Efficient method for in situ agitation of liquids directly inside NMR spectrometer.

The objective of the method is to allow agitation and fast homogenization of liquid systems in NMR tubes, directly inside the NMR spectrometer. The setup makes it possible to record spectra of samples that are macroscopically not stable, as dispersions of large particles. It makes also possible to fasten the homogeneization of liquid during a reaction or a phase transition. In the present paper, the method has been evaluated using homogeneous liquid extraction (HLLE). This configuration can also be used to introduce gases in different systems to perform various types of experiments. The set up consists in a Teflon tube inserted in the NMR tube bringing gas that yields agitation by bubbling. The gas flow is tuned using an electronically operated valve connected to gas line and to the NMR console. The method details how to reach proper homogenization without any perturbation, as liquid leaks.•An easy method for agitation of liquids inside NMR spectrometers.•The set up can be used for the insertion of gases in the NMR tube inside the spectrometer.•The method allows the study of the mixing of biphasic systems by NMR techniques.

Solid-state NMR study of structural heterogeneity of the apo WT mouse TSPO reconstituted in liposomes.

In the last decades, ligand binding to human TSPO has been largely used in clinical neuroimaging, but little is known about the interaction mechanism. Protein conformational mobility plays a key role in the ligand recognition and both, ligand-free and ligand-bound structures, are mandatory for characterizing the molecular binding mechanism. In the absence of crystals for mammalian TSPO, we have exploited solid-state nuclear magnetic resonance (ssNMR) spectroscopy under magic-angle spinning (MAS) to study the apo form of recombinant mouse TSPO (mTSPO) reconstituted in lipids. This environment has been previously described to permit binding of its high-affinity drug ligand PK11195 and appears therefore favourable for the study of molecular dynamics. We have optimized the physical conditions to get the best resolution for MAS ssNMR spectra of the ligand-free mTSPO. We have compared and combined various ssNMR spectra to get dynamical information either for the lipids or for the mTSPO. Partial assignment of residue types suggests few agreements with the published solution NMR assignment of the PK11195-bound mTSPO in DPC detergent. Moreover, we were able to observe some lateral chains of aromatic residues that were not assigned in solution. 13C double-quantum NMR spectroscopy shows remarkable dynamics for ligand-free mTSPO in lipids which may have significant implications on the recognition of the ligand and/or other protein partners.

Stressing the differences in alizarin and purpurin dyes through UV-visible light absorption and 1H-NMR spectroscopies.

Three anthraquinone-based chromophores (9,10-anthraquinone, alizarin, purpurin) are compared from the point of view of their experimental and computed NMR and UV-visible light absorption spectra. Using a hybrid (explicit/implicit) solvent model, each proton chemical shift can be reproduced with an error of less than 7%, even when such protons are engaged in inter-molecular hydrogen bonds with the solvent or when the analyzed sample contains a significant amount of impurities, for instance, 9,10-anthraquinone in purpurin. All the steady-state UV-visible absorption spectra feature a significant vibrational progression in the first absorption band. The shape of the corresponding computed spectra, including vibronic couplings obtained with the adiabatic Hessian approach and the Franck-Condon and Herzberg-Teller approximation of the transition dipole, are in excellent agreement with the experimental ones. The importance and the nature of the vibronic couplings are different for the three molecules, even if they only differ by the number of hydroxyl groups.

Carbamoyl phosphate and its substitutes for the uracil synthesis in origins of life scenarios.

The first step of pyrimidine synthesis along the orotate pathway is studied to test the hypothesis of geochemical continuity of protometabolic pathways at the origins of life. Carbamoyl phosphate (CP) is the first high-energy building block that intervenes in the in vivo synthesis of the uracil ring of UMP. Thus, the likelihood of its occurrence in prebiotic conditions is investigated herein. The evolution of carbamoyl phosphate in water and in ammonia aqueous solutions without enzymes was characterised using ATR-IR, 31P and 13C spectroscopies. Carbamoyl phosphate initially appears stable in water at ambient conditions before transforming to cyanate and carbamate/hydrogenocarbonate species within a matter of hours. Cyanate, less labile than CP, remains a potential carbamoylating agent. In the presence of ammonia, CP decomposition occurs more rapidly and generates urea. We conclude that CP is not a likely prebiotic reagent by itself. Alternatively, cyanate and urea may be more promising substitutes for CP, because they are both "energy-rich" (high free enthalpy molecules in aqueous solutions) and kinetically inert regarding hydrolysis. Energy-rich inorganic molecules such as trimetaphosphate or phosphoramidates were also explored for their suitability as sources of carbamoyl phosphate. Although these species did not generate CP or other carbamoylating agents, they exhibited energy transduction, specifically the formation of high-energy P-N bonds. Future efforts should aim to evaluate the role of carbamoylating agents in aspartate carbamoylation, which is the following reaction in the orotate pathway.

Surface-Dependent Activation of Model α-Al2 O3 -Supported P-Doped Hydrotreating Catalysts Prepared by Spin Coating.

Requirements for improved catalytic formulations is continuously driving research in hydrotreating (HDT) catalysis for biomass upgrading and heteroatom removal for cleaner fuels. The present work proposes a surface-science approach for the understanding of the genesis of the active (sulfide) phase in model P-doped MoS2 hydrotreating catalysts supported on α-Al2 O3 single crystals. This approach allows one to obtain a surface-dependent insight by varying the crystal orientations of the support. Model phosphorus-doped catalysts are prepared via spin-coating of Mo-P precursor solutions onto four α-Al2 O3 crystal orientations, C(0001), A(11 2 ‾ 0), M(10 1 ‾ 0) and R(1 1 ‾ 02) that exhibit different speciations of surface -OH. 31 P and 95 Mo liquid-state NMR are used to give a comprehensive description of the Mo and P speciation of the phospho-molybdic precursor solution. The speciation of the deposition solution is then correlated with the genesis of the active MoS2 phase. XPS quantification of the surface P/Mo ratio reveal a surface-dependent phosphate aggregation driven by the amount of free phosphates in solution. Phosphates aggregation decreases in the following order C(0001)≫M(10 1 ‾ 0)>A(11 2 ‾ 0), R(1 1 ‾ 02). This evolution can be rationalized by an increasing strength of phosphate/surface interactions on the different α-Al2 O3 surface orientations from the C(0001) to the R(1 1 ‾ 02) plane. Retardation of the sulfidation with temperature is observed for model catalysts with the highest phosphate dispersion on the surface (A(11 2 ‾ 0), R(1 1 ‾ 02)), suggesting that phosphorus strongly intervene in the genesis of the active phase through a close intimacy between phosphates and molybdates. The surface P/Mo ratio appears as a key descriptor to quantify this retarding effect. It is proposed that retardation of sulfidation is driven by two effects: i) a chemical inhibition through formation of hardly reducible mixed molybdo-phosphate structures and ii) a physical inhibition with phosphate clusters inhibiting the growth of MoS2 . The surface-dependent phosphorus doping on model α-Al2 O3 supports can be used as a guide for the rational design of more efficient HDT catalysts on industrial γ-Al2 O3 carrier.

Amino hydroxyapatite/chitosan hybrids reticulated with glutaraldehyde at different pH values and their use for diclofenac removal.

Diclofenac sodium (DS) is an emergent pollutant, and among the methods investigated for its removal, adsorption is the most widely utilized technique. Hydroxyapatite and chitosan are biomaterials often used for adsorption. However, both biomaterials are limited due to their low chemical stability in an acidic medium; furthermore, pure hydroxyapatite interacts poorly with diclofenac. In this work, hydroxyapatite was organofunctionalized with 3-aminopropyltrimethoxysilane and further used to obtain amino hydroxyapatite /chitosan hybrids by crosslinking with glutaraldehyde at pH 3, 4, 5, and 6. X-ray diffraction patterns indicated the preservation of the hydroxyapatite phase under all pH conditions. Based on the control reaction of the amino hydroxyapatite with glutaraldehyde and its further reduction in sodium borohydride, the formation of CN moieties was highlighted as the main interaction mechanism between the aldehyde and amino groups. Therefore, crosslinking with glutaraldehyde was evaluated by infrared, Raman spectroscopy, and 13C NMR techniques; the results suggested contributions of imine formation and hydrogen bonding. The hybrid obtained at pH 3 exhibited an enhanced adsorption capacity of 125 mg g-1 at 15 min. The synergy between amino hydroxyapatite and chitosan crosslinked by glutaraldehyde was demonstrated.

The degradation of organic compounds impacts the crystallization of clay minerals and vice versa.

Expanding our capabilities to unambiguously identify ancient traces of life in ancient rocks requires laboratory experiments to better constrain the evolution of biomolecules during advanced fossilization processes. Here, we submitted RNA to hydrothermal conditions in the presence of a gel of Al-smectite stoichiometry at 200 °C for 20 days. NMR and STXM-XANES investigations revealed that the organic fraction of the residues is no longer RNA, nor the quite homogeneous aromatic-rich residue obtained in the absence of clays, but rather consists of particles of various chemical composition including amide-rich compounds. Rather than the pure clays obtained in the absence of RNA, electron microscopy (SEM and TEM) and diffraction (XRD) data showed that the mineralogy of the experimental residues includes amorphous silica and aluminosilicates mixed together with nanoscales phosphates and clay minerals. In addition to the influence of clay minerals on the degradation of organic compounds, these results evidence the influence of the presence of organic compounds on the nature of the mineral assemblage, highlighting the importance of fine-scale mineralogical investigations when discussing the nature/origin of organo-mineral microstructures found in ancient rocks.

Confinement and Time Immemorial: Prebiotic Synthesis of Nucleotides on a Porous Mineral Nanoreactor.

We report the successful one-pot synthesis of adenosine mono-, di-, and triphosphate in the confined space of a mordenite zeolite. This is also the first report of ATP synthesized onto a porous mineral surface. The results revealed a plausible prebiotic route to ribonucleotides and highlighted the contribution of microporous minerals in the origins of life.

A new durable pigment with hydrophobic surface based on natural nanotubes and indigo: Interactions and stability.

Covering with polyorganosilane (POS) was proved as an effective way to enhance the chemical and thermal stability of clay/dye hybrid pigments. But the photostability and interactions with clay minerals, dyes and POS layer has never been reported. In order to investigate above issues, new organic-inorganic hybrid pigments based on halloysite (Hal) and indigo (In) were prepared by grinding method. X-ray diffraction, transmission electron microscopy, thermogravimetry, Fourier transform infrared spectroscopy were applied to characterize the structure of In-Hal (without POS layer) and In-Hal-POS (with POS layer) pigments. Solid state nuclear magnetic resonance (NMR) was employed to reveal the interactions between Hal, In and POS. Reflection spectra and CIE 1976 color space system were used to evaluate the color parameters and color changes of pigments. Thermal stability, chemical resistance to ethanol, 1 mol·L-1 HCl and 1 mol⋅L-1 NaOH, and light fastness to visible light were tested. Indigo molecules dispersed on the surface of Hal nanotubes. POS layer homogeneously covered on the surface of hybrid pigments, without changing the crystal structure and morphology of Hal. Covering with POS layer seldomly affect the color of hybrid pigments. However, In-Hal-POS exhibited better stability than In-Hal, due to hydrophobic surface which can prevent indigo molecules from chemical reactions and degradation. A new route was proposed to prepare organic-inorganic hybrid pigments, ignoring the interaction between dye molecules and substrates.

Author Correction: Proton irradiation: a key to the challenge of N-glycosidic bond formation in a prebiotic context.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has been fixed in the paper.

Ion-specificity and surface water dynamics in protein solutions.

Ion-specific effects at the protein surface are investigated here in light of the changes they infer to surface water dynamics, as observed by 1H NMR relaxation (at 20 MHz). Two well-known proteins, hen egg-white lysozyme (LZM) and bovine serum albumin (BSA), show qualitatively opposite trends in the transverse relaxation rate, R2(1H), along a series of different monovalent salt anions in the solution. Presence of salt ions increases R2(1H) in the case of lysozyme and diminishes it in the case of BSA. The effect magnifies for larger and more polarizable ions. The same contrasting effect between the two proteins is observed for protein-solvent proton exchange. This hints at subtle effects ion-binding might have on the accessibility of water surface sites on the protein. We suggest that the combination of the density of surface charge residues and surface roughness, at the atomic scale, dictates the response to the presence of salt ions and is proper to each protein. Further, a dramatic increase in R2(1H) is found to correlate closely with the formation of protein aggregates. The same ordering of salts in their ability to aggregate lysozyme, as seen previously by cloud point measurements, is reproduced here by R2(1H). 1H NMR relaxation data is supplemented by 35Cl and 14N NMR relaxation for selected salt ions to probe the ion-binding itself.

Going through the wine fining: Intimate dialogue between organics and clays.

Wine chemistry inspires and challenges with its complexity and intriguing composition. In this context, the composites based on the use of a model protein, a polyphenol of interest and montmorillonite in a model hydroalcoholic solution have been studied. A set of experimental characterization techniques highlighted the interactions between the organic and the inorganic parts in the composite. The amount of the organic part was determined by ultraviolet-visible (UV-VIS) and thermal analysis. X-ray diffraction (XRD) and transmission electronic microscopy (TEM) informed about the stacking/exfoliation of the layers in the composites. Vibrational and nuclear magnetic resonance spectroscopies methods stressed on the formation of a complex between the protein and the polyphenol before adsorption on the clay mineral. The mobility/rigidity of the organic parts were determined by fluorescence time resolved spectroscopy. Changes in the secondary structure of the protein occured upon complexation with polyphenol on clay mineral due to strong interactions. Although not representating faithfully enological conditions, these results highlight the range and nature of mechanisms possibly involved in wine fining.

Proton irradiation: a key to the challenge of N-glycosidic bond formation in a prebiotic context.

The formation of nucleosides in abiotic conditions is a major hurdle in origin-of-life studies. We have determined the pathway of a general reaction leading to the one-pot synthesis of ribo- and 2'-deoxy-ribonucleosides from sugars and purine nucleobases under proton irradiation in the presence of a chondrite meteorite. These conditions simulate the presumptive conditions in space or on an early Earth fluxed by slow protons from the solar wind, potentially mimicking a plausible prebiotic scenario. The reaction (i) requires neither pre-activated precursors nor intermediate purification/concentration steps, (ii) is based on a defined radical mechanism, and (iii) is characterized by stereoselectivity, regioselectivity and (poly)glycosylation. The yield is enhanced by formamide and meteorite relative to the control reaction.

A 19th Century "Ideal" Oil Paint Medium: A Complex Hybrid Organic-Inorganic Gel.

British 19th century painters such as J. M. W. Turner, commonly modified the properties of their paint by using gels called "gumtions". These gels allowed them to easily tune the paint handling and drying properties. The fascinating properties of these "gumtions" were obtained by adding lead acetate to a ternary system based on mastic resin, linseed oil and turpentine. Herein, we report and investigate in depth the rheological properties of these gels as well as their structure at a molecular and supra-molecular scale.

Inhibition of palm oil oxidation by zeolite nanocrystals.

The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species.

Zinc and cobalt complexes based on tripodal ligands: synthesis, structure and reactivity toward lactide.

The coordination chemistry of a series of pro-ligands ([L¹]-[L6]) with cobalt and zinc derivatives has been studied. All complexes have been characterized by multinuclear NMR, elemental analysis, and by single-crystal X-ray diffraction studies. Polymerization of rac-lactide takes place at 130 °C in the presence of cobalt and zinc complexes to yield polymers under solvent free conditions with controlled molecular masses and narrow polydispersities.

[Good clinical practices and inpatient antibiotics: optimization of fluoroquinolone switch therapy]. / Bon usage des antibiotiques: optimisation du relais per os des fluoroquinolones.

OBJECTIVE: Intravenous-to-oral switch therapy is strongly recommended in the medical literature. The aim of this study was to assess how we can improve fluoroquinolone switch therapy. METHODS: In this comparative prospective study, we analyzed 243 intravenous ciprofloxacin treatments and assessed the impact of promoting a switch to oral step-down therapy. RESULTS: This study found that switches from intravenous to oral therapy increased, mainly in medical wards, and led to significant savings in direct costs. DISCUSSION: Promoting switch therapy has improved clinical practices in antibiotic use and led to lower direct and probably indirect drug-related costs. CONCLUSION: Our findings will help define the role of switch therapy in improving clinical practices in inpatient antibiotic use.