Chemometric tools to point out benchmarks and chromophores in pigments through spectroscopic data analyses

Spectral preprocessing data and chemometric tools are analytical methods widely applied in several scientific contexts i.e., in archaeometric applications. A systematic classification of natural powdered pigments of organic and inorganic nature through Principal Component Analysis with a multi-instruments spectroscopic study is presented here. The methodology allows the access to elementary and molecular unique benchmarks to guide and speed up the identification of an unknown pigment and its recipe. This study is conducted on a set of 48 powdered pigments and tested on a real-case sample from the wall painting in S. Maria Delle Palate di Tusa (Messina, Italy). Four spectroscopic techniques (X-ray Fluorescence, Raman, Attenuated Total Reflectance and Total Reflectance Infrared Spectroscopies) and six different spectrometers are tested to evaluate the impact of different setups. The novelty of the work is to use a systematic approach on this initial dataset using the entire spectroscopic energy range without any windows selection to solve problems linked with the manipulation of large analytes/materials to find an indistinct property of one or more spectral bands opening new frontiers in the dataset spectroscopic analyses

Evaluation of the imaging performance of the TECNOMUSE muon tomograph and its feasibility in a real scenario

Muon tomography is a very promising imaging technique for the control of cargo containers. It takes advantage of cosmic muons and their interaction mechanisms to reconstruct images of the volume traversed by these particles. In the present work, the imaging performance of a novelmuon tomography scanner based on resistive plate chambers detectors is investigated. By means of several Monte Carlo simulations, some imaging parameters are evaluated. The results in terms of spatial resolution, field-of-view and volume and material recognition make the presented scanner and its geometry suitable for muon tomograph

De novo RANBP2 variant in a fetal demise case with cerebral intraparenchymal hemorrhage.

Fetal intracranial hemorrhage (ICH) may result from a wide array of causes, either associated with maternal or fetal risk factors. In the last decade, monogenic causes of susceptibility to fetal ICH have been described, in particular in association with COL4A1 and COL4A2 genes. A peculiar form of ICH is acute necrotizing encephalitis (ANE), which is characterized by a rapid-onset severe encephalopathy following an abnormal inflammatory response to an otherwise banal infection. It usually affects healthy children and it is thought to be multifactorial, with a genetic predisposition. RANBP2 gene has been extensively associated with ANE susceptibility. We hereby present a unique case of a 42-year-old secundigravida with intrauterine fetal demise at 35 weeks of gestation. Trio-based whole-exome sequencing performed on both parents and fetal DNA showed a de novo likely pathogenic variant in the RANBP2 gene on 2q13. At the fetal autopsy, subtentorial hematoma and cerebral intraparenchymal hemorrhage were present. We speculate that this might be a new phenotypic presentation of RANBP2-associated disease. However, more similar fetal cases need to be reported in order to reinforce this hypothesis

The instrument suite of the European Spallation Source

An overview is provided of the 15 neutron beam instruments making up the initial instrument suite of the European Spallation Source (ESS), and being made available to the neutron user community. The ESS neutron source consists of a high-power accelerator and target station, providing a unique long-pulse time structure of slow neutrons. The design considerations behind the time structure, moderator geometry and instrument layout are presented. The 15-instrument suite consists of two small-angle instruments, two reflectometers, an imaging beamline, two single-crystal diffractometers; one for macromolecular crystallography and one for magnetism, two powder diffractometers, and an engineering diffractometer, as well as an array of five inelastic instruments comprising two chopper spectrometers, an inverse-geometry single-crystal excitations spectrometer, an instrument for vibrational spectroscopy and a high-resolution backscattering spectrometer. The conceptual design, performance and scientific drivers of each of these instruments are described. All of the instruments are designed to provide breakthrough new scientific capability, not currently available at existing facilities, building on the inherent strengths of the ESS long-pulse neutron source of high flux, flexible resolution and large bandwidth. Each of them is predicted to provide world-leading performance at an accelerator power of 2 MW. This technical capability translates into a very broad range of scientific capabilities. The composition of the instrument suite has been chosen to maximise the breadth and depth of the scientific impact o

Chemometrics tools for Advanced Spectroscopic Analyses

Any system is described by several variables, often in the form of hidden information, able to describe and explain functional mechanisms for the majority of the processes which can be evaluated analytically only when we consider entire complex datasets. The relationship between those variables is the key to identify and quantify correlations among the parameters describing the data in a strictly model-free manner. In chemometrics one uses mathematical and statistical methods to improve the understanding of chemical information through the correlation of physical parameters or properties to analytical instrument data. This approach is currently used across chemistry, materials science, biology, with a growing impact is the field of spectroscopy. This paper presents the ability of chemometric technique applied to Advanced Spectroscopic Analyses, examples include spectroscopic data collected from both the High- resolution neutron Spectrometer TOSCA, operating at the ISIS pulsed Neutron and Muon Source (UK) and X-ray fluorescence (XRF) spectroscopy. This work demonstrates the high-resolution of the Principal Component Analysis (PCA) to a spectroscopic data-set dealing with the determination of marker bands from Inelastic Neutron Scattering (INS) spectra of a large data- set, the presence of a probably additional transition phase of one globular molecule and evidencing the metallic nature of the black/brownish inscriptions on daily-use textiles used in ancient Egypt. This study will pave the way for the analysis of multi-parametric, high-throughput INS data, now within reach using state-of-the-art chemical neutron spectrometers such as VESPA

A 4.2 kDa synthetic peptide as a potential probe to evaluate the antibacterial activity of coumarin drugs

The coumarin antibiotics are potent inhibitors of DNA replication whose target is the enzyme DNA gyrase, an ATP-dependent bacterial type II topoisomerase. The coumarin drugs inhibit gyrase action by competitive binding to the ATP-binding site of DNA gyrase B protein. The production of new biologically active products has stimulated additional studies on coumarin-gyrase interactions. In this regard, a 4.2 kDa peptide mimic of DNA gyrase B protein from Escherichia coli has been designed and synthesized. The peptide sequence includes the natural fragment 131-146 (coumarin resistance-determining region) and a segment containing the gyrase-DNA interaction region (positions 753-770). The peptide mimic binds to novobiocin (K-a = 1.4 +/- 0.3 x 10(5) m(-1)), plasmid (K-a = 1.6 +/- 0.5 x 10(6) m(-1)) and ATP (K-a = 1.9 f 0.4 x 10(3) m(-1)), results previously found with the intact B protein. on the other hand, the binding to novobiocin was reduced when a mutation of Arg-136 to Leu-136 was introduced, a change previously found in the DNA gyrase B protein from several coumarin-resistant clinical isolates of Escherichia coLi. In contrast, the binding to plasmid and to ATP was not altered. These results suggest that synthetic peptides designed in a similar way to that described here could be used as mimics of DNA gyrase in studies which seek a better understanding of the ATP, as well as coumarin, binding to the gyrase and also the mechanism of action of this class of antibacterial drugs. Copyright (C) 2004 European Peptide Society and John Wiley Sons, Ltd

Neutron sensing at spallation neutron sources by SERS

Neutron detectors are paramount in many applications from medical science to homeland security and aerospace. A miniaturized solid-state device based on a nanostructured-gold thin film grown by pulsed laser ablation under deposition-controlled conditions and functionalized with a monolayer of 4-mercaptophenyboronic acid (4-MPBA) was fabricated as a neutron dose detector. The device is tested with slow neutron detection in the thermal and epithermal energy range at ISIS spallation neutron source (UK). After the neutron irradiation, 4-MPBA is converted into thiophenol (TP), and the chemical modification is monitored by the intensity of related vibrational bands at 1586 cm−1 (4-MPBA) and 1574 cm−1 (TP). The latter are used as a vibrational signature of the absorbed dose by surface-enhanced Raman spectroscopy (SERS). The conversion of 4-MPBA to TP is due to the loss of the boron-containing group after the absorption of a slow neutron by 10B isotope. The I1574/I1586 ratio is used to estimate the ratio of 10B nuclei absorption reactions due to the thermal and epithermal contributions and it is proposed for the development of neutron dosimetry for nuclear medicine, aerospace, and security applications

A non-invasive spectroscopic study to evaluate both technological features and conservation state of two types of ancient Roman coloured bricks

The study of both original and decaying compounds is relevant in understanding the chemistry behind the deterioration processes, above all in open museum contexts where environmental stressors affect the artefacts. In this sense, a combination of non-invasive spectroscopy techniques (Raman spectroscopy, μ-X-ray fluorescence and X-ray diffraction) was applied on an ancient Roman building (130 CE), the “Casa di Diana” Mithraeum at Ostia Antica archaeological site. The aim is to study the raw materials, manufacturing and decaying products of the two observed types of Roman fired bricks (red and yellow) that compose the building. The present study estimates an illite raw material of carbonate-bearing marine clay likely referring to the common deposits of central/southern Italy, which contain calcite as accessory phase and a-plastic fraction constituted by quartz, feldspar and opaques. This clay material was added with volcanic temper characterised by abundant clinopyroxene and analcime (from analcimization of leucite) that are typical of the Roman Province volcanism. The firing would be probably the result of oxidizing conditions, as proved by the hematite presence. Thanks to the existence of specific neoformed mineral phases during firing it was possible to assess different temperatures ranges. In detail, the red/orange bricks, for the existence of gehlenite (formed from calcite and its reaction with silicates), were fired at 800–900 °C range; whereas, the yellow ones are characterised by the lack of gehlenite and the disappearance of illite/muscovite, which indicates firing temperature at over 900 °C. Regarding the decaying products, the gypsum covers most of the surface of most bricks, both red and the yellow ones, but these latter are more susceptible to environmental stressors (sulphates and carbonates). Therefore, this work points out how by integrated non-invasive approaches it is possible trace back to original firing temperature, technology of manufacture, interpreting ceramic data

Probing the binding of the coumarin drugs using peptide fragments of DNA gyrase B protein

Bacterial DNA gyrase, has been identified as the target of several antibacterial agents, including the coumarin drugs. The coumarins inhibit the gyrase action by competitive binding to the ATP-binding site of DNA gyrase B (GyrB) protein. The high in vitro inhibitory potency of coumarins against DNA gyrase reactions has raised interest in studies on coumarin-gyrase interactions. In this context, a series of low-molecular weight peptides, including the coumarin resistance-determining region of subunit B of Escherichia coli gyrase, has been designed and synthesized. The first peptide model was built using the natural fragment 131-146 of GyrB and was able to bind to novobiocin (K a = 1.8 ± 0.2 × 105/M) and ATP (Ka = 1.9 ± 0.4 × 103/M). To build the other sequences, changes in the Arg136 residue were introduced so that the binding to the drug was progressively reduced with the hydrophobicity of this residue (Ka = 1.3 ± 0.1 × 105/M and 1.0 ± 0.2 × 105/M for Ser and His, respectively). No binding was observed for the change Arg136 to Leu. In contrast, the binding to ATP was not altered, independently of the changes promoted. On the contrary, for peptide-coumarin and peptide-ATP complexes, Mg2+ appears to modulate the binding process. Our results demonstrate the crucial role of Arg 136 residue for the stability of coumarin-gyrase complex as well as suggest a different binding site for ATP and in both cases the interactions are mediated by magnesium ions. Copyright Blackwell Munksgaard, 2005