The carbon isotope composition of CO2 respired by trunks: comparison of four sampling methods

The (13)C natural abundance of CO(2) respired by plants has been used in the laboratory to examine the discrimination processes that occur during respiration. Currently, field measurements are being expanded to interpret the respiration delta(13)C signature measured at ecosystem and global levels. In this context, forests are particularly important to consider as they represent 80% of the continental biomass. The objective of this investigation was to compare four methods of sampling the CO(2) respired by trunks for the determination of its carbon isotope composition: three in situ methods using chambers placed on the trunk, and one destructive method using cores of woody tissues. The in situ methods were based either on a Keeling plot approach applied at the tissue level or on an initial flush of the chamber with nitrogen or with CO(2)-free air. In parallel, we investigated the possibility of an apparent discrimination during tissue respiration by comparing the delta(13)C signature of the respired CO(2) and that of the organic matter. The study was performed on six tree species widely distributed in temperate and mediterranean areas. The four methods were not significantly different when overall means were considered. However, considering the individual data, the Keeling plot approach and the nitrogen flush methods gave fairly homogeneous results, whereas the CO(2)-free air method produced more variable results. The core method was not correlated with any of the chamber methods. Regardless of the methodology, the respired CO(2) generally was enriched in (13)C relative to the total organic matter. This apparent enrichment during respiration was variable, reaching as much as 3-5 per thousand. This study showed that, on the whole, the different sampling techniques gave similar results, but one should be aware of the variability associated with each method.     

Analyse par activation neutronique des lanthanides dans les eaux naturelles

A new method of neutron activation analysis of rare earths in natural waters is proposed and applied to thermal and superficial waters. Natural waters samples are irradiated in a liquid state, without preconcentration. The rare earths are separated, after irradiation, from interfering elements by stationary phase chromatography and precipitation. Determination are carried out by gamma spectrometry with a germanium (lithium) detector. The method is applied to quantitative analysis of Dy, Eu, Sm, La, in natural waters, thermal or superficial, coming from Massif Central and Pyrénées (France).      

Column selection and method development for the separation of nucleoside phosphotriester diastereoisomers, new potential anti-viral drugs. Application to cellular extract analysis

Analytical HPLC methods using derivatized cellulose and amylose chiral stationary phases used in normal and reversed-phase modes were developed for the diastereoisomeric separation of mononucleotide prodrugs (pronucleotides) of 3'-azido-2',3'-dideoxythymidine (AZT). The resolutions were performed with two silica-based celluloses using normal and reversed-phase methodologies: Tris-3,5-dimethylphenylcarbamate (Chiralcel OD-H and Chiracel OD-RH) and Tris-methylbenzoate (Chiralcel OJ and OJ-R). Two amyloses phases, Tris-3,5-dimethylphenylcarbamate (Chiralpak AD) and Tris-(S)-1-phenylethylcarbamate (Chiralpak AS), were used in normal-phase mode. Additionally, we developed separation using two stationary phases with immobilized cyclodextrins in reversed-phase and polar-organic modes. The mobile phase and the chiral stationary phase were varied to achieve the best resolution. Different types and concentration of aliphatic alcohols, acetonitrile or water in the mobile phase were also tested for the different separation modes. An optimal baseline separation (Rs > 1.5) was readily obtained with all silica-based celluloses and amyloses using a normal-phase methodology. The different columns gave complementary results in term of resolution. Limits of detection and quantification were 0.12-0.20 and 0.40-0.67 microm, respectively. This analytical method was applied in a preliminary study for the pronucleotide 2 quantification in cellular extract.     

Correlation between 19F environment and isotropic chemical shift in barium and calcium fluoroaluminates

High-speed MAS (19)F NMR spectra are recorded and reconstructed for 10 compounds from BaF(2)-AlF(3) and CaF(2)-AlF(3) binary systems which leads to the determination of 77 isotropic (19)F chemical shifts in various environments. A first attribution of NMR lines is performed for 8 compounds using a superposition model as initially proposed by B. Bureau et al. The phenomenological parameters of this model are then refined to improve the NMR line assignment. A satisfactory reliability is reached with a root-mean-square (RMS) deviation between calculated and measured values equal to 6 ppm. The refined parameters are then successfully tested on alpha-BaCaAlF(7) whose structure was recently determined. Finally, the isotropic chemical shift ranges are defined for shared, unshared, and "free" fluorine atoms encountered in the investigated binary systems. So, the fluorine surroundings can be deduced from the NMR line positions in compounds whose structure is unknown. Such an approach can also be applied to fluoride glasses.     

A Simple and Inexpensive Method for Etherification of Hydroxylated Polyethers in the Absence of Solvent

Alkylation of polyethers primary or secondary hydroxyl functions is performed in a solid/liquid medium, using halogenated derivatives of various structures in the absence of solvent. Selectivity is complete and yields are high, no matter what reagents are used.     

A Simplified Wittig Synthesis Using A Solid-Liquid Transfer Process : VII - Direct Transformation of Aromatic and Heteroaromatic Aldehydes into Functionalised Allylic Ethers

Synthesis of allylic ethers from various aldehyde alcohols and β-hydroxylated phosphonium salts was carried out in a single manipulation and with excellent yields.