Efficient recycling of a chiral palladium catalytic system for asymmetric allylic substitutions in ionic liquid

Chiral carbohydrate-based diphosphites were used for Pd-catalysed asymmetric allylic substitution (alkylation, amination, phosphination) in neat ionic liquids (ILs). Pyrrolidinium-based IL led to the best activities, allowing an efficient catalyst immobilization. In the allylic amination (TOF > 3100 h(-1)), the catalyst could be recycled nine times preserving both activity and enantioselectivity.     

Fast screening for presence of muddy/earthy odorants in wine and in wine must using a hyphenated gas chromatography-differential ion mobility spectrometry (GC/DMS)

Rapid, hyphenated detection techniques involving a gas chromatograph (GC) coupled to a classical time-of-flight ion mobility (IMS) spectrometer, or more recently, to a micro-machined, miniature differential ion mobility spectrometer (DMS) are quite attractive for in-situ detection of many kinds of volatile organic compounds (VOCs) of concern and notably of natural contaminants appearing in the headspaces of selected foodstuff. This work aims at a rapid detection, identification and quantification of geosmin in the headspace of grape must and of wine. Samples of white and red wines have both been analyzed with a hyphenated GC/DMS and by Solid Phase Micro-Extraction (SPME) coupled to GC/MS taken as a reference. The detection of geosmin at concentrations below the human olfactory threshold of 50 ng/L has been demonstrated.     

Superparamagnetic iron oxide particles and positive enhancement for myocardial perfusion studies assessed by subsecond T1-weighted MRI

Superparamagnetic iron oxide particles (SPIOs) are usually referred to as T₂ MR contrast agents, reducing signal intensity (SI) on T₂-weighted MR images (negative enhancement). This study reports the original use of SPIOs as T₁-enhancing contrast agents, primarily assessed in vitro, and then applied to an in vivo investigation of a myocardial perfusion defect. Using a strongly T₁-weighted subsecond MR sequence with SPIOs intravenous (IV) bolus injection, MR imaging of myocardial vascularization after reperfusion was performed, on a dog model of coronary occlusion followed by reperfusion. Immediately after the intravenous bolus injection of 20 μmol/kg of SPIOs, a positive signal intensity enhancement was observed respectively, in the right and left ventricular cavity and in the nonischemic left myocardium. Moreover, compared to normal myocardium, the remaining ischemic myocardial region (anterior wall of the left ventricle) appeared as a lower and delayed SI enhancing area (cold spot). Mean peak SIE in the nonischemic myocardium (posterior wall) was significantly higher than in the ischemic myocardium (anterior wall) (110 ± 23% vs. 74 ± 22%, Mann-Whitney test < 1%, n₁ = 6, n₂ − n₁ = 0, U > 2). In conclusion, the T₁ effect of SPIOs at low dose, during their first intravascular distribution, suggests their potential use as positive markers to investigate the regional myocardial blood flow and some perfusion defects such as the “no-reflow phenomenon”.     

Detection of 20‐hydroxyecdysone in calf urine by comparative liquid chromatography/high‐resolution mass spectrometry and liquid chromatography/tandem mass spectrometry measurements: application to the control of the potential misuse of ecdysteroids in cattle

Ecdysteroids, which are steroid hormones in invertebrates, but which are also present in plants, could potentially be used as anabolic agents in food‐producing animals. The control of ecdysteroid misuse in cattle relies on the development of an efficient method for their detection in biological matrices at trace levels (µg L⁻¹). In order to propose an analytical procedure dedicated to the identification of excreted 20‐hydroxyecdysone (20E) in urine and faecal samples of breeding animals, a comparative study of the spectrometric behaviour of these compounds was carried out both by LC/(ESI‐)/HRMSⁿ (hybrid linear ion trap – orbital trap) and by LC/(ESI+)/MS/MS (triple quadrupole). This study revealed the formation of a large number of product ions both in positive and negative ion mode, corresponding to losses of water molecules and specific cleavages on the side chain. The sample preparation consisted of sequential purification on two solid‐phase extraction cartridges (SPE octadecylsilyl and SPE silica). The detection limits were around 0.5 µg L⁻¹ in the selected reaction monitoring (SRM) mode and recoveries above 60% were obtained. The method was successfully applied to the analysis of real samples collected from calves treated with 60 mg 20E over 4 days. Analysis of the samples allowed the investigation of the kinetics of elimination of 20E in calf urine and determination of the time‐frame for the control of potential abuse. Copyright © 2008 John Wiley & Sons, Ltd.     

Latex bead immobilisation in PDMS matrix for the detection of p53 gene point mutation and anti-HIV-1 capsid protein antibodies

Two diagnostic chemiluminescent biochips were developed for either the detection of p53 gene point mutation or the serological detection of anti-HIV-1 p24 capsid protein. Both biochips were composed of 24 microarrays of latex beads spots (4×4) (150 m in diameter, 800 m spacing) entrapped in a poly(dimethylsiloxane) elastomer (PDMS). The latex beads, bearing oligonucleotide sequences or capsid protein, were spotted with a conventional piezoelectric spotter and subsequently transferred at the PDMS interface. The electron microscopy observation of the biochips showed how homogeneous and well distributed the spots could be. Point mutation detection on the codon 273 of the p53 gene was performed on the basis of the melting temperature difference between the perfect match sequence and the one base pair mismatch sequence. The hybridisation of a 20-mer oligonucleotide form the codon 273 including a one base pair mutation in its sequence on a biochip arrayed with non-muted and the muted complementary sequences, enabled a clear discrimination at 56°C between muted and wild sequences. Moreover, the quantitative measurement of the amount of muted sequence in a sample was possible in the range 0.4–4 pmol. Serological measurement of anti-HIV-1 p24 capsid protein on the biochip, prepared with 1-m-diameter latex beads, enabled the detection of monoclonal antibodies in the range 1.55–775 ng mL^–1. Such a range could be lowered to 0.775 ng mL^–1 when using 50-nm-diameter beads, which generated a higher specific surface. The validation of the biochip for the detection of anti-HIV-1 capsid protein antibodies was performed in human sera from seropositive and seronegative patients. The positivity of the sera was easily discriminated at serum dilutions below 1:1,000.     

Growth of tertiary dendritic arms during the transient directional solidification of hypoeutectic Pb–Sb alloys

Despite the importance of a complete characterization of dendritic patterns in castings, the availability of studies on the development of tertiary dendrite arms is scarce in the literature. In the present study, the tip cooling rate, local solidification time, primary and tertiary dendrite arm spacings have been determined in Pb–Sb alloys castings directionally solidified under unsteady-state heat flow conditions. The alloys compositions experimentally examined are widely used in the as-cast condition for the manufacture of positive and negative grids of lead-acid batteries. The initial growth of tertiary dendritic arms from the secondary branches was found to occur only for a Pb–3.5 wt% Sb alloy at cooling rates in the range 0.4–0.2?K/s, with no evidence of this spacing pattern for Pb–Sb alloys having lower solute content. Tertiary dendritic branches have been observed along the entire casting lengths for alloys of the Pb–Sb hypoeutectic range having compositions higher than 4.0 wt% Sb. It is shown that a power function experimental law with a characteristic ?0.55 exponent is able to characterize the tertiary spacing evolution with the solidification cooling rate for alloys compositions ≥4.0 wt% Sb. The only exception was the Pb–3.5 wt% Sb alloy for which λ ₃ exhibited significant lower values when compared with the experimental values obtained for the other Pb–Sb alloys for a same solidification cooling rate.     

Separations of antifungal compounds in capillary electrophoresis with two anionic cyclodextrins

CD‐CZE methods were developed for complete stereoisomeric separations of a series of six γ‐lactam analogues, of which some were neutral, or cationic depending on the background electrolyte nature. The tested cyclodextrin was the versatile sulfobutylether‐ β‐CD, used either in a phosphate buffer using capillaries dynamically coated with polyethylene oxide or in a borate buffer using uncoated capillaries. Long‐end and short‐end modes and concentration variations of chiral selectors allowed finding conditions of complete separation of four out of the six derivatives (i.e., 1 , 2 , 3, and 4 ) in short run times, confirming their broad range of applications. To separate the two last compounds, the highly sulfated‐ γ‐CD was examined as chiral selector in acidic phosphate conditions. The enantiomers of the γ‐lactam analogues 5 and 6 were baseline resolved with 5.5 and 4%, respectively as concentration in the buffer.     

Fluorescent P-Hydroxyphosphole for Peptide Labeling through P-N Bond Formation

Synthesis of fluorescent P-hydroxybinaphtylphosphole-oxide or -sulfide was achieved by trapping a binaphtyl dianion with methyl dichlorophosphite or P-(N,N-diethylamino)dichlorophosphine, followed by oxidation or sulfuration of the P-center. After saponification or acid hydrolysis, the P-hydroxyphospholes were coupled to peptides using the coupling agent BOP, under the conditions required for the synthesis in solution or on a solid support. This new method was illustrated by the labeling of the JMV2959, a potent antagonist of the Growth Hormone Secretagogue Receptor type 1a (GHS−R1a). The labeled conjugates were used to characterize GHSR ligands by competition assays, based on Fluorescence Resonance Energy Transfer (FRET). Such P-hydroxyphosphole-oxide or -sulfide constitute a promising new class of compact fluorophores with large Stokes shift, for labeling biomolecules by grafting through the phosphorus atom.     

Optimised Desorption Electrospray Ionisation Mass Spectrometry Imaging (DESI-MSI) for the Analysis of Proteins/Peptides Directly from Tissue Sections on a Travelling Wave Ion Mobility Q-ToF

Desorption electrospray ionisation mass spectrometry imaging (DESI-MSI) is typically known for the ionisation of small molecules such as lipids and metabolites, in singly charged form. Here we present a method that allows the direct detection of proteins and peptides in multiply charged forms directly from tissue sections by DESI. Utilising a heated mass spectrometer inlet capillary, combined with ion mobility separation (IMS), the conditions with regard to solvent composition, nebulising gas flow, and solvent flow rate have been explored and optimised. Without the use of ion mobility separation prior to mass spectrometry analysis, only the most abundant charge series were observed. In addition to the dominant haemoglobin subunit(s) related trend line in the m/z vs drift time (DT) 2D plot, trend lines were found relating to background solvent peaks, residual lipids and, more importantly, small proteins/large peptides of lower abundance. These small proteins/peptides were observed with charge states from 1+ to 12+, the majority of which could only be resolved from the background when using IMS. By extracting charge series from the 2D m/z vs DT plot, a number of proteins could be tentatively assigned by accurate mass. Tissue images were acquired with a pixel size of 150 μm showing a marked improvement in protein image resolution compared to other liquid-based ambient imaging techniques such as liquid extraction surface analysis (LESA) and continuous-flow liquid microjunction surface sampling probe (LMJ-SSP) imaging.

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