An integrated analytical study of crayons from the original art materials collection of the MUNCH museum in Oslo.

Among the artists' materials of the nineteenth century, pastel crayons merit scientific interest since their early commercial formulations are mostly unknown and, until now, have been considerably less studied with respect to other contemporary painting materials. In this framework, research herein reports the results of a comprehensive multi-analytical study of 44 pastel crayons of two recognized brands (LeFranc and Dr. F. Schoenfeld) from the Munch museum collection of original materials belonging to Edvard Munch. The integrated use of complementary spectroscopic and hyphenated mass-spectrometry techniques allowed the compositional profiles of the crayons to be traced providing the identification of the inorganic and organic pigments, the fillers/extenders and the binders. All crayons resulted to be oil- based and the binder was identified to be a mixture of a drying oil (safflower or linseed oil), palm oil or Japan wax and beeswax. Among others, pigments such as ultramarine, chrome yellows, Prussian blue, manganese violet, viridian and madder lake have been identified. A significant alignment in formulations of the brands was observed with the only exception of the greens which showed distinctive pigment and filler compositions. The analytical information provided for these commercial artists' materials will be of great interest for academia, museum and other institutions hosting art collections dating from the same period and it will be used by the Munch museum to draw proper conservation strategies of its own artwork collections.

UV Absorption Spectroscopy in Water-Filled Antiresonant Hollow Core Fibers for Pharmaceutical Detection.

Due to a worldwide increased use of pharmaceuticals and, in particular, antibiotics, a growing number of these substance residues now contaminate natural water resources and drinking supplies. This triggers a considerable demand for low-cost, high-sensitivity methods for monitoring water quality. Since many biological substances exhibit strong and characteristic absorption features at wavelengths shorter than 300 nm, UV spectroscopy presents a suitable approach for the quantitative identification of such water-contaminating species. However, current UV spectroscopic devices often show limited light-matter interaction lengths, demand sophisticated and bulky experimental infrastructure which is not compatible with microfluidics, and leave large fractions of the sample analyte unused. Here, we introduce the concept of UV spectroscopy in liquid-filled anti-resonant hollow core fibers, with large core diameters and lengths of approximately 1 m, as a means to overcome such limitations. This extended light-matter interaction length principally improves the concentration detection limit by two orders of magnitude while using almost the entire sample volume-that is three orders of magnitude smaller compared to cuvette based approaches. By integrating the fibers into an optofluidic chip environment and operating within the lowest experimentally feasible transmission band, concentrations of the application-relevant pharmaceutical substances, sulfamethoxazole (SMX) and sodium salicylate (SS), were detectable down to 0.1 µM (26 ppb) and 0.4 µM (64 ppb), respectively, with the potential to reach significantly lower detection limits for further device integration.

Plasmonic nanoparticle-functionalized exposed-core fiber-an optofluidic refractive index sensing platform.

Here, we show that immobilizing ensembles of gold nanospheres within tailored areas on the open side of an exposed-core microstructured fiber yields a monolithic, highly sensitive plasmon-based refractive index sensor. The nanoparticle densities (average nanoparticle diameter: 45 nm) on the small-core fiber (core diameter: 2.5 µm) are controlled electrostatically, yielding densities of 4 nanoparticles/µm2. Refractive index sensitivities of 200 nm/RIU for aqueous analytes at high fringe contrast levels (-20 dB) have been observed. Our concept presents an easy-to-use, efficient, and multiplex-compatible sensing platform for rapid small-volume detection with the capacity for integration into a bioanalytic, optofluidic, or microfluidic system.

Nanoparticle functionalised small-core suspended-core fibre - a novel platform for efficient sensing.

Detecting small quantities of specific target molecules is of major importance within bioanalytics for efficient disease diagnostics. One promising sensing approach relies on combining plasmonically-active waveguides with microfluidics yielding an easy-to-use sensing platform. Here we introduce suspended-core fibres containing immobilised plasmonic nanoparticles surrounding the guiding core as a concept for an entirely integrated optofluidic platform for efficient refractive index sensing. Due to the extremely small optical core and the large adjacent microfluidic channels, over two orders of magnitude of nanoparticle coverage densities have been accessed with millimetre-long sample lengths showing refractive index sensitivities of 170 nm/RIU for aqueous analytes where the fibre interior is functionalised by gold nanospheres. Our concept represents a fully integrated optofluidic sensing system demanding small sample volumes and allowing for real-time analyte monitoring, both of which are highly relevant within invasive bioanalytics, particularly within molecular disease diagnostics and environmental science.

An uncovered XIII century icon: particular use of organic pigments and gilding techniques highlighted by analytical methods.

The restoration of a panel painting depicting a Madonna and Child listed as an unknown Tuscan artist of the nineteenth century, permitted the hidden original version, a XIII century Medieval icon to be uncovered. It is discovery provided the opportunity for an extensive in situ campaign of non-invasive analytical investigations by portable imaging and spectroscopic techniques (infrared, X-ray fluorescence and diffraction, UV-Vis absorption and emission), followed by aimed micro-destructive investigations (Raman and SEM-EDS). This approach permitted characterization of the original ground and paint layers by complementary techniques. Furthermore, this protocol allowed supplementary particularities of great interest to be highlighted. Namely, numerous original gilding techniques have been accentuated in diverse areas and include the use of surrogate gold (disulphur tin), orpiment as a further false gold and an area with an original silver rich layer. Moreover, pigments including azurite mixed with indigo have been non-invasively identified. Micro-invasive analyses also allowed the diagnosis of organic colorants, namely, an animal anthraquinone lake, kermes and an unusual vegetal chalcone pigment, possibly safflower. The identification of the latter is extremely rare as a painting pigment and has been identified using an innovative adaption to surface enhanced Raman techniques on a cross-section. The resulting data contributes new hypotheses to the historic and artistic knowledge of materials and techniques utilized in XIII century icon paintings and ultimately provides scientific technical support of the recent restoration.

Non-invasive and micro-destructive investigation of the Domus Aurea wall painting decorations.

The paper reports on the exploitation of an educated multi-technique analytical approach based on a wide non invasive step followed by a focused micro-destructive step, aimed at the minimally invasive identification of the pigments decorating the ceiling of the Gilded Vault of the Domus Aurea in Rome. The combination of elemental analysis with molecular characterization provided by X-ray fluorescence and UV-vis spectroscopies, respectively, allowed for the in situ non-invasive identification of a remarkable number of pigments, namely Egyptian blue, green earth, cinnabar, red ochre and an anthraquinonic lake. The study was completed with the Raman analysis of two bulk samples, in particular, SERS measurements allowed for the speciation of the anthraquinonic pigment. Elemental mapping by scanning electron microscopy-energy dispersive spectrometer combined with micro-fluorimetry on cross-section gave an insight into both the distribution of different blend of pigments and on the nature of the inorganic support of the red dye.

Unilateral NMR, 13C CPMAS NMR spectroscopy and micro-analytical techniques for studying the materials and state of conservation of an ancient Egyptian wooden sarcophagus.

A multi-technique approach was employed to study a decorated Egyptian wooden sarcophagus (XXV-XXVI dynasty, Third Intermediate Period), belonging to the Museo del Vicino Oriente of the Sapienza University of Rome. Portable non-invasive unilateral NMR was applied to evaluate the conservation state of the sarcophagus. Moreover, using unilateral NMR, a non-invasive analytical protocol was established to detect the presence of organic substances on the surface and/or embedded in the wooden matrix. This protocol allowed for an educated sampling campaign aimed at further investigating the state of degradation of the wood and the presence of organic substances by (13)C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The composition of the painted layer was analysed by optical microscopy (OM), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), Raman and surface enhanced (resonance) Raman spectroscopy (SERS/SERRS), infrared and GC-MS techniques, evidencing original components such as clay minerals, Egyptian green, indigo, natural gums, and also highlighting restoration pigments and alteration compounds. The identification of the wood, of great value for the reconstruction of the history of the artwork, was achieved by means of optical microscopy.

On the use of overtone and combination bands for the analysis of the CaSO4-H2O system by mid-infrared reflection spectroscopy.

With the aim of characterizing ground preparations of paintings by infrared reflection spectroscopy, the CaSO(4)-H(2)O system (gypsum/bassanite/anhydrite) has been re-investigated, evaluating and assigning the SO(4)(2-) and OH overtone and combination bands, respectively, in the ranges 1900-2700 cm(-1) and 5000-6000 cm(-1) resulting from reflection and high concentration transmission spectra. The second-order modes have been proven to be highly specific, reliable, and less affected by overlap with bands of organic binders and can hence be exploited for the identification of the sulfate hydration phase using infrared (IR) reflection spectroscopy. Subsequently, the characterization and identification of hydration phases in unknown sulfate-based ground preparations on authentic artworks have been carried out noninvasively by fiber-optic reflection IR spectroscopy and on cross-sections by infrared reflection micro-spectroscopy. The spectroscopic data collected both on standards and artworks have been cross-validated by X-ray diffraction.

Noninvasive testing of art and cultural heritage by mobile NMR.

Nuclear magnetic resonance (NMR) has many applications in science, medicine, and technology. Conventional instrumentation is large and expensive, however, because superconducting magnets offer maximum sensitivity. Yet NMR devices can also be small and inexpensive if permanent magnets are used, and samples need not be placed within the magnet but can be examined externally in the stray magnetic field. Mobile stray-field NMR is a method of growing interest for nondestructive testing of a diverse range of materials and processes. A well-known stray-field sensor is the commercially available NMR-MOUSE, which is small and can readily be carried to an object to be studied. In this Account, we describe mobile stray-field NMR, with particular attention to its use in analyzing objects of cultural heritage. The most common data recorded are relaxation measurements of (1)H because the proton is the most sensitive NMR nucleus, and relaxation can be measured despite the inhomogeneous magnetic field that typically accompanies a simple magnet design. Through NMR relaxation, the state of matter can be analyzed locally, and the signal amplitude gives the proton density. A variety of stray-field sensors have been designed. Small devices weighing less than a kilogram have a shallow penetration depth of just a few millimeters and a resolution of a few micrometers. Access to greater depths requires larger sensors that may weigh 30 kg or more. The use of these sensors is illustrated by selected examples, including examinations of (i) the stratigraphy of master paintings, (ii) binder aging, (iii) the deterioration of paper, (iv) wood density in master violins, (v) the moisture content and moisture profiles in walls covered with paintings and mosaics, and (vi) the evolution of stone conservation treatments. The NMR data provide unique information to the conservator on the state of the object--including past conservation measures. The use of mobile NMR remains relatively new, expanding from field testing of materials such as roads, bridge decks, soil, and the contents of drilled wells to these more recent studies of objects of cultural heritage. As a young field, noninvasive testing of artworks with stray-field NMR thus offers many opportunities for research innovation and further development.

In situ non-invasive investigation on the painting techniques of early Meissen Stoneware.

In situ, non-invasive investigations by means of portable X-ray fluorescence and fibre optic reflectance mid-infrared (mid-FTIR) spectroscopy of painted Böttger Stoneware objects have been carried out through the MOLAB transnational access to the Porcelain Collection of the Staatliche Kunstsammlungen in Dresden. It has been possible to gather information regarding the composition of the black glaze by applying a principal component analysis to the elemental analysis to distinguish between the variations of lead, iron and manganese compositions of each glaze. It has been furthermore feasible to combine molecular spectroscopy for characterization of the constituent painting materials, namely lead white as cerusite and hydrocerusite, the use of cinnabar, azurite and Prussian blue leading to a better knowledge of the state of conservation and utility of certain pigments that may give rise to chronology of the decorative artwork. The identification of oxalates namely whedellite and moolooite are assigned as degradation products relative to the decorative areas.

A patient-centric, Internet-based application for the data management of a multi-centre respiratory syncytial virus prophylaxis program.

The success of respiratory syncytial virus (RSV) prophylaxis programs is partially dependent upon meticulous tracking of at risk infants, and excellent data management. We designed and built an integrated, shared, user-driven but infant-centric data management application that enables an infants healthcare provider to determine an infants RSV prophylaxis status throughout the RSV season. The security and confidentiality of each infants information is protected by rigorous integrity constraints that have been integrated into the database schema.

A randomized trial of ganciclovir versus ganciclovir plus immune globulin for prophylaxis against Epstein-Barr virus related posttransplant lymphoproliferative disorder.

BACKGROUND: Transplant recipients who are Epstein-Barr virus (EBV)-seronegative and receive organs from seropositive donors (EBV D+/R-) are at increased risk for posttransplant lymphoproliferative disorder (PTLD) and may benefit from antiviral prophylaxis. We performed a multi-center trial assessing two different antiviral regimens and their effect on EBV replication. METHODS: EBV D+/R- solid organ transplant recipients were randomized to receive either ganciclovir and placebo or ganciclovir and immunoglobulin (IG) for 3 months. Following this, patients were unblinded and IG patients received additional IG therapy until 6 months. EBV viral loads were done at least monthly. RESULTS.: Thirty-four patients (25 pediatric, 9 adult) completed the protocol (16 placebo; 18 IG). The incidence of a detectable viral load within the first year posttransplant was 13/16 (81.3%) in the ganciclovir arm vs. 13/18 (72.2%) in the ganciclovir and IG arm (P=0.8). Time to first detectable viral load, and time to high-level viral load were not significantly different. By repeated measures ANOVA analysis, and by estimation of viral load AUC, no significant effect of randomization group was observed on EBV viral loads. PTLD developed in 3 (8.8%) patients (all in IG arm; P=0.23). CONCLUSIONS: No significant difference in EBV viral load suppression was observed when ganciclovir was compared with ganciclovir and IG in high-risk EBV D+/R- patients.