Anionic pH-sensitive pegylated lipoplexes to deliver DNA to tumors.

Anionic pegylated lipoplexes have been prepared from the combined formulation of cationic lipoplexes and pegylated anionic liposomes. To this end, two original (bis- and tetra-) carboxylated cholesterol derivatives have been synthesised. Titration of the particle surface charge was realised to determine the ratio between anionic and cationic lipids that would give pH-sensitive complexes. This ratio has been optimised to form particles sensitive to pH change in the range 5.5-6.5. Compaction of DNA into these newly formed anionic complexes was checked by DNA accessibility to picogreen and DNA electrophoresis on an agarose gel. Gene expression of the formulated gene was similar for the cationic formulation taken as a control and the anionic formulations prepared. The pH-sensitive properties of these formulations was shown in vitro using bafilomycin, a vacuolar H(+)ATPase inhibitor. The efficiency of the new formulations to deliver DNA to the tumor was compared with cholesteryl hemisuccinate (CHEMS) formulations. The tetracarboxylated compound gave the most efficient formulations for tumor delivery in vivo.

Comparison of the bulk geochemical features and thermal reactivity of kerogens from Mol (Boom Clay), Bure (Callovo-Oxfordian argillite) and Tournemire (Toarcian shales) underground research laboratories.

Deep argillaceous formations are potential repositories for the long-term disposal of nuclear waste because of their low permeability and high sorption capacity with respect to radioelements and heavy metals. Such sedimentary rocks contain organic matter, mostly macromolecular and insoluble (kerogen). Upon temperature elevation related to high-level long-lived radioactive waste disposal, the kerogen may release significant quantities of gaseous and liquid effluents, especially oxygen-containing ones, which may influence the ability of the clay to retain radionuclides. The aim of the present study is to assess the global geochemical features and the thermal reactivity of the kerogens isolated from samples collected in the Bure and Tournemire sites, France (Callovo-Oxfordian Clay and Toarcian Shales, respectively) and to draw comparisons with data previously obtained for the Mol site, Belgium (Boom Clay). The study is based on a combination of elemental, spectroscopic (FTIR, solid state (13)C NMR) and pyrolytic (Rock-Eval pyrolysis, Curie point pyrolysis-gas chromatography/mass spectrometry) analyses. Different levels of maturity and resulting differences in the relative abundance of oxygen-containing groups were thus observed for the three kerogens. This is linked with differences in their ability to generate CO(2) and various oxygen-containing, low molecular weight, water-soluble compounds under thermal stress, decreasing from Mol to Bure and to Tournemire.

Botryococcus braunii: a rich source for hydrocarbons and related ether lipids.

This paper presents a review on Botryococcus braunii, a cosmopolitan green colonial microalga characterised by a considerable production of lipids, notably hydrocarbons. Strains like wild populations of this alga differ in the type of hydrocarbons they synthesise and accumulate: (1) n-alkadienes and trienes, (2) triterpenoid botryococcenes and methylated squalenes, or (3) a tetraterpenoid, lycopadiene. In addition to hydrocarbons and some classic lipids, these algae produce numerous series of characteristic ether lipids closely related to hydrocarbons. This review covers the algal biodiversity, the chemical structures and biosynthesis of hydrocarbons and ether lipids and the biotechnological studies related to hydrocarbon production.

Characterization and comparison of two ligno-cellulosic substrates by (13)C CP/MAS NMR, XPS, conventional pyrolysis and thermochemolysis.

Ligno-cellulosic substrates (LCSs) isolated from wheat straw and bran exhibit high complexing capacities and may have important applications for metal removal from industrial effluents. These two LCSs were examined in the present work by spectroscopic and pyrolytic methods (solid state cross polarization magic angle spinning (CP/MAS) (13)C NMR, XPS, conventional Curie pyrolysis (Cupy)/GC/MS, and TMAH thermochemolysis/GC/MS). This combined study highlighted the limitation of some of the above methods when applied to ligno-cellulosic materials and the resulting biases and the usefulness of TMAH thermochemolysis. A large difference in composition was observed between bran- and straw-LCS due to a much higher contribution of alkyl moieties in the former. These moieties correspond to fatty acids esterified to the ligno-cellulosic macromolecular structure and such carboxylic functions should play an important role for metal complexation.

Changes in the organic composition of wastewater during biological treatment as studied by NMR and IR spectroscopies.

Despite its importance, relatively little is known about the composition and fate of wastewater organic matter (OM) in treatment plants. Monitoring the chemical changes in OM during activated sludge treatment can improve our knowledge of the processes involved in the biological elimination of OM. Direct chemical analyses of treated water OM typically account for about 20% of the OM, and structural information was obtained in this study using Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FTIR) spectroscopic techniques. Distinct changes in the OM during wastewater biological treatment were underlined. 13C and 1H NMR showed that aromatic carbons were minor constituents of the samples. Alkyl chains exhibited a more highly branched character in treated water, as compared to long chain aliphatic carbons present in wastewater. Carboxyl signals in the 13C NMR spectrum of wastewater could be due to peptide bonds in proteins, whereas in the treated water spectrum, this signal could be related to the presence of non-proteinaceous nitrogen. Besides the non-degraded compounds, treated water OM could contain recondensation products of simple molecules. Their refractory character probably derives from their complex structures rather than from particular chemical functions, as suggested by the lack of fundamental differences in the chemical structures of wastewater and treated water OM.

[Lipids from fossil plants and their relation to modern plants. Example s of Cenomanian flora from Anjou and Bohemia]. / Les lipides des plantes fossiles dans leurs rapports avec les plantes actuelles. Exemples des flores cénomaniennes d'Anjou et de Bohême.

Comparative analyses of lipids from fossil plants and from their extant counterparts were undertaken in order to test the taxonomic significance of lipids in palaeobotany. The comparison between lipids from a fossil Ginkgoaceae, Eretmophyllum andegavense, and its extant counterpart, Ginkgo biloba, revealed the presence of original molecules, dimethoxyalkylcoumarins, in lipids from both plants. Such compounds confirm, on chemical grounds the relationship between these extant and fossil Ginkgoaceaes. Moreover, differences in n-alkane distribution between E. andegavense and E. obtusum which are very similar morphologically, confirm that these fossil plants do not belong to the same species. Furthermore, comparative analyses of a fossil Cheirolepidiaceae, Frenelopsis alata, and its extant counterpart, the Cupressaceae Tetraclinis articulata, revealed some similarities between these two species although they do not belong to the same family. Otherwise, comparative analyses of fungi-infected and uninfected samples of F. alata demonstrated that these micro-organisms can significantly affect the chemical composition of fossil plant lipids. In conclusion, even if chemical analyses alone are not sufficient to determine the genus or species of a given fossil plant, they can precise the taxonomy of some specimens that have been previously studied by palaeobotanists.

Lipids of Thermococcus hydrothermalis, an archaea isolated from a deep-sea hydrothermal vent.

The membrane lipids of a deep-sea hydrothermal vent archaea, Thermococcus hydrothermalis, were isolated, purified, and structurally characterized. On the basis of acid methanolysis and spectroscopic studies, the polar lipids, amounting to 4.5% (w/w) of the dry cells, comprised diphytanyl glycerol diethers and dibiphytanyldiglycerol tetraethers, in a 45:55 ratio. No cyclopentane ring was present in the tetraethers. From the neutral lipids, accounting for 0.4% (w/w) of the dry cells, besides low amounts of di- and tetraethers occurring in a free form, four acyclic tetraterpenoid hydrocarbons, di- and tri-unsaturated were identified. All were structurally related to lycopane. The presence of these hydrocarbons provides some evidence that lycopane, widely distributed in oceans, could be derived, at least partially, from the hydrocarbons synthesized by some thermophilic Archaea. Finally, analysis of the uninoculated culture medium indicates that fatty acid derivatives and some steroid and triterpenoid compounds identified in the lipidic extract of the archaea originated from the culture medium.

Hydrocarbon recovery and biocompatibility of solvents for extraction from cultures of Botryococcus braunii.

Various water-immiscible solvents were tested for biocompatibility and hydrocarbon recovery under different contact conditions with the hydrocarbon-rich microalga Botryococcus braunii. Eighteen solvents were first selected from a database of 1500 compounds (compiled for solvent selection for ethanol recovery from Saccharomyces cerevisiae fermentation). Nine of these candidate solvents were shown to be biocompatible with B. braunii following short contact times. This biocompatibility tends to be associated with high molecular weights and high boiling points but strongly depends on solvent chemical structure. A low polarity is essential to biocompatibility and calculated octanol-water partition coefficients, or capacity factors determined by reversed-phase high-performance liquid chromatography (HPLC), are suitable predictors of biocompatibility with B. braunii. High recoveries of hydrocarbons directly from the algal culture require relatively polar solvents and are, therefore, inimical with maintenance of cell viability. The inaccessibility of weakly polar solvents to the cell surface appears to protect the algae but also prevents substantial recovery of the hydrocarbons stored in B. braunii outer walls. In order to achieve a high recovery, contact with the solvent must be carried out on algae concentrated by filtration. Then, a large fraction of B. braunii hydrocarbons can be recovered, after a short contact time, without impairing cell viability. Under these conditions, the pertinent solvent property is affinity for the nonpolar hydrocarbons, and the highest recovery yield, approximately 70% after contact for 30 min, is achieved with hexane.

Studies on batch and continuous cultures of Botryococcus braunii: hydrocarbon production in relation to physiological state, cell ultrastructure, and phosphate nutrition.

The growth of the hydrocarbon-rich alga Botryococcus braunii was studied under "air-lift" conditions using batch and continuous cultures. Large variations in the physiological state of B. braunii were achieved in batch cultures and in continuous cultures with various dilution rates. The possible effects of these variations upon hydrocarbons (nature, relative abundance, location, level, productivity) and also on the production of exocellular polysaccharides were examined. The relationships between the physiological state of B. braunii and its hydrocarbon and polysaccharide production were discussed and compared with those generally observed in unicellular algae. The factors giving rise to the transition from high to low productivity stages were considered. To this end we examined, at first, the variations in cell ultrastructure and the resulting degeneration occurring during batch cultures. Afterward the parallel changes in some parameters of the medium (pH, phosphate level) were determined and their possible relationships with B. braunii growth and hydrocarbon production were discussed. The main features of phosphate nutrition in B. braunii and its effects on hydrocarbons were finally examined.