Solvent-Free NaHSO4-SiO2-Catalyzed Efficient Tetrahydropyranylation of Alcohols and Phenols

A simple and efficient tetrahydropyranylation of alcohols and phenols has been developed using NaHSO₄-SiO₂ (0.5 mol%) as a catalyst under solvent-free conditions to yield corresponding tetrahydropyranyl ethers in excellent yields.     

Online coupling of high-resolution chromatography with extreme UV photon activation tandem mass spectrometry: Application to the structural investigation of complex glycans by dissociative photoionization

The activation of ions by extreme-energy photons (XUV) produced by a synchrotron radiation beamline is a powerful method for characterizing complex glycans using tandem mass spectrometry (MS). As previously described, this activation method leads to rich fragmentation spectra with many structurally valuable cross-ring cleavages while maintaining labile modifications on the glycan structures. However, until now, the tandem MS event was too long to be compatible with liquid chromatography elution times. In this work, the duty cycle of the activation and detection of fragments was shortened, and the background signal on the spectra was drastically reduced. Both improvements allowed, for the first time, the successful coupling of a UHPLC system to XUV-activated tandem MS. The approach was used to characterize a complex mixture of oligo-porphyrans, which are a class of highly sulfated oligosaccharides, in a fully automated way. Due to an enhanced dynamic range and an increased sensitivity, some hypothetical structures of low abundance have been unequivocally confirmed in this study and others have been revised. Some previously undescribed species of oligo-porphyrans that exhibit lateral branching have been fully resolved. This work contributes to the scarce knowledge of the structure of porphyrans in red algae and pushes the current capacities of XUV-activation tandem MS by demonstrating the possibility of a direct coupling with UHPLC. This study will considerably broaden the applicability and practicality of this method in many fields of analytical biology.     

Magnetic Eigenmaps for the visualization of directed networks

We propose a framework for the visualization of directed networks relying on the eigenfunctions of the magnetic Laplacian, called here Magnetic Eigenmaps. The magnetic Laplacian is a complex deformation of the well-known combinatorial Laplacian. Features such as density of links and directionality patterns are revealed by plotting the phases of the first magnetic eigenvectors. An interpretation of the magnetic eigenvectors is given in connection with the angular synchronization problem. Illustrations of our method are given for both artificial and real networks.     

Albumin-mediated alteration of plasma zinc speciation by fatty acids modulates blood clotting in type-2 diabetes

Zn²⁺ is an essential regulator of coagulation and is released from activated platelets. In plasma, the free Zn²⁺ concentration is fine-tuned through buffering by human serum albumin (HSA). Importantly, the ability of HSA to bind/buffer Zn²⁺ is compromised by co-transported non-esterified fatty acids (NEFAs). Given the role of Zn²⁺ in blood clot formation, we hypothesise that Zn²⁺ displacement from HSA by NEFAs in certain conditions (such as type 2 diabetes mellitus, T2DM) impacts on the cellular and protein arms of coagulation. To test this hypothesis, we assessed the extent to which increasing concentrations of a range of medium- and long-chain NEFAs reduced Zn²⁺-binding ability of HSA. Amongst the NEFAs tested, palmitate (16 : 0) and stearate (18 : 0) were the most effective at suppressing zinc-binding, whilst the mono-unsaturated palmitoleate (16 : 1c9) was markedly less effective. Assessment of platelet aggregation and fibrin clotting parameters in purified systems and in pooled plasma suggested that the HSA-mediated impact of the model NEFA myristate on zinc speciation intensified the effects of Zn²⁺ alone. The effects of elevated Zn²⁺ alone on fibrin clot density and fibre thickness in a purified protein system were mirrored in samples from T2DM patients, who have derranged NEFA metabolism. Crucially, T2DM individuals had increased total plasma NEFAs compared to controls, with the concentrations of key saturated (myristate, palmitate, stearate) and mono-unsaturated (oleate, cis-vaccenate) NEFAs positively correlating with clot density. Collectively, these data strongly support the concept that elevated NEFA levels contribute to altered coagulation in T2DM through dysregulation of plasma zinc speciation.

Zn²⁺ is an essential regulator of coagulation. In plasma, Zn²⁺ availability is fine-tuned by human serum albumin (HSA). Here we show that elevated fatty acid levels contribute to altered coagulation in type-2 diabetes through Zn²⁺ mishandling by HSA.