Guillaume Voyard

Analysis of electrophoretic soil humic acids fractions by reversed-phase high performance liquid chromatography with on-line absorbance and fluorescence detection

A combination of reversed-phase high performance liquid chromatography (RP HPLC) with on-line absorbance and fluorescence detection was used for analysis of chernozem soil humic acids (HAs) and their fractions A, B and C+D with different electrophoretic mobility (EM) and molecular size (MS). Samples were injected onto the column at the identical volume and absorbance. All chromatograms exhibit the resolution of seven peaks. The estimation of relative recovery of HAs and fractions from the reverse-phase column has been done. High MS fraction A, which possesses the low EM, is essentially more hydrophobic (73% of the fraction amount remained adsorbed on the column) and aliphatic than medium MS and EM fraction B (33% of the fraction amount remained adsorbed on the column). The most hydrophilic and aromatic properties belong to low MS fraction C+D, which possess the highest EM and practically was not adsorbed on the column. The hydrophobicity of the bulk HAs lies within the range of fractions hydrophobicity. The absorption spectra of bulk HAs, electrophoretic fractions A, B, C+D and corresponding RP HPLC peaks were featureless but had differences in the values of absorbance ratio at 300 and 400 nm (A3/A4). For fractions A and B this ratio gradually decreased from peak 1 to 7 (from 3.05 to 2.80 and 3.00 to 2.40, respectively). This trend was less pronounced in HAs and practically absent in fraction C+D, where ratio A3/A4 varied within a small range. The strong relationship between fluorescence properties, EM, MS, polarity and aliphaticity/aromaticity of HAs fractions was found. Humic and protein-like fluorescence had different polarity nature. The protein-like fluorescence is located in humic material which irreversibly adsorbed on the reverse-phase column and not subjected to RP HPLC characterization. The humic-like fluorescence at Ex/Em 270/450 nm is mostly located in the hydrophilic peak of low MS fraction C+D. Taking into account that high MS fraction A consisted mainly of aliphatic components it is reasonable to suggest that these associations are capable of organizing into micellar structures. These data could be of great environmental importance, because the different fractions might reflect different soil physical-chemical properties.

Improving the characterization of dissolved organic carbon in cloud water: Amino acids and their impact on the oxidant capacity

Improving our understanding of cloud chemistry depends on achieving better chemical characterization (90% of the organic carbon [OC] fraction remains uncharacterized) and, consequently, assessing the reactivity of this complex system. In this manuscript, we report for the first time the concentrations of 16 amino acids (AAs) in 25 cloud water samples. The concentrations of individual AAs ranged from a few nM up to ~2.0 μM, and the average contribution of AAs corresponded to 9.1% (4.4 to 21.6%) of the dissolved OC (DOC) concentration. Considering their occurrence and concentrations, AAs were expected to represent an important hydroxyl radical (HO•) sink in aqueous cloud samples. In this work, we estimated that approximately 17% (from 7 to 36%) of the hydroxyl radical-scavenging ability of the DOC could be attributed to the presence of AAs, whereas comparing the AAs suggested that an average of 51% (from 22 to 80%) of their reactivity with HO• could account for the presence of tryptophan. These results clearly demonstrate that the occurrence and reactivity of AAs must be considered to better estimate the chemical composition and oxidant capacity of the cloud aqueous phase.

Characterizing mesh size distributions (MSDs) in thermosetting materials using a high-pressure system.

The thermoporosimetry method was adapted to determine the mesh size distribution of an acrylate thermoset clearcoat. This goal was achieved by increasing the solvent rate transfer by increasing the pressure and temperature. A comparison of the results obtained using this approach with those obtained by DMA (dynamic mechanical analysis) underlined the accuracy of thermoporosimetry in characterizing the macromolecular architecture of thermosets. The thermoporosimetry method was also used to analyze the effects of photoaging on cross-linking, which result from the photodegradation of the acrylate thermoset. It was found that the formation of a three-dimensional network followed by densification generates a modification of the average mesh size that leads to a dramatic decrease of the meshes of the polymer.

Molecular Size distribution of Fluorophores in Aquatic Natural Organic Matter: Application of HPSEC with Multi-Wavelength Absorption and Fluorescence Detection Following LPSEC-PAGE Fractionation

Analytical high performance size exclusion liquid chromatography (HPSEC) with multiwavelength absorbance and fluorescence detections was used for the analysis of molecular size distribution and optical properties of dissolved natural organic matter. Experiments were conducted on Suwannee River organic matter (SRNOM) and its fractions A, B, C+D preliminary obtained by combination of preparative low pressure size exclusion chromatography and polyacrylamide gel electrophoresis (LPSEC-PAGE) and purified by dialysis on membrane with nominal cutoff 10 kDa, the fractions molecular size varied in order A > B > C + D > 10 kDa. The multistep fractionation of SRNOM enabled the size-separation of at least five types of humic-like fluorophores within NOM showing emission maxima at 465, 450, 435, 420, and 405 nm. The decrease of the humic-like emission maxima paralleled the decrease of the nominal molecular size of fluorescent SRNOM. The protein-like fluorescence was split into tyrosine-like and tryptophan-like fluorophores and only detected in fractions A and B. This work provides new data on the optical properties of size-fractionated NOM, which consistent with the formation of supramolecular NOM assemblies, likely controlled by association of low-molecular size components. It is clearly observed for the high molecular size fraction A, containing free amino acids or short peptides. The combination of several different fractionation procedures is very useful for obtaining less complex NOM compounds and understanding the NOM function in the environment.

Photocatalysis of the Organophosphorus Fenamiphos: Insight into the Degradation Mechanism

The photocatalytic degradation of the organophosphorus fenamiphos (FN) was studied using titanium dioxide as a photocatalyst and 365 nm as an excitation wavelength. Under our experimental conditions and in aerated solutions, the irradiation in the presence of TiO2 P25 (1.0 g L−1) permitted the evaluation of the half lifetime to 9.5 minutes. Laser flash photolysis experiments showed the formation of an initial species owing to the attack of the hydroxyl radical on FN. It was identified as the adduct -FN. The second order rate constant for its formation was evaluated to moL−1 L s−1. All the products are formed via the formation of such transient intermediate. They were identified by means of HPLC/MS using electrospray in positive mode (). Two main processes are responsible for FN photocatalytic transformation: (i) hydroxylation on the aromatic structure and (ii) the scission of the C–O bond. A mechanistic scheme was proposed for the photocatalytic process of FN using titanium dioxide. An efficient mineralization was observed within 24 hours by using a suntest setup.

Dietary supplementation with cysteine prevents adverse metabolic outcomes of repeated cures with paracetamol in old rats

Cysteine (Cys), a conditionally indispensable amino acid, is required for the detoxification of paracetamol (acetaminophen, N-acetyl-para-aminophenol, 4-hydroxy-acetanilide, APAP), a drug of widespread use in older persons. We recently reported that repeated APAP cures could worsen sarcopenia in old rats, likely to be due to the impairment of Cys/GSH homoeostasis. The aim of the study was to evaluate whether a dietary Cys supplementation during APAP cures could improve Cys/GSH homoeostasis and thus preserve skeletal muscle. Male 21·5-month-old Wistar rats received three 2-week-long cures of APAP (1 % of diet) alone or with extra Cys (0·5 % of diet), intercalated with washout periods of 2 weeks (APAP and APAP-Cys groups, respectively). They were compared with untreated control rats (CT group). CT and APAP-Cys groups were pair-fed to the APAP group. Dietary Cys supplementation was efficient to prevent increase in liver mass (P<0·0001), decrease in liver GSH (P<0·0001), increase in blood GSH concentration (P<0·0001), and to some extent, decrease in plasma free Cys concentration (P<0·05), all induced by repeated APAP cures. The addition of Cys to APAP cures decreased plasma alanine transaminase (P<0·05), the fractional synthesis rate of liver proteins (P<0·01), and increased masses of extensor digitorum longus (P<0·01), and soleus (P<0·05), compared with the APAP group. Cys supplementation prevented alteration in Cys/GSH homoeostasis and increased some muscle masses in old rats under repeated cures with a non-toxic dose of APAP.