Among the most renowned natural products from brown algae, phlorotannins are phloroglucinol polymers that have been extensively studied, both for their biotechnological potential and their interest ...in chemical ecology. The accurate quantification of these compounds is a key point to understand their role as mediators of chemical defense. In recent years, the Folin–Ciocalteu assay has remained a classic protocol for phlorotannin quantification, even though it frequently leads to over-estimations. Furthermore, the quantification of the whole pool of phlorotannins may not be relevant in ecological surveys. In this study, we propose a rapid 1H qNMR method for the quantification of phlorotannins. We identified phloroglucinol as the main phenolic compound produced by the brown macroalga Cystoseira tamariscifolia. This monomer was detected in vivo using 1H HR-MAS spectroscopy. We quantified this molecule through 1H qNMR experiments using TSP as internal standard. The results are discussed by comparison with a standard Folin–Ciocalteu assay performed on purified extracts. The accuracy and simplicity of qNMR makes this method a good candidate as a standard phlorotannin assay.
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•Phloroglucinol is quantified using qNMR in Cystoseira tamariscifolia.•qNMR stands as an accurate phlorotannin quantification method.•qNMR specificity is a key advantage for chemical ecology.
Liquid-Crystalline Aqueous Clay Suspensions Michot, Laurent J.; Bihannic, Isabelle; Maddi, Solange ...
Proceedings of the National Academy of Sciences - PNAS,
10/2006, Letnik:
103, Številka:
44
Journal Article
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This article demonstrates the occurrence of a true isotropic/nematic transition in colloidal Brownian aqueous suspensions of natural nontronite clay. The liquid-crystalline character is further ...evidenced by polarized light microscopy and small-angle x-ray scattering experiments in the presence and absence of modest external magnetic fields. The complete phase diagram ionic strength/volume fraction then exhibits a clear biphasic domain in the sol region just before the gel transition in contrast with the situation observed for other swelling clays in which the sol/gel transition hinders the isotropic/ nematic transition. Small-angle x-ray scattering measurements of gel samples reveal strong positional and orientational orders of the particles, proving unambiguously the nematic character of the gel and, thus, clearly refuting the still prevalent "house of cards" model, which explains the gel structure by means of attractive interactions between clay platelets. Such order also is observed in various other swelling clay minerals; therefore, this very general behavior must be taken into account to reach a better understanding of the rheological properties and phase behavior of these systems.
Five native Sargassaceae species from Brittany (France) living in rockpools were surveyed over time to investigate photoprotective strategies according to their tidal position. We gave evidences for ...the existence of a species distribution between pools along the shore, with the most dense and smallest individuals in the highest pools. Pigment contents were higher in lower pools, suggesting a photo-adaptive process by which the decreasing light irradiance toward the low shore was compensated by a high production of pigments to ensure efficient photosynthesis. Conversely, no xanthophyll cycle-related photoprotective mechanism was highlighted because high levels of zeaxanthin rarely occurred in the upper shore. Phlorotannins were not involved in photoprotection either; only some lower-shore species exhibited a seasonal trend in phlorotannin levels. The structural complexity of phlorotannins appears more to be a taxonomic than an ecological feature:
produced simple phloroglucinol while
and
species exhibited polymers. Consequently, tide pools could be considered as light-protected areas on the intertidal zone, in comparison with the exposed emerged substrata where photoprotective mechanisms are essential.
Sponges consume dissolved silicon (DSi) to build their skeletons. Few studies have attempted to quantify DSi utilization by these organisms and all available determinations come from laboratory ...measurements. Here we measured DSi consumption rates of the sponge Tethya citrina in its natural habitat, conducting 24h incubations in benthic chambers. Sponges consumed DSi at an average rate of 0.046 ± 0.018 μmol h-1 mL-1 when DSi availability in its habitat was 8.3 ± 1.8 μM. Such DSi consumption rates significantly matched the values predicted by a kinetic model elsewhere developed previously for this species through laboratory incubations. These results support the use of laboratory incubations as a suitable approach to learn about DSi consumption. During the field incubations, utilization of other dissolved inorganic nutrients by this low-microbial-abundance (LMA) sponge was also measured. The sponges were net sources of ammonium (-0.043 ± 0.031 μmol h-1 mL-1), nitrate (-0.063 ± 0.031 μmol h-1 mL-1), nitrite (-0.007 ± 0.003 μmol h-1 mL-1), and phosphate (-0.004 ± 0.005 μmol h-1 mL-1), in agreement with the general pattern in other LMA species. The detected effluxes were among the lowest reported for sponges, which agreed with the low respiration rates characterizing this species (0.35 ± 0.11 μmol-O2 h-1 mL-1). Despite relatively low flux, the dense population of T. citrina modifies the availability of dissolved inorganic nutrients in the demersal water of its habitat, contributing up to 14% of nitrate and nitrite stocks. Through these effects, the bottom layer contacting the benthic communities where siliceous LMA sponges abound can be partially depleted in DSi, but can benefit from inputs of N and P dissolved inorganic nutrients that are critical to primary producers.
In this article, we present a general overview of the organization of colloidal charged clay particles in aqueous suspension by studying different natural samples with different structural charges ...and charge locations. Small-angle X-ray scattering experiments (SAXS) are first used to derive swelling laws that demonstrate the almost perfect exfoliation of clay sheets in suspension. Using a simple approach based on geometrical constraints, we show that these swelling laws can be fully modeled on the basis of morphological parameters only. The validity of this approach was further extended to other clay data from the literature, in particular, synthetic Laponite. For all of the investigated samples, experimental osmotic pressures can be properly described by a Poisson-Boltzmann approach for ionic strength up to 10(-3) M, which reveals that these systems are dominated by repulsive electrostatic interactions. However, a detailed analysis of the Poisson-Boltzmann treatment shows differences in the repulsive potential strength that are not directly linked to the structural charge of the minerals but rather to the charge location in the structure for tetrahedrally charged clays (beidellite and nontronites) undergoing stronger electrostatic repulsions than octahedrally charged samples (montmorillonites, laponite). Only minerals subjected to the strongest electrostatic repulsions present a true isotropic to nematic phase transition in their phase diagrams. The influence of ionic repulsions on the local order of clay platelets was then analyzed through a detailed investigation of the structure factors of the various clay samples. It appears that stronger electrostatic repulsions improve the liquidlike positional local order.
Abstract
Toxicity mechanisms of metal oxide nanoparticles towards bacteria and underlying roles of membrane composition are still debated. Herein, the response of lipopolysaccharide-truncated
...Escherichia coli
K12 mutants to TiO
2
nanoparticles (TiO
2
NPs, exposure in dark) is addressed at the molecular, single cell, and population levels by transcriptomics, fluorescence assays, cell nanomechanics and electrohydrodynamics. We show that outer core-free lipopolysaccharides featuring intact inner core increase cell sensitivity to TiO
2
NPs. TiO
2
NPs operate as membrane strippers, which induce osmotic stress, inactivate cell osmoregulation and initiate lipid peroxidation, which ultimately leads to genesis of membrane vesicles. In itself, truncation of lipopolysaccharide inner core triggers membrane permeabilization/depolarization, lipid peroxidation and hypervesiculation. In turn, it favors the regulation of TiO
2
NP-mediated changes in cell Turgor stress and leads to efficient vesicle-facilitated release of damaged membrane components. Remarkably, vesicles further act as electrostatic baits for TiO
2
NPs, thereby mitigating TiO
2
NPs toxicity. Altogether, we highlight antagonistic lipopolysaccharide-dependent bacterial responses to nanoparticles and we show that the destabilized membrane can generate unexpected resistance phenotype.
The coagulation of sodium montmorillonite by inorganic salts (NaNO3, Ca(NO3)2 and La(NO3)3) was studied by combining classical turbidity measurements with wide-angle-X-ray scattering (WAXS), ...small-angle-X-ray scattering (SAXS), and transmission X-ray microscopy (TXM). Using size-selected samples, such a combination, associated with an original quantitative treatment of TXM images, provides a true multiscale investigation of the formed structures in a spatial range extending from a few ångstroms to a few micrometers. We then show that, at neutral pH and starting with fully Na-exchanged samples, coagulation proceeds via the formation of stacks of particles with a slight mismatch between layers. These stacks arrange themselves into larger porous anisotropic particles, the porosity of which depends on the valence of the cation used for coagulation experiments. Face-face coagulation is clearly dominant under those conditions, and no evidence for significant face-edge coagulation was found. These structures appear to arrange as larger clusters, the organization of which should control the mechanical properties of the flocs.
Natural Na-Wyoming montmorillonite was size fractionated by successive centrifugation. Polydisperse particles with average sizes of 400, 290, and 75 nm were then obtained. As the structural charge of ...the particles belonging to three fractions (determined by cationic exchange capacity measurements) is the same, such a procedure allows studying the effect of particle anisotropy on the colloidal phase behavior of swelling clay particles. Osmotic stress experiments were carried out at different ionic strengths. The osmotic pressure curves display a plateau whose beginning systematically coincides with the sol/gel transition determined by oscillatory stress measurements. The concentration corresponding to the sol/gel transition increases linearly with particle anisotropy, which shows that the sol/gel transition is not directly related to an isotropic/nematic transition of individual clay particles. Indeed, a reverse evolution should be observed for an I/N transition involving the individual clay particles. Still, when observed between crossed polarizer and analyzer, the gel samples exhibit permanent birefringent textures, whereas in the "sol" region, transient birefringence is observed when the samples are sheared. This suggests that interacting clay particles are amenable to generate, at rest and/or under shear, large anisotropic particle associations.
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