Effect of gestational age on cerebral lesions in neonatal encephalopathy.

Objective: To determine the risk on brain lesions according to gestational age (GA) in neonates with neonatal encephalopathy.

Design: Secondary analysis of the prospective national French population-based cohort, Long-Term Outcome of NeonataL EncePhALopathy.

Setting: French neonatal intensive care units.

Mechanical ordering of pigment crystallites in oil binder: can electron paramagnetic resonance reveal the gesture of an artist?

Is it possible to reconstruct the gesture of an ancient artist applying a paint layer, considering that the orientation distribution of crystallites of an inorganic pigment remains definitively imprinted on the support after drying of the layer? If the pigment contains paramagnetic transition metal ions whose magnetic interactions are themselves anisotropic, then the shape of the electron paramagnetic resonance (EPR) spectrum should reflect the distribution of grain orientations. We have demonstrated this effect in the case of Egyptian blue CaCuSiO, a pigment used for at least 3 millennia in antiquity, by reconstructing the probability density of crystallite orientations under various modes of application, such as brush painting, dabbing and droplet deposition.

Development and Validation of a Non-Targeted Screening Method for Most Psychoactive, Analgesic, Anaesthetic, Anti-Diabetic, Anti-Coagulant and Anti-Hypertensive Drugs in Human Whole Blood and Plasma Using High-Resolution Mass Spectrometry.

(1) Background: In toxicological laboratories, various screening methods can be used to identify compounds involved in intoxication. High-resolution mass spectrometry has been increasingly used in this context for the last years, because of its sensitivity and reliability. Here, we present the development and validation of a screening method that uses liquid chromatography coupled with a high-resolution mass spectrometer.

Insight into the structure of black coatings of ancient Egyptian mummies by advanced electron magnetic resonance of vanadyl complexes.

Ancient Egyptian mummies from the Late Period to the Greco-Roman Period were covered by a black coating consisting of complex and heterogeneous mixtures of conifer resins, wax, fat and oil with variable amounts of bitumen. Natural bitumen always contains traces of vanadyl porphyrin complexes that we used here as internal probes to explore the nanoscale environment of V ions in these black coatings by electron nuclear double resonance (ENDOR) and hyperfine sub-level correlation spectroscopy (HYSCORE). Four types of vanadyl porphyrin complexes were identified from the analysis of N hyperfine interactions.

Antiphospholipid syndrome-induced ischemic stroke following pembrolizumab: Case report and systematic review.

Immune checkpoint inhibitors (ICI) improve the prognosis of patients with advanced non-small cell lung cancer. However, clinicians should be aware of potentially life-threatening immune-related adverse events (irAEs). We report a case of a 67-year-old man with lung adenocarcinoma who developed an acute ischemic stroke after the second administration of pembrolizumab.

Heterogeneity of germinal center B cells: New insights from single-cell studies.

Upon antigen exposure, activated B cells in antigen-draining lymphoid organs form microanatomical structures, called germinal centers (GCs), where affinity maturation occurs. Within the GC microenvironment, GC B cells undergo proliferation and B cell receptor (BCR) genes somatic hypermutation in the dark zone (DZ), and affinity-based selection in the light zone (LZ). In the current paradigm of GC dynamics, high-affinity LZ B cells may be selected by cognate T- follicular helper cells to either differentiate into plasma cells or memory B cells, or re-enter the DZ and initiate a new round of proliferation and BCR diversification, before migrating back to the LZ.

Relevance of Single-Transmetalated Resting States in Iron-Mediated Cross-Couplings: Unexpected Role of σ-Donating Additives.

Control of the transmetalation degree of organoiron(II) species is a critical parameter in numerous Fe-catalyzed cross-couplings to ensure the success of the process. In this report, we however demonstrate that the selective formation of a monotransmetalated Fe species during the catalytic regime counterintuitively does not alone ensure an efficient suppression of the nucleophile homocoupling side reaction. It is conversely shown that a fine control of the transmetalation degree of the transient Fe intermediates obtained after the activation of alkyl electrophiles by a single-electron transfer (SET), achievable using σ-donating additives, accounts for the selectivity of the cross-coupling pathway.

Nondestructive Analysis of Mummification Balms in Ancient Egypt Based on EPR of Vanadyl and Organic Radical Markers of Bitumen.

The black matter employed in the funeral context by ancient Egyptians is a complex mixture of plant-based compounds with variable amounts of bitumen. Asphaltene, the most resistant component of bitumen, contains vanadyl porphyrins and carbonaceous radicals, which can be used as paramagnetic probes to investigate embalming materials without sample preparation. Electron paramagnetic resonance (EPR) at the X-band, combining in-phase and out-of-phase detection schemes, provides new information in a nondestructive way about the presence, the origin, and the evolution of bitumen in these complex materials.

Quantification of methadone, buprenorphine, naloxone, opioids, and their derivates in whole blood by liquid chromatography-high-resolution mass spectrometry: Analysis of their involvement in fatal forensic cases.

Opioids represent a broad family of compounds that can be used in several indications: analgesics, antitussives, opioid substitution therapy (e.g. methadone, buprenorphine…).

Photochemical Origin of the Darkening of Copper Acetate and Resinate Pigments in Historical Paintings.

Copper acetate and copper resinate pigments are bimetallic Cu complexes in which metal atoms are bridged by four carboxylate ligands (acetate or abietate). Prepared with lindseed oil as binder, these green pigments were particularly used in easel paintings between the 15th and 17th centuries. Unfortunately, they had the tendency to darken in an irreversible way, explaining why they fell into disuse.

Ubiquinone Biosynthesis over the Entire O Range: Characterization of a Conserved O-Independent Pathway.

Most bacteria can generate ATP by respiratory metabolism, in which electrons are shuttled from reduced substrates to terminal electron acceptors, via quinone molecules like ubiquinone. Dioxygen (O) is the terminal electron acceptor of aerobic respiration and serves as a co-substrate in the biosynthesis of ubiquinone. Here, we characterize a novel, O-independent pathway for the biosynthesis of ubiquinone.

Increased risk of rejection after basiliximab induction in sensitized kidney transplant recipients without pre-existing donor-specific antibodies - a retrospective study.

Depleting induction therapy is recommended in sensitized kidney transplant recipients (KTRs), though the detrimental effect of nondonor-specific anti-HLA antibodies is not undeniable. We compared the efficacy and safety of basiliximab and rabbit anti-thymocyte globulin (rATG) in sensitized KTRs without pre-existing donor-specific antibodies (DSAs). This monocentric retrospective study involved all sensitized KTR adults without pre-existing DSAs (n = 218) who underwent transplantation after June 2007.

A spin crossover porous hybrid architecture for potential sensing applications.

Spin crossover cations have been successfully synthesized in the pores of a mesoporous robust Metal-Organic Framework (MOF) MIL-100(Al) through sequential introduction of Fe(iii) cations and a sal2trien ligand. The MIL-100(Al)@Fe(sal2trien) hybrid material retains its crystallinity and partial porosity compared to the parent MOF. The spin state of the Fe(sal2trien)+ cations can be modulated at room temperature through sorption of guest molecules, paving the way to the design of a new generation of sensors based on MOF@spin crossover complex solids.

A phase transformable ultrastable titanium-carboxylate framework for photoconduction.

Porous titanium oxide materials are attractive for energy-related applications. However, many suffer from poor stability and crystallinity. Here we present a robust nanoporous metal-organic framework (MOF), comprising a TiO oxocluster and a tetracarboxylate ligand, achieved through a scalable synthesis.

Population pharmacokinetics of articaine with 1:200,000 epinephrine during third molar surgery and simulation of high-dose regimens.

Background And Objectives: Articaine is more and more used in third molar surgery under local anesthesia (LA). The objectives of this analysis were to characterize the pharmacokinetics of articaine for this type of surgery and to simulate dosing regimens.

Methods: Non-linear mixed-effects modeling conducted in Monolix 4.

Nonredox thiolation in tRNA occurring via sulfur activation by a [4Fe-4S] cluster.

Sulfur is present in several nucleosides within tRNAs. In particular, thiolation of the universally conserved methyl-uridine at position 54 stabilizes tRNAs from thermophilic bacteria and hyperthermophilic archaea and is required for growth at high temperature. The simple nonredox substitution of the C2-uridine carbonyl oxygen by sulfur is catalyzed by tRNA thiouridine synthetases called TtuA.

[Pleuroperitoneal communication: pleural effusion subsequent to the initiation of peritoneal dialysis, about a case].

We report the case of a patient with pleural effusion occurring after initiation of a peritoneal dialysis. This phenomenon is favoured by the existence of a pleuroperitoneal communication. The latter is described at the origin of other diseases like catamenial pneumothorax and pleural effusion in connection with cirrhotic ascites.

Controlling disorder in the ZnGaO:Cr persistent phosphor by Mg substitution.

We have studied in this work the effect of increasing structural disorder on the persistent luminescence of a Cr doped zinc gallate spinel. This disorder was introduced by progressive substitution of Zn by Mg ions, and was studied by photoluminescence, X-ray diffraction, extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES) and electron paramagnetic resonance (EPR) spectroscopy. It was found that increasing the Mg/Zn substitution decreases the number of Cr in undistorted sites and increases the number of Cr with neighbouring antisite defects and with neighbouring Cr ions (referred to as Cr clusters), which in turn decreases the intensity of persistent luminescence.

Interaction of Cr(3+) with valence and conduction bands in the long persistent phosphor ZnGa2O4:Cr(3+), studied by ENDOR spectroscopy.

Cr(3+)-doped zinc gallate ZnGa2O4 is a red-near infrared (IR) long persistent phosphor that can be excited by orange-red light, in the transparency window of living tissues. With this property, persistent luminescence nanoparticles were recently used for in vivo optical imaging of tumors in mice. In order to understand the origin of the excitability of persistent luminescence by visible light in this material, a Q-band ENDOR investigation of (71/69)Ga and (53)Cr nuclei was performed in ZnGa2O4:Cr(3+) to get information on the interaction of Cr(3+) with valence and conduction bands.

Validation of a fast UPLC-MS/MS method for quantitative analysis of opioids, cocaine, amphetamines (and their derivatives) in human whole blood.

Background: Conventional methods for analysis of drugs of abuse require multiple assays which can be both expensive and time-consuming. This work describes a novel, rapid, simple and sensitive method for the quantification of 14 illicit drugs and their metabolites in whole blood. Results/methodology: This method employed a rapid liquid-liquid sample extraction of whole blood followed by UPLC-MS/MS analysis.

Nuclear magnetic biosignatures in the carbonaceous matter of ancient cherts: comparison with carbonaceous meteorites.

The search for organic biosignatures is motivated by the hope of understanding the conditions of emergence of life on Earth and the perspective of finding traces of extinct life in martian sediments. Paramagnetic radicals, which exist naturally in amorphous carbonaceous matter fossilized in Precambrian cherts, were used as local structural probes and studied by electron paramagnetic resonance (EPR) spectroscopy. The nuclear magnetic resonance transitions of elements inside and around these radicals were detected by monitoring the nuclear modulations of electron spin echo in pulsed EPR.

Validation of a fast method for quantitative analysis of elvitegravir, raltegravir, maraviroc, etravirine, tenofovir, boceprevir and 10 other antiretroviral agents in human plasma samples with a new UPLC-MS/MS technology.

Therapeutic drug monitoring (TDM) of antiretrovirals requires accurate and precise analysis of plasma drug concentrations. This work describes a simple, fast and sensitive UPLC-MS/MS method for determination of the commonly used protease inhibitors such as amprenavir, atazanavir, darunavir, indinavir, lopinavir, ritonavir, saquinavir and tipranavir, tenofovir a nucleoside reverse transcriptase inhibitor (NRTI), the non-NRTI such as efavirenz, nevirapine, etravirine, the CCR5 antagonist maraviroc as well as the more recent antiretrovirals, the integrase inhibitors such as raltegravir, elvitegravir and the new direct acting anti-HCV boceprevir. Adapted deuterated internal standard was added to plasma aliquots (100μl) prior to protein precipitation with methanol and acetonitrile.

Implementing a new EPR lineshape parameter for organic radicals in carbonaceous matter.

Background: Electron Paramagnetic Resonance (EPR) is a non-destructive, non-invasive technique useful for the characterization of organic moieties in primitive carbonaceous matter related to the origin of life. The classical EPR parameters are the peak-to-peak amplitude, the linewidth and the g factor; however, such parameters turn out not to suffice to fully determine a single EPR line.

Results: In this paper, we give the definition and practical implementation of a new EPR parameter based on the signal shape that we call the R10 factor.

Origin of the decoherence of the extended electron spin state in Ti-doped β-Ga2O3.

The mechanism of decoherence of the electron spin of Ti(3+) in β-Ga2O3 was investigated by pulsed electron paramagnetic resonance. At 4.2 K, both instantaneous and spectral diffusion contribute to the decoherence.