Unambiguous identification of thiouracil residue in urine collected in non-treated bovine by tandem and high-resolution mass spectrometry

Thyrostats are banned compounds in Europe since 1981 (directive 81/602/EC) because of their carcinogenic and teratogenic properties. However, the occurrence of thiouracil (TU) in bovine urines from national monitoring plans with quantifications in the range 1-10 microg . L(-1) occasionally raises the question of its origin which might either be the consequence of an illegal administration or the result of 'endogenous' production. In order to definitively and unambiguously identify the so-called thiouracil signal in non-treated bovine urines, independent mass spectrometry (MS) approaches have been used. Different reagents (3-IBBr, 3-BrBBr and PFBBr) were used to derivatise and to extract TU from urine samples and characterisation of the residues was performed by means of different MS approaches [LC/(ESI-)MS/MS, GC/(EI+)MS/MS and HRMS (EI and NCI)]. These combined strategies allowed for an independent and confident identification of TU in bovine urine samples collected from animals never treated with any thyrostatic drugs. This result is of prime importance for laboratories and risk managers involved in the field of forbidden growth promoters control: detection of TU residue in bovine urine will have to be carefully considered as a non-systematic proof of illegal administration.     

Persulfurated aromatic compounds

Persulfurated arenes have been known for about 50 years but they were underexploited in chemistry in spite of facile, mild, and high-yielding syntheses. Their properties (redox potentials, UV/Vis absorption, conductivity, nonlinear optical properties, etc.) are mainly due to the aromaticity of the ring with sp2-hybridized carbon atoms and to the electronic contribution from numerous divalent sulfur ligands, which also stabilize negative or positive charges. The characteristic conformational patterns of the sulfur ligands often facilitate preorganization in supramolecular assemblies, with or without thiophilic metal cations, for designing redox sensors, ion-selective membranes, clathrates, organic conductors, nonlinear optical materials, liquid crystals, coordination polymers, and bioinorganic systems. A new class of supramolecules with various molecular shapes such as asterisks, chains, wheels, and windmills were reported.     

Phase-amplitude characterization of a high-repetition-rate quantum dash passively mode-locked laser

We apply a novel phase-amplitude characterization method to a one-section quantum dash-based passively mode-locked laser at a 42.2 GHz repetition rate. The method relies on the measurement of the spectral phase of the longitudinal modes by the successive analysis of the correlation signal of a group of three adjacent modes. It provides both the temporal shape of the intensity and the phase of the emitted signal. A pulse of 1.5 ps of width is measured, and a pedestal is exhibited. Extinction ratio limitation is explained by investigating the origin of this pedestal. The accuracy of the method is estimated by comparing the measured autocorrelation signal and the calculated one from the phase analysis.     

Germanium based photonic components toward a full silicon/germanium photonic platform

Lately, germanium based materials attract a lot of interest as they can overcome some limits inherent to standard Silicon Photonics devices and can be used notably in Mid-Infra-Red sensing applications. The quality of epitaxially grown intrinsic and doped materials is critical to reach the targeted performances. One of the main challenges in the field remains the fabrication of efficient group-IV laser sources compatible with the microelectronics industry, seen as an alternative to the complexity of integration of III-V lasers on Si. The difficulties come from the fact that the group-IV semiconductor bandgap has to be transformed from indirect to direct, using high tensile strains or by alloying germanium with tin. Here, we review recent progresses on critical germanium-based photonic components such as waveguides, photodiodes and modulators and discuss the latest advances towards germanium-based lasers. We show that novel optical germanium-On-Insulator (GeOI) substrates fabricated by the Smart Cut? technology is a key feature for future Si - Complementary Metal Oxide Semiconductor (CMOS) - compatible laser demonstration. This review hints at a future photonics platform based on germanium and Silicon.     

Temporary Intramolecular Generation of Pyridine Carbenes in Metal‐Free Three‐Component C?H Bond Functionalisation/Aryl‐Transfer Reactions

Nucleophilic addition of pyridines to benzyne generates zwitterionic adducts that evolve by a rapid intramolecular proton shift to produce the corresponding pyridine carbenes, N‐phenyl pyrid‐2‐ylidenes. In the presence of electrophilic ketones (isatin derivatives), the pyridylidenes can further react by an original bis‐arylation reaction of the carbonyl compounds involving a formal pyridine C? H bond functionalisation. The overall transformation is an unprecedented three‐component reaction featuring a carbene intermediate. The mechanism of this transformation was examined in detail by using both experimental and theoretical approaches. It was found that the generation of N‐phenyl pyrid‐2‐ylidene from pyridine and benzyne is energetically favoured, and that the corresponding carbene dimer can also form easily. Under the three‐component reaction conditions, the pyridylidene preferentially adds to the ketone group of the isatin derivative to produce a zwitterionic adduct amenable to an intramolecular aryl transfer reaction by a concerted nucleophilic aromatic substitution. This peculiar reactivity for a carbene was compared to possibly competitive known reactions of stable carbenes with carbonyl compounds, and the reaction was found to be under thermodynamic control. The reported method of generation of N‐phenyl pyrid‐2‐ylidenes and their reactivity with carbonyl compounds unlock new perspectives in organic synthesis.     

A multimodal magnetic resonance imaging nanoplatform for cancer theranostics

We describe an innovative multimodal system, which combines magnetic targeting of therapeutic agents with both magnetic resonance and fluorescence imaging into one system. This new magnetic nanoplatform consists of superparamagnetic γFe(2)O(3) nanoparticles, used clinically as an MRI contrast agent, conjugated to therapeutic molecules of the hydroxylmethylene bisphosphonate family (HMBPs): alendronate with an amine function as the terminal group. In vitro tests with breast cancer cells show that the γFe(2)O(3)@alendronate hybrid nanomaterial reduces cell viability and acts as a drug delivery system. We also investigated the anti-tumoural properties in vivo in nude mice xenografted with MDA-MB-231 tumours. We show that the presence of both γFe(2)O(3)@alendronate and a magnetic field significantly reduced the development of tumours. The amine functionalities can be used as precursor groups for the covalent coupling of peptides or monoclonal antibodies for specific biological targeting. The feasibility of this process was demonstrated by coupling rhodamine B, a fluorescence marker, to the γFe(2)O(3)@alendronate nanohybrid. The system showed fluorescent properties and high affinity for cells. Flow cytometry and fluorescence microscopy were used to study the kinetics of γFe(2)O(3)@alendronate uptake by cells. The magnetic and fluorescent nanoparticles are potential candidates for smart drug-delivery systems. Also, the superparamagnetic behaviour of such nanoparticles may be exploited as MRI contrast agents to improve therapeutic diagnostics.     

Tailored coordination nanoparticles: assessing the magnetic single-domain critical size

Negatively charged nanocrystals of the magnetic coordination network CsNiCr(CN)(6) were prepared in water through a seed-mediated growth with a few atomic layers accuracy and final sizes tailored from 6 to 30 nm. A lower limit of the magnetic single-domain critical size was determined to be around 15 nm possessing a blocking temperature above 20 K.     

Intramolecular Borylation via Sequential B−Mes Bond Cleavage for the Divergent Synthesis of B,N,B‐Doped Benzo[4]helicenes

New symmetric and unsymmetric B,N,B‐doped benzo[4]helicenes 3 – 6 a/b have been achieved in good yields, using a three‐step process, starting from N(tolyl)₃ in a highly divergent manner (7 examples). A borinic acid functionalized 1,4‐B,N‐anthracene 1 was found to display unprecedented reactivity, acting as a convenient and highly effective precursor for selective formation of bromo‐substituted B,N,B‐benzo[4]helicenes 2 a / 2 b via intramolecular borylation and sequential B?Mes bond cleavage in the presence of BBr₃. Subsequent reaction of 2 a / 2 b with Ar‐Li provided a highly effective toolbox for the preparation of symmetrically/unsymmetrically functionalized B,N,B‐helicenes. Their high photoluminescence quantum yields along with the small ΔE_ST suggest their potential as thermally activated delayed fluorescence (TADF) emitters for organic light‐emitting diodes (OLEDs).