Following the new (EU) regulation 2022/2292 with regard to requirements for the entry into the Union of consignments of food-producing animals and certain goods intended for human consumption, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been optimized to identify and quantify 17 banned veterinary drugs in dry or brined casings from different species. Casings are used to manufacture various meat specialties (sausages,···) in Europe, and it is important to take into account the risk of contamination of these manufactured casings entering the European Union. The metabolites of seven nitrofurans, seven nitroimidazoles, chloramphenicol, and dapsone were simultaneously identified and quantified by the developed standard operating procedure, which was successfully validated according to the criteria of the Commission Implementing Regulation (EU) 2021/808, using the regulatory limits or levels of interest in force in Europe. The reliability of the method has been demonstrated by the analysis of proficiency testing reference materials. Additional data on a challenged nitrofuran marker residue are discussed.

The archaeal ribosome is of the eukaryotic type. TACK and Asgard superphyla, the closest relatives of eukaryotes, have ribosomes containing eukaryotic ribosomal proteins not found in other archaea, eS25, eS26 and eS30. Here, we investigate the case of Saccharolobus solfataricus, a TACK crenarchaeon, using mainly leaderless mRNAs. We characterize the small ribosomal subunit of S. solfataricus bound to SD-leadered or leaderless mRNAs. Cryo-EM structures show eS25, eS26 and eS30 bound to the small subunit. We identify two ribosomal proteins, aS33 and aS34, and an additional domain of eS6. Leaderless mRNAs are bound to the small subunit with contribution of their 5'-triphosphate group. Archaeal eS26 binds to the mRNA exit channel wrapped around the 3' end of rRNA, as in eukaryotes. Its position is not compatible with an SD:antiSD duplex. Our results suggest a positive role of eS26 in leaderless mRNAs translation and possible evolutionary routes from archaeal to eukaryotic translation.

The electrochemical and photophysical properties of two series of ruthenium bis(bipyridine) complexes featuring either a pyridine-phosphonium ylide (PC) or a pyridine-iminophosphorane (PN) ligand were synthesized. Three different bipyridines were employed allowing the synthesis of six P-ylide RuII complexes. All the complexes were fully characterized by multinuclear NMR spectroscopy, HR-mass spectrometry, as well as X-ray crystallography, and no major difference was observed between them. In cyclic voltammetry, the measured potentials agree with the electronic properties of the bipyridine ligands and underline the strong electron donation of the phosphonium ylide. Indeed, the oxidation is facilitated and the reductions become more difficult compared to the corresponding [Ru(Rbpy)3] complexes. The absorption spectra of the PC and PN RuII complexes are similar, with a bathochromic shift compared to polypyridine RuII complexes, which is amplified in the presence of electron-withdrawing substituents on the bipyridine. Regarding luminescence, the PC complexes emit at a lower energy than the PN analogues. In addition, the associated lifetime depends on both the nature of the P-ylide and the substituents on the bipyridine ligand. This was related to the different adiabatic 3MC/3MLCT gap calculated at the DFT level, which is larger for two iminophosphorane complexes exhibiting a lifetime of the order of a few hundred nanoseconds.

Two novel gallium precursors for Atomic Layer Deposition (ALD), LGaMe2 and LGa(NMe2)2 with L = N,N '-di-tert-butylacetamidinato, were successfully synthesised from a carbodiimide and gallium trichloride. The compounds were characterised by NMR spectroscopy and HR-mass spectrometry, confirming their monomeric nature. Their surface reactivity under ALD conditions with H2O and H2S co-reactants was explored using in situ quartz crystal microbalance (QCM) measurements. LGaMe2, bearing methyl ligands, was found to inhibit film growth, with deposition halting after three cycles. In contrast, LGa(NMe2)2 facilitated the successful growth of films using both H2O and H2S leading to Ga2O3 and Ga2S3 respectively, as confirmed by additional thin film ex situ characterisation. This study underscores the critical role of auxiliary X ligands (here Me or NMe2) in determining ALD process efficiency, and emphasises the complexity and unique nature of surface chemistry compared to solution-phase behaviour.

Tridentate NNN ligands combining three different N-coordinating groups; a pyridine, a secondary amine, and an iminophosphorane were synthesized (LR, R = Et, Cy, Ph). They were coordinated to FeII, CoII, and MnII to yield high spin complexes as indicated by the magnetic moment measured in solution. They were also characterized by 1H NMR spectroscopy, HR-MS, elemental analysis, as well as X-ray diffraction for some of them. Depending on the nature of the P-substituent, ligand exchange occurs in solution leading to octahedral complexes featuring two LCy ligand coordinated in a kappa 2 mode. The latter were also independently prepared. All the synthesized complexes were compared in the catalytic transfer hydrogenation of ketones. LEt supported complexes performed better and the reaction was optimized for the CoII and MnII complexes because these metals are more rarely employed for this reaction than FeII. Both complexes proved able to efficiently reduce a range of aromatic and aliphatic ketones within 24 h at 70 degrees C using 1 mol% catalyst in presence of 20 mol% of tBuOK. The reaction is facilitated by the presence of electron-withdrawing and the absence of coordinating atom in the substrate. Moreover, for aliphatic ketones, while acyclic derivatives and linear methylketones convert very efficiently, substrates with long linear alkyl chain did not react. Regarding the mechanism, some additional experiments allow to suggest, despite the paramagnetic nature of the precatalysts, the involvement of M-H species.

An original bis(iminophosphorane)phosphine NPN ligand was synthesised and coordinated to CoII. Both the ligand and the complex were characterised by multinuclear NMR spectroscopy and X-ray crystallography. The CoII complex (1.5 mol%) in the presence of NaOMe (3 mol%) catalyses the hydrosilylation of olefins within a few hours at 60 °C. Both 1-alkenes and less reactive internal ones built upon a norbornene skeleton were efficiently transformed.

Catalytic hydrosilylation of CC and CO bonds with an original iminophosphorane ONP ligand-supported Ni II complex.

The ability to predict the thermal properties of molecular compounds is essential for their successful integration into vapor-phase processes such as atomic layer deposition (ALD) and chemical vapor deposition (CVD), as well as in catalysis and materials synthesis. In this work, we present a systematic study of 24 gallium amidinate complexes, designed to explore the relationship between molecular structure and thermal behavior. The series encompasses a range of structural variations: different ligand substituents, molecular symmetry, and co-ligands. Structural characterization, including in some cases single-crystal X-ray diffraction, was combined with detailed thermal analysis using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) under both atmospheric and reduced pressure conditions. The results reveal clear correlations between thermal properties and ligand architecture, with features such as alkyl chain type, methyl group presence, and overall symmetry playing key roles in determining volatility and stability. Importantly, both symmetric and dissymmetric complexes were found to possess the desired thermal characteristics for vapor-phase deposition processes. Beyond offering valuable design principles for gallium precursors, the dataset generated herein provides a foundation for improving predictive models-empirical and AI-driven alike-towards the rational development of next-generation functional molecular compounds.

Vulcanodinium rugosum is a benthic dinoflagellate known for producing pinnatoxins, pteriatoxins, portimines and kabirimine. In this study, we aimed to identify unknown analogs of these emerging toxins in mussels collected in the Ingril lagoon, France. First, untargeted data acquisitions were conducted by means of liquid chromatography coupled to hybrid quadrupole-orbitrap mass spectrometry. Data processing involved a molecular networking approach, and a workflow dedicated to the identification of biotransformed metabolites. Additionally, targeted analyses by liquid chromatography coupled to triple quadrupole mass spectrometry were also implemented to further investigate and confirm the identification of new compounds. For the first time, a series of 13-O-acyl esters of portimine-A (n = 13) were identified, with fatty acid chains ranging between C12:0 and C22:6. The profile was dominated by the palmitic acid conjugation. This discovery was supported by fractionation experiments combined with the implementation of a hydrolysis reaction, providing further evidence of the metabolite identities. Furthermore, several analogs were semi-synthesized, definitively confirming the discovery of these metabolization products. A new analog of pinnatoxin, with a molecular formula of C42H65NO9, was also identified across the year 2018, with the highest concentration observed in August (4.5 μg/kg). The MS/MS data collected for this compound exhibited strong structural similarities with PnTX-A and PnTX-G, likely indicating a substituent C2H5O2 in the side chain at C33. The discovery of these new analogs will contribute to deeper knowledge of the chemodiversity of toxins produced by V. rugosum or resulting from shellfish metabolism, thereby improving our ability to characterize the risks associated with these emerging toxins.

The reduction of [CoLBr2], a Co-II complex supported by a diisopropylphosphinoquinoline (L) ligand, induced a ligand coupling giving access to a (PNNP) supported Co-II complex which was isolated in 70% yield. This complex was formed using a minimum of 2 equivalents of a reductant (either Mn or KC8). The fate of [CoLBr2] in the presence of 1 equivalent of a reductant was more difficult to study; nevertheless, a Co-I complex was characterised in the solid state. In order to determine whether this ligand coupling could occur with other 3d metals, L supported Fe-II and Ni-II complexes were synthesised. While no compound could be identified upon reduction of [FeLBr2], both [NiLBr2] and [NiL2Br](Br) led to the reduction at the metal center allowing the isolation of an original Ni-0 trimer in a satisfactory yield. This study shows the different behaviours of these 3d metal complexes in the presence of a reductant.

A series of quinoidal molecules were synthesized via a new variant of the indophenine reaction. The previously reported synthetic route of indophenine dyes involves a one pot procedure starting with isatin and an appropriate 5-membered aromatic heterocycle in the presence of catalytic amount of sulfuric acid. However, the reaction conditions lead to a low yield and a poor selectivity with the formation of several by-products. Herein, we propose a modification of the standard reaction to increase the yield, using tertiary alcohol as a starting material instead of isatin. This modified protocol is highly selective and allows for a very clean reaction, i.e. high yields, isomer-free synthesis and avoids any complex purification issues. Further, this protocol allows access to quinoidal compounds with variable termini and π-conjugated core. The influence of the conjugation length of the π-bridge on the quinoidal electronic structure is investigated by spectroscopic and electrochemical measurements. Meanwhile, the charge carrier mobilities of selected compounds were determined by the space-charge-limited-current method. Their utility as a hole transport material for the perovskite solar cells is demonstrated.

The Hock rearrangement is an acid catalyzed reaction involving organic hydroperoxides and resulting in an oxidative cleavage of adjacent C–C bonds. It has significant industrial applications, like the production of phenol (cumene process), but it remains scarcely used in organic synthesis. In addition, its detailed mechanism has never been studied. Thus, we re-port herein a theoretical study of the Hock rearrangement, using InCl3 as a Lewis acid catalyst. The aim of this work was to fully understand the mechanism of this fundamental reaction, and to rationalize the influence of the substrate electronic properties on the reaction outcome. Furthermore, the structure of the active indium(III) catalyst interacting with the per-oxide substrate was investigated, showing the superiority of a coordinated monomeric form of the Lewis acid as the active catalytic species, compared to dimeric species. However, we show that In2Cl6 species coordinated to the substrate are cen-tral in this catalytic cycle, serving as a reservoir of active monomeric species.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Theacid-catalyzed rearrangement of organic peroxides is generallyassociated with C-C-bond cleavages (Hock and Criegee rearrangements),with the concomitant formation of an oxocarbenium intermediate. Thisarticle describes the tandem process between a Hock or Criegee oxidativecleavage and a nucleophilic addition onto the oxocarbenium species(in particular a Hosomi-Sakurai-type allylation), under InCl3 catalysis. It was applied to the synthesis of 2-substitutedbenzoxacycles (chromanes and benzoxepanes), including a synthesisof the 2-(aminomethyl)chromane part of sarizotan, and a total synthesisof erythrococcamide B.

We report two ESIPT active novel fluorescent probes, 1 and 2, based on benzoxazole and benzimidazole units, respectively. Their sensing aptitude towards metal ions in aqueous media is reported. A specific response of 1 to Al3+ and, to a lesser extent, Zn2+, was found, while the emission of 2 is highly impacted by the Al3+, Cu2+, Fe2+ and Fe3+ metal ions by either a blue shift or a quenching of the emission. Emission of 2 also shows a relative sensitivity to the Ni2+ and Hg2+ cations. Anions sensing studies on 2 revealed a unique emission in presence of hypochlorite ions, while glyphosate and aminomethylphosphonic acid have the effect to decrease the emission intensity by 40% and 75%, respectively. Investigations on the recognition mechanism led to the conclusion that Al3+ was inhibiting the ESIPT process by deprotonation of the phenol group, and that a fast but weak interaction was taking place between the hypochlorite ion and 2.

Photolysis experiments of chlorphenesin, used as a preservative in cosmetic products, were performed in aqueous solution and on a cream used in cosmetics. Three by-products resulting from the direct UV-visible photodegradation of chlorphenesin were characterized by chromatography (gas and liquid) coupled with tandem mass spectrometry (GC-MS/MS and LC-HR MS/MS) and found in both solutions. In vitro tests on Vibrio fischeri bacteria showed that the overall ecotoxicity of chlorphenesin increased with increasing irradiation time in both samples. In silico QSAR (Quantitative Structure Activity Relationship) tests were performed using T.E.S.T. (Toxicity Estimation Software Tool). Among the degradation compounds identified, 4-chlorophenol must contribute to the increased ecotoxicity of the photolyzed solution since the in silico LC50 estimated for all tests performed are always lower than those obtained for chlorphenesin.

Cross-contamination of animal feed with antibiotics may occur during manufacturing in feed mills, because shared production lines can be used for medicated and non-medicated feed, but may also occur during transport, storage and at the farm level. This is a major issue in the current context where antimicrobial usage must be controlled in order to maintain their effectiveness. A LC-MS/MS method was developed for the determination of colistin, bacitracin A and virginiamycin M1 in feed for pigs, poultry and rabbits at concentrations similar to those encountered in cross-contamination. After investigating various issues related to colistin behaviour and matrix effects, we successfully validated this method according to the requirements of European regulations in terms of linearity, trueness, precision, limit of quantification and limit of decision. Trueness ranged 88.6-107.8% and precision ranged 12.6-21.2%. We then applied this method to the analysis of medicated pig feed to check the performance of the method on "real" samples of medicated feed. We subsequently analysed non-medicated pig, and rabbit feed samples, collected directly on farms, to check the rate of cross-contamination. No samples were contaminated by colistin, bacitracin, or virginiamycin.

The reaction between a 1-azido-(2-halogenomethyl)benzene and a phosphine gives different products depending on the nature of the halogen, the phosphine itself, and the solvent employed. While PPh3 (2 equiv) reacts with the chloro reagent in toluene to give the expected iminophosphorane-phosphonium adduct, trialkylphosphines (PCy3 and PEt3) surprisingly furnish an aminophosphonium substituted by a zwitterionic indazole. The bicyclic product can also form from PPh3 using the bromo reagent in acetonitrile. A mechanism is proposed for this cyclization based on DFT calculations.

Archaeal translation initiation occurs within a macromolecular complex containing the small ribosomal subunit (30S) bound to mRNA, initiation factors aIF1, aIF1A and the ternary complex aIF2:GDPNP:Met-tRNA i Met . Here, we determine the cryo-EM structure of a 30S:mRNA:aIF1A:aIF2:GTP:Met-tRNA i Met complex from Pyrococcus abyssi at 3.2 Å resolution. It highlights archaeal features in ribosomal proteins and rRNA modifications. We find an aS21 protein, at the location of eS21 in eukaryotic ribosomes. Moreover, we identify an N-terminal extension of archaeal eL41 contacting the P site. We characterize 34 N 4 -acetylcytidines distributed throughout 16S rRNA, likely contributing to hyperthermostability. Without aIF1, the 30S head is stabilized and initiator tRNA is tightly bound to the P site. A network of interactions involving tRNA, mRNA, rRNA modified nucleotides and C-terminal tails of uS9, uS13 and uS19 is observed. Universal features and domain-specific idiosyncrasies of translation initiation are discussed in light of ribosomal structures from representatives of each domain of life.

We report on the synthesis and characterization of three iron(III) phosphasalen complexes, [FeIII (Psalen)(X)] differing in the nature of the counter-anion/exogenous ligand (X- =Cl- , NO3 - , OTf- ), as well as the neutral iron(II) analogue, [FeII (Psalen)]. Phosphasalen (Psalen) differs from salen by the presence of iminophosphorane (P=N) functions in place of the imines. All the complexes were characterized by single-crystal X-ray diffraction, UV/Vis, EPR, and cyclic voltammetry. The [FeII (Psalen)] complex was shown to remain tetracoordinated even in coordinating solvent but surprisingly exhibits a magnetic moment in line with a FeII high-spin ground state. For the FeIII complexes, the higher lability of triflate anion compared to nitrate was demonstrated. As they exhibit lower reduction potentials compared to their salen analogues, these complexes were tested for the coupling of 2-naphthol using O2 from air as oxidant. In order to shed light on this reaction, the interaction between 2-naphthol and the FeIII (Psalen) complexes was studied by cyclic voltammetry as well as UV/Vis spectroscopy.