices remains challenging, in part due to integration challenges with current fabrication and manufacturing processes. Thus, scalable methods for in situ fabrication of high-quality graphene-like materials are essential. Low-cost CO2 laser engravers can be used for site-selective conversion of polyimide under ambient conditions to create 3-D, rotationally disordered, few-layer, porous, graphene-like electrodes. However, the influences of non-linear parameter terms and interactions between key parameters on the graphitization process present challenges for rapid, resource-efficient optimization. An iterative optimization strategy was developed to identify promising regions in parameter space for two key parameters, laser power and scan speed, with the goal of optimizing electrode performance while maximizing scan speed and hence fabrication throughput. The strategy employed iterations of Design of Experiments Response Surface (DoE-RS) methods combined with choices of readily measurable parameters to minimize measurement resources and time. The initial DoE-RS experiment set employed visual response parameters, while subsequent iterations used sheet resistance as the optimization parameter. The final model clearly demonstrates that laser graphitization through raster scanning is a highly non-linear process requiring polynomial terms in scan speed and laser power up to fifth order. Two regions of interest in parameter space were identified using this strategy: Region 1 represents the global minimum for sheet resistance for this laser (â¼16 Ω/sq), found at a low scan speed (70 mm/s) and a low average power (2.1 W) . Region 2 is a local minimum for sheet resistance (36 Ω/sq), found at higher values for scan speed (340 mm/s) and average power (3.4 W), allowing â¼5-fold reduction in write time. Importantly, these minima do not correspond to constant ratios of average laser power to scan speed. This highlights the benefits of DoE-RS methods in rapid identification of optimum parameter combinations that would be difficult to discover using traditional one-factor-at-a-time optimization. Verification data from Raman spectroscopy showed sharp 2D peaks with mean full-width-at-half-maximum intensity values <80 cm-1 for both regions, consistent with high-quality 3D graphene-like carbon. Graphene-based electrodes fabricated using the parameters from the respective regions yielded similar performance when employed as capacitive humidity sensors with hygroscopic dielectric layers. Devices fabricated using Region 1 parameters (16 Ω/sq) yielded capacitance responses of 0.78 ± 0.04 pF at 0% relative humidity (RH), increasing to 31 ± 7 pF at 85.1% RH. Region 2 devices (36 Ω/sq) showed comparable responses (0.88 ± 0.04 pF at 0% RH, 28 ± 5 pF at 85.1% RH).
For the first time, this paper reports a smart museum archive box that features a fully integrated wireless powered temperature and humidity sensor. The smart archive box has been specifically developed for microclimate environmental monitoring of stored museum artifacts in cultural heritage applications. The developed sensor does not require a battery and is wirelessly powered using Near Field Communications (NFC). The proposed solution enables a convenient means for wireless sensing with the operator by simply placing a standard smartphone in close proximity to the cardboard archive box. Wireless sensing capability has the advantage of enabling long-term environmental monitoring of the contents of the archive box without having to move and open the box for reading or battery replacement. This contributes to a sustainable preventive conservation strategy and avoids the risk of exposing the contents to the external environment, which may result in degradation of the stored artifacts. In this work, a low-cost and fully integrated NFC sensor has been successfully developed and demonstrated. The developed sensor is capable of wirelessly measuring temperature and relative humidity with a mean error of 0.37 °C and ±0.35%, respectively. The design has also been optimized for low power operation with a measured peak DC power consumption of 900 µW while yielding a 4.5 cm wireless communication range. The power consumption of the NFC sensor is one of the lowest found in the literature. To the author's knowledge, the NFC sensor proposed in this paper is the first reporting of a smart archive box that is wirelessly powered and uniquely integrated within a cardboard archive box.
Artifacts , Wireless Technology , Humidity , Museums , Temperature
Plastic materials are increasingly becoming part of private and public collections worldwide, either as design objects or artistic sculptures. The preservation of these highly degradable materials requires novel analytical approaches able to reveal their chemical composition to inform the tailoring of appropriate conservation procedures. In this work Raman spectroscopy and Surface-enhanced Raman Scattering (SERS) were proposed as methods for the characterization of ABS-based contemporary and historical LEGO® objects. Twenty-three objects of twelve different colors were analyzed by handheld and benchtop Raman instrumentation. In all cases clear identification of the constituent polymer matrices (ABS, polycarbonate, poly(methyl metacrylate)) was obtained. In addition, identification of major color components was achieved, such as copper phthalocyanines in green and blue objects. Low cost handheld instrumentation provided acceptable sensitivity towards polymers and coloring media, and was found suitable for initial screening of the objects. Benchtop Raman was used to confirm and further extend identification, as well as for building background information. Finally, SERS sensitivity was found comparable to the sensitivity achieved by benchtop Raman instrumentation. However, the associated minimally-invasive sampling method made SERS a valid alternative to direct Raman spectroscopy for the analysis of immovable and/or large-sized objects. Overall, this work represents the first systematic investigation on the potential of Raman and SERS spectroscopies as methods for minimal invasive and/or in situ analysis of historical and contemporary plastic objects.
The development of three-dimensional (3D) porous graphitic structures is of great interest for electrochemical sensing applications as they can support fast charge transfer and mass transport through their extended, large surface area networks. In this work, we present the facile fabrication of conductive and porous graphitic electrodes by direct laser writing techniques. Irradiation of commercial polyimide sheets (Kapton tape) was performed using a low-cost laser engraving machine with visible excitation wavelength (405 nm) at low power (500 mW), leading to formation of 3D laser-induced graphene (LIG) structures. Systematic correlation between applied laser dwell time per pixel ("dwell time") and morphological/structural properties of fabricated electrodes showed that conductive and highly 3D porous structures with spectral signatures of nanocrystalline graphitic carbon materials were obtained at laser dwell times between 20 and 110 ms/pix, with graphenelike carbon produced at 50 ms/pix dwell time, with comparable properties to LIG obtained with high cost CO2 lasers. Electrochemical characterization with inner and outer sphere mediators showed fast electron transfer rates, comparable to previously reported 2D/3D graphene-based materials and other graphitic carbon electrodes. This work opens the way to the facile fabrication of low-cost, disposable electrochemical sensor platforms for decentralized assays.
Raman spectroscopy and Surface Enhanced Raman Scattering (SERS) were applied to the analysis of blue and black writing inks. SERS was performed by application of plasmonic nanopastes constituted by Ag nanoparticles and Au nanorods directly on inks deposited on paper substrates under laser irradiation of 514 nm. It was found that SERS spectra were largely enhanced compared to Raman spectra and that Ag nanopastes produced much larger enhancements than Au nanopastes, due to a combination of plasmonic resonance, charge transfer, and molecular resonance effects. All analyzed writing inks resulted constituted by Crystal Violet and other triarylmethane dye mixtures, to which sometimes phthalocyanine dyes were also added (for example in Bic pens). SERS was also used for the identification of degradation processes occurring in artificially aged blue pens deposited on paper substrates. It was found that color alteration changed from ink to ink and varied from darkening to discoloration to slight fading, depending on the initial chemical composition. For inks containing Crystal Violet, two mechanisms associated to de-methylation and photo-reduction of excited dye to colorless leuco forms were identified.
The fabrication of flexible and transparent Surface Enhanced Raman Scattering (SERS) substrates enabling fast, sensitive and on site detection is relevant for the practical application of SERS for real world analysis, such as food safety and organic pollutants monitoring. In this work novel Ag NPs/PDMS composites were fabricated and employed for the SERS detection of food contaminants directly on food surfaces. Ag NPs/PDMS composites were obtained by self-assembly of organic Ag nanoparticle solutions on flexible PDMS surfaces. Preliminary evaluation of the suitability of Ag NPs/PDMS probes for SERS analysis showed that composites were characterized by a SERS enhancement factor (EF) of 3.1â¯×â¯105, good stability and resistance to harsh conditions as well as good uniformity and batch to bach reproducibility. The "sticky" nature of Ag NPs/PDMS composites was exploited to "paste" them on irregular analytical surfaces, thus enabling the detection in situ of food contaminant crystal violet (CV) and pesticide thiram, respectively. Specifically, CV and thiram concentrations as low as 1â¯×â¯10-7â¯M and 1â¯×â¯10-5â¯M were measured on contaminated fish skin and orange peel, respectively. Furthermore, efficient SERS detection by micro-extraction of CV from fish skin and thiram from fruit surfaces was achieved, showing the analytical versatility of the fabricated SERS composites.
Food Contamination/analysis , Metal Nanoparticles/chemistry , Nanocomposites/chemistry , Silicones/chemistry , Silver/chemistry , Animals , Anti-Infective Agents, Local/analysis , Citrus sinensis/chemistry , Fishes , Fungicides, Industrial/analysis , Gentian Violet/analysis , Reproducibility of Results , Silicones/chemical synthesis , Skin/chemistry , Spectrum Analysis, Raman/methods , Thiram/analysis
The development of protocols for the protection of the large patrimony of works of art created by felt tip pen media since the 1950's requires detailed knowledge of the main dyes constituting commercial ink mixtures. In this work Surface Enhanced Raman Scattering (SERS) and UV-vis spectroscopy were used for the first time for the systematic identification of dye composition in commercial felt tip pens. A large selection of pens comprising six colors of five different brands was analyzed. Intense SERS spectra were obtained for all colors, allowing identification of main dye constituents. Poinceau 4R and Eosin dyes were found to be the main constituents of red and pink colors; Rhodamine and Tartrazine were found in orange and yellow colors; Erioglaucine was found in green and blue colors. UV-vis analysis of the same inks was used to support SERS findings but also to unequivocally assign some uncertain dye identifications, especially for yellow and orange colors. The spectral data of all felt tip pens collected through this work were assembled in a database format. The data obtained through this systematic investigation constitute the basis for the assembly of larger reference databases that ultimately will support the development of conservation protocols for the long term preservation of modern art collections.
Surface-enhanced Raman spectroscopy (SERS) has been identified as a suitable technique for the analysis of colorants in works of art. Herein, the application of SERS to the identification of dye compositions in historical felt-tip pens is reported, which is of paramount importance for the development of appropriate conservation protocols for historical drawings. In this study, three pens (pink, green, and blue colors) belonging to the film director Federico Fellini were analyzed. SERS measurements were performed directly on the pen lines drawn on a commercial paper by the deposition of Ag colloidal pastes, which allowed fast in situ dye identification without the need for extraction or hydrolysis treatments. Eosin Y was identified as the only dye present in the pink pen ink, whereas erioglaucine was found to be the main dye component in green and blue pen inks. SERS also resulted in highly efficient identification of the individual dyes erioglaucine, crystal violet, and rhodamine present as a mixture in the blue pen ink. The high SERS sensitivity was ascribed to the plasmonic effects and efficient quenching of the fluorescence interference of dyes. A comparison with contemporary pen inks highlighted minor differences in the chemical composition. These results prove that SERS can be used as a fast and sensitive analytical tool for ink analysis that provides invaluable support for the general assessment of the date, provenance, and originality of the historical drawings as well as for the development of preventive conservation protocols.
Nanoscale heating production using nanowires has been shown to be particularly attractive for a number of applications including nanostructure growth, localized doping, transparent heating and sensing. However, all proof-of-concept devices proposed so far relied on the use of highly conductive nanomaterials, typically metals or highly doped semiconductors. In this article, we demonstrate a novel nanoheater architecture based on a single semiconductor nanowire field-effect transistor (NW-FET). Nominally undoped ZnO nanowires were incorporated into three-terminal devices whereby control of the nanowire temperature at a given source-drain bias was achieved by additional charge carriers capacitatively induced via the third gate electrode. Joule-heating selective ablation of poly(methyl methacrylate) deposited on ZnO nanowires was shown, demonstrating the ability of the proposed NW-FET configuration to enhance by more than one order of magnitude the temperature of a ZnO nanowire, compared to traditional two-terminal configurations. These findings demonstrate the potential of field-effect architectures to improve Joule heating power in nanowires, thus vastly expanding the range of suitable materials and applications for nanowire-based nanoheaters.
Au nanorods were used as plasmonic transducers for investigation of mercury detection through a mechanism of amalgam formation at the nanorod surfaces. Marked scattering color transitions and associated blue shifts of the surface plasmon resonance peak wavelengths (λmax) were measured in individual nanorods by darkfield microscopy upon chemical reduction of Hg(II). Such changes were related to compositional changes occurring as a result of Hg-Au amalgam formation as well as morphological changes in the nanorods' aspect ratios. The plot of λmax shifts vs. Hg(II) concentration showed a linear response in the 10-100 nM concentration range. The sensitivity of the system was ascribed to the narrow width of single nanorod scattering spectra, which allowed accurate determination of peak shifts. The system displayed good selectivity as the optical response obtained for mercury was one order of magnitude higher than the response obtained with competitor ions. Analysis of mercury content in river and tap water were also performed and highlighted both the potential and limitation of the developed method for real sensing applications.
Poly(9,9-dioctlylfluorene) (PFO) nanofibers were fabricated by solution template wetting of anodic alumina membranes. Nanofibers with controlled thickness of 23 nm and length between 0.8 and 10 µm, were obtained, regulated by the dimensions of the used template. Nanofibers displayed spectroscopic characteristics associated with the formation of significant percentages of planar and elongated ß phase within the amorphous PFO glassy-phase. Optical polarized microscopy displayed high birefringence resulting from the high degree of internal order induced by ß phase generation within the fibers. The structural intra-chain reorganization associated with formation of ß phase was promoted by the strong geometrical confinement imposed on the material by the porous template during polymer wetting and solvent evaporation. Flow and shear force alignment techniques were used to control the orientation of fabricated PFO nanofibers, yielding to formation of large oriented nanofiber arrays on transparent substrates.
