Farm production diversity and women's dietary diversity: Evidence from central Tunisia.

In the context of studies on the effects of agricultural production diversity, there are debates in the scientific community as to the level of diversification appropriate for improving dietary diversity. In Tunisia, agriculture is a strategic sector for the economy and a critical pillar of its food sovereignty. Using instrumental variable methods to account for endogeneity, we have estimated the association between agricultural production diversity and women's dietary diversity among smallholder farming households in the Sidi Bouzid governorate (central Tunisia). Although we found a low level of agricultural production diversity and a fairly diversified diet among women, we observed a systematic weak positive association between five different indicators of agricultural production diversity and women's dietary diversity. We observed a stronger positive association between women's dietary diversity and women being more educated and households being wealthier. Neither diversity of food supplies in food markets nor market distance were associated with women's dietary diversity, whereas we observed a higher level of consumption of some products (dairy) when they were produced on the farm.

Nanoparticles as Anti-Microbial, Anti-Inflammatory, and Remineralizing Agents in Oral Care Cosmetics: A Review of the Current Situation.

Many investigations have pointed out widespread use of medical nanosystems in various domains of dentistry such as prevention, prognosis, care, tissue regeneration, and restoration. The progress of oral medicine nanosystems for individual prophylaxis is significant for ensuring bacterial symbiosis and high-quality oral health. Nanomaterials in oral cosmetics are used in toothpaste and other mouthwash to improve oral healthcare performance. These processes cover nanoparticles and nanoparticle-based materials, especially domains of application related to biofilm management in cariology and periodontology. Likewise, nanoparticles have been integrated in diverse cosmetic produces for the care of enamel remineralization and dental hypersensitivity. This review summarizes the indications and applications of several widely employed nanoparticles in oral cosmetics, and describes the potential clinical implementation of nanoparticles as anti-microbial, anti-inflammatory, and remineralizing agents in the prevention of dental caries, hypersensitivity, and periodontitis.

Phenolic distribution in apple epidermal and outer cortex tissue by multispectral deep-UV autofluorescence cryo-imaging.

Phenolic compounds in fruit are involved in responses to biotic and abiotic stresses and are responsible for organoleptic properties. To establish the distribution of these secondary metabolites at the tissue and sub-cellular scales, mapping of fluorescence in apple epidermis and outer cortex tissue in cryogenic condition was performed after deep-UV excitation at 275 nm. Douce Moën and Guillevic cider apple varieties were sampled and frozen after harvest, after 30 days at 4 °C and after 20 days at room temperature. Image analysis of fluorescence emission images acquired between 300 and 650 nm allowed the assignment of fluorescence signals to phenolic compound families based on reference molecules. Emission attributed to monomeric and/or condensed flavanol was localized in whole tissue with major fluorescence in the cuticle region. Hydroxycinnamic acids were found predominantly in the outer cortex and appeared in the cell wall. Fluorescent pigments were mostly found in the epidermis. The distribution of flavanols in the sub-cuticle and phenolic acids in the outer cortex distinguished apple varieties. Storage conditions had no impact on phenolic distribution. The proposed fluorescent imaging and analysis approach enables studies on phenolic distribution in relation to fruit development, biotic/abiotic stress resistance and quality.

Increased diffusivity of lycopene in hot break vs. cold break purees may be due to bioconversion of associated phospholipids rather than differential destruction of fruit tissues or cell structures.

Lycopene bioaccessibility is enhanced by processing, as explained by the destructuration of plant tissues, making diffusion easier. However, in tomato, the relationship between grinding intensity and lycopene release from purees suffers from uncertainty. In particular, hot break puree exhibited twice as much diffusible lycopene as compared to cold break, while both were processed with the same grinding intensity. To explain the difference, we systematically studied the diffusivity of particles according to their size and integrity, and used microscopic and physical analyses to reveal structural differences. Neither particle size distribution, nor cell destruction, nor plastid transformation exhibited any correlation to the differences in diffusivity. However, Raman microspectroscopy combined with a chemometric analysis revealed significant changes in lycopene spectra and a putative linkage to phospholipid transformation. Phospholipid profiling of five pairs of contrasted purees revealed that, during the cold break, a transition from complex phospholipids to more simple phosphatidic acid molecules systematically occurred.

Cryo-laser scanning confocal microscopy of diffusible plant compounds.

BACKGROUND: The in vivo observation of diffusible components, such as ions and small phenolic compounds, remains a challenge in turgid plant organs. The analytical techniques used to localize such components in water-rich tissue with a large field of view are lacking. It remains an issue to limit compound diffusion during sample preparation and observation processes. RESULTS: An experimental setup involving the infusion staining of plant tissue and the cryo-fixation and cryo-sectioning of tissue samples followed by fluorescence cryo-observation by laser scanning confocal microscopy (LSCM) was developed. This setup was successfully applied to investigate the structure of the apple fruit cortex and table grape berry and was shown to be relevant for localizing calcium, potassium and flavonoid compounds. CONCLUSION: The cryo-approach was well adapted and opens new opportunities for imaging other diffusible components in hydrated tissues.

A "Fork-to-Farm" Multi-Scale Approach to Promote Sustainable Food Systems for Nutrition and Health: A Perspective for the Mediterranean Region.

Mediterranean countries are undergoing dietary and nutritional changes that affect their inhabitants' health, while facing massive environmental challenges. The increasing demand of water in agriculture, the capacity to maintain local food production, and the growing dependence on food imports are interconnected issues that must be addressed to ensure food security and nutrition in the Mediterranean region. Here, we present the conceptual framework and methodologies developed by the MEDINA-Study Group for rethinking food systems toward sustainable consumption and production modes. Based on its multidisciplinary expertise, the MEDINA-Study Group designed a "fork-to-farm" multi-scale approach, stemming from current dietary habits and examining how some options to nutritionally improve these habits might affect the food systems. This approach was developed for research activities in the South of France and Tunisia, two areas with very different diet-agriculture-environment nexus. The conceptual framework is based on the analysis of elements of the food systems (from consumption to production) at different levels (individual, household, regional and national levels). The methods include: (i) modeling options of dietary changes at different scales, in order to nutritionally optimize food consumption-production without increasing the environmental impact, (ii) translating the best-choice changes into possible policy actions, (iii) testing the acceptability and feasibility of these actions with several stakeholders, and (iv) producing guidelines for sustainable food choices and production. The MEDINA-Study Group identified additional issues that could be included in a future framework to help designing ambitious agricultural, food and health policies in the Mediterranean region.

Reuse of red algae waste for the production of cellulose nanocrystals and its application in polymer nanocomposites.

Red algae is widely available around the world and its exploitation for the production of agar products has become an important industry in recent years. The industrial processing of red algae generates a large quantity of solid fibrous wastes, which constitutes a source of serious environmental problems. In the present work, the utilization of red algae waste as raw material to produce high-quality cellulose nanocrystals (CNC) has been investigated, and the ability of the as-isolated CNC to reinforce polymer has been studied. Red algae waste was chemically treated via alkali, bleaching and acid hydrolysis treatments, in order to obtain pure cellulose microfibers and CNC. The raw waste and the as-extracted cellulosic materials were successively characterized at different stages of treatments using serval analysis techniques. It was found that needle-like shaped CNC were successfully isolated at nanometric scale with diameters and lengths ranged from 5.2±2.9 to 9.1±3.1nm, and from 285.4±36.5 to 315.7±30.3nm, respectively, and the crystallinity index ranged from 81 to 87%, depending on the hydrolysis time (30, 40 and 80min). The as-extracted CNC were used as nanofillers for the production of polyvinyl alcohol (PVA)-based nanocomposite films with improved thermal and tensile properties, as well as optical transparency. It is shown that the addition of 8wt% CNC into the PVA matrix increased the Young's modulus by 215%, the tensile strength by 150%, and the toughness by 45%. Additionally, the nanocomposite films maintained the same transparency level of the neat PVA film (transmittance of ∼90% in the visible region), suggesting that the CNC were dispersed at the nanoscale.

Catanionic Coacervate Droplets as a Surfactant-Based Membrane-Free Protocell Model.

We report on the formation of surfactant-based complex catanionic coacervate droplets in mixtures of decanoic acid and cetylpyridinium chloride or cetyltrimethylammonium bromide. We show that coacervation occurs over a broad range of composition, pH, and ionic strength. The catanionic coacervates consist of elongated micelles, sequester a wide range of solutes including water-soluble organic dyes, polysaccharides, proteins, enzymes, and DNA, and can be structurally stabilized by sodium alginate or gelatin-based hydrogelation. These results suggest that catanionic coacervates could be exploited as a novel surfactant-based membrane-free protocell model.

Mechanical Properties of Membranes Composed of Gel-Phase or Fluid-Phase Phospholipids Probed on Liposomes by Atomic Force Spectroscopy.

In many liposome applications, the nanomechanical properties of the membrane envelope are essential to ensure, e.g., physical stability, protection, or penetration into tissues. Of all factors, the lipid composition and its phase behavior are susceptible to tune the mechanical properties of membranes. To investigate this, small unilamellar vesicles (SUV; diameter < 200 nm), referred to as liposomes, were produced using either unsaturated 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) or saturated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) in aqueous buffer at pH 6.7. The respective melting temperatures of these phospholipids were -20 and 41 °C. X-ray diffraction analysis confirmed that at 20 °C DOPC was in the fluid phase and DPPC was in the gel phase. After adsorption of the liposomes onto flat silicon substrates, atomic force microscopy (AFM) was used to image and probe the mechanical properties of the liposome membrane. The resulting force-distance curves were treated using an analytical model based on the shell theory to yield the Young's modulus (E) and the bending rigidity (kC) of the curved membranes. The mechanical investigation showed that DPPC membranes were much stiffer (E = 116 ± 45 MPa) than those of DOPC (E = 13 ± 9 MPa) at 20 °C. The study demonstrates that the employed methodology allows discrimination of the respective properties of gel- or fluid-phase membranes when in the shape of liposomes. It opens perspectives to map the mechanical properties of liposomes containing both fluid and gel phases or of biological systems.

Self-Assembling Behavior of Glycerol Monoundecenoate in Water.

The self-assembling properties of glycerol esters in water are well known. Still, few data on glycerol monoesters of undecylenic acid are available. The aim of this study was to highlight the behavior of glycerol monoundecenoate (GM-C11:1) in different diluted and concentrated states. Its self-assembling properties in water and upon solid inorganic surfaces were investigated in the diluted state using surface tension experiments, atomic force microscopy, and cryogenic transmission electron microscopy studies. In the concentrated state, the gelling properties in the presence of water were investigated using polarized light microscopy, differential scanning calorimetry (DSC), and small-angle X-ray scattering (SAXS) experiments. GM-C11:1 at 100 mg/L self-assembles at the liquid/air interfaces as aggregates of approximately 20 nm in diameter, organized into concentric forms. These aggregates are spherical globules composed of several molecules of GM-C11:1. At higher concentrations (1000 and 104 mg/L), GM-C11:1 is able to uniformly coat liquid/air and liquid/solid interfaces. In bulk, GM-C11:1 forms spontaneously aggregates and vesicles. In a more concentrated state, GM-C11:1 assembles into lamellar Lß and Lα forms in water. By cross-referencing SAXS and DSC findings, we were able to distinguish between interlamellar water molecules strongly bound to GM-C11:1 and other molecules remaining unbound and considered to be "mobile" water. The percentage of water strongly bound was proportional to the percentage of GM-C11:1 in the system. In this case, GM-C11:1 appears to be an effective molecule for surface treatments for which water retention is important.

Structural, Viscoelastic, and Electrochemical Characteristics of Self-Assembled Amphiphilic Comblike Copolymers in Aqueous Solutions.

Self-assembly in aqueous solutions of an amphiphilic comblike polyelectrolyte (80C12) that consists of a polystyrene (PS) backbone onto which quaternary ammonium pendant moieties have been grafted has been investigated by light scattering and cryo-transmission electron microscopy measurements in the presence of KCl and methylviologen dication (MV2+) under conditions mimicking those for electrochemical measurements. Polymer chains self-assemble within branched cylindrical micelles that display viscoelastic properties, characterized by a relaxation time of 4 s. To tune this time, 80C12 was mixed with a polyoxyethylene nonionic surfactant (Brij C12E10). Relatively increasing the amount of the latter leads to a decrease in the relaxation time of the 80C12 solution. Correlatively, electrochemical experiments with a rotating disk electrode show a transition of the mass transport rate, which deviates from the classical Newtonian behavior in the same velocity domain. This result generalizes what has been already observed with solutions of linear polymers of high molecular weight and wormlike micelles based on surfactants subjected to elongational deformations. Moreover, the critical times derived from rheological and electrochemical experiments display the same trend.

Impact of Nonthermal Atmospheric Plasma on the Structure of Cellulose: Access to Soluble Branched Glucans.

We have investigated the effect of non-thermal atmospheric plasma (NTAP) on the structure of microcrystalline cellulose. In particular, by means of different characterization methods, we demonstrate that NTAP promotes the partial cleavage of the ß-1,4 glycosidic bond of cellulose leading to the release of short-chain cellodextrins that are reassembled in situ, preferentially at the C6 position, to form branched glucans with either a glucosyl or anhydroglucosyl terminal residue. The ramification of cellulosic chain induced by NTAP yields branched glucans that are soluble in DMSO or in water, thus opening a straightforward access to processable glucans from cellulose. Importantly, the absence of solvent and catalyst considerably facilitates downstream processing as compared to (bio)catalytic processes which typically occur in diluted conditions.

Data on characterization of nano- and micro-structures resulting from glycine betaine surfactant/kappa-carrageenan interactions by Laser Scanning Confocal Microscopy and Transmission Electron Microscopy.

This article contains data on the Laser Scanning Confocal Microscopy (LSCM) and Transmission Electron Microscopy (TEM) images related to multi-scaled self-assemblies resulting from 'green' cationic glycine betaine surfactant/anionic kappa-carrageenan interactions. These data gave clear evidence of the evolution of the micron-, nano-sized structures obtained at two surfactant/polymer molar ratios (3.5 and 0.8) and after the dilution of the aqueous dispersions with factors of 5 and 10 times. This data article is related to the research article entitled, "Monitoring the architecture of anionic ĸ-carrageenan/cationic glycine betaine amide surfactant assemblies by dilution: A multiscale approach" (Gaillard et al., 2017) [1].

Fast and effective quantum-dots encapsulation and protection in PEO based photo-cross-linked micelles.

Cadmium-based quantum dots (QDs) were easily, quickly and efficiently transferred from an organic medium to water without modification of their surface chemistry by the simple emulsion/solvent evaporation technique using micelles of amphiphilic diblock copolymers based on poly(ethylene oxide) and poly(2-methacryloyloxyethyl acrylate) (PEO-b-PMEA) as hosts. The resulting hybrid micelles were stabilized very rapidly by photo-cross-linking the hydrophobic core around the QDs. The encapsulation and photo-cross-linking process were shown to barely affect the photoluminescence properties. Grafting a short octyl chain at the end of the hydrophobic block enhanced both the colloidal stability of the QDs dispersed in water and prevented the quenching of their fluorescence by copper ions. Grafting a longer hexadecyl chain at the end of the PMEA block decreased the efficiency of the corona cross-linking and led to poorer stabilization and protection.

On the interaction of alginate-based core-shell nanocarriers with keratinocytes in vitro.

Calcium alginate nanocarriers (CaANCs) were developed as a potential tool for delivery of hydrophobic active molecules such as pharmaceutical and cosmetic active ingredients. In this study, we focused on interactions between CaANCs and keratinocytes in culture and examined toxicity, internalization and drug release. Prior to cellular interactions, cryogenic transmission electron microscopy images showed that CaANCs appear as regular, spherical and dense particles, giving evidence of the surface gelation of CaANCs. Their size, around 200nm, was stable under tested conditions (temperature, culture media, presence of serum and presence of encapsulated dye), and their toxicity on keratinocytes was very low. Flow cytometry assays showed that CaANCs are internalized into keratinocytes by endocytosis with a predominant implication of the caveolae-mediated route. Förster resonance energy transfer (FRET) demonstrated that after a 2h contact, the release of CaANC contents in the cytoplasm of keratinocytes was almost complete. The endocytosis of CaANCs by a lysosome-free pathway, and the rapid release of their contents inside keratinocytes, will allow vectorized molecules to fully exhibit their pharmacological or cosmetic activity.

Ester Cross-Link Profiling of the Cutin Polymer of Wild-Type and Cutin Synthase Tomato Mutants Highlights Different Mechanisms of Polymerization.

Cuticle function is closely related to the structure of the cutin polymer. However, the structure and formation of this hydrophobic polyester of glycerol and hydroxy/epoxy fatty acids has not been fully resolved. An apoplastic GDSL-lipase known as CUTIN SYNTHASE1 (CUS1) is required for cutin deposition in tomato (Solanum lycopersicum) fruit exocarp. In vitro, CUS1 catalyzes the self-transesterification of 2-monoacylglycerol of 9(10),16-dihydroxyhexadecanoic acid, the major tomato cutin monomer. This reaction releases glycerol and leads to the formation of oligomers with the secondary hydroxyl group remaining nonesterified. To check this mechanism in planta, a benzyl etherification of nonesterified hydroxyl groups of glycerol and hydroxy fatty acids was performed within cutin. Remarkably, in addition to a significant decrease in cutin deposition, mid-chain hydroxyl esterification of the dihydroxyhexadecanoic acid was affected in tomato RNA interference and ethyl methanesulfonate-cus1 mutants. Furthermore, in these mutants, the esterification of both sn-1,3 and sn-2 positions of glycerol was impacted, and their cutin contained a higher molar glycerol-to-dihydroxyhexadecanoic acid ratio. Therefore, in planta, CUS1 can catalyze the esterification of both primary and secondary alcohol groups of cutin monomers, and another enzymatic or nonenzymatic mechanism of polymerization may coexist with CUS1-catalyzed polymerization. This mechanism is poorly efficient with secondary alcohol groups and produces polyesters with lower molecular size. Confocal Raman imaging of benzyl etherified cutins showed that the polymerization is heterogenous at the fruit surface. Finally, by comparing tomato mutants either affected or not in cutin polymerization, we concluded that the level of cutin cross-linking had no significant impact on water permeance.

Self-Assembly of Bilayer Vesicles Made of Saturated Long Chain Fatty Acids.

Saturated long chain fatty acids (sLCFA, e.g., C14:0, C16:0, and C18:0) are potentially the greenest and cheapest surfactants naturally available. However, because aqueous sodium soaps of sLCFA are known to crystallize, the self-assembly of stable bilayer vesicles has not been reported yet. Here, by using such soaps in combination with guanidine hydrochloride (GuHCl), which has been shown recently to prevent crystallization, we were capable of producing stable bilayer vesicles made of sLCFA. The phase diagrams were established for a variety of systems showing that vesicles can form in a broad range of composition and pH. Both solid state NMR and small-angle neutron scattering allowed demonstrating that in such vesicles sLCFA are arranged in a bilayer structure which exhibits similar dynamic and structural properties as those of phospholipid membranes. We expect these vesicles to be of interest as model systems of protocells and minimal cells but also for various applications since fatty acids are potentially substitutes to phospholipids, synthetic surfactants, and polymers.

Smart Nonaqueous Foams from Lipid-Based Oleogel.

Oil foams are composed of gas bubbles dispersed in an oil phase. These systems are scarcely studied despite their great potential in diverse fields such as the food and cosmetic industries. Contrary to aqueous foams, the production of oil foams is difficult to achieve due to the inefficiency of surfactant adsorption at oil-air interfaces. Herein, we report a simple way to produce oil foams from oleogels, whose liquid phase is a mixture of sunflower oil and fatty alcohols. The temperature at which the oleogel formed was found to depend on both fatty alcohol chain length and concentration. The air bubbles in the oleogel foam were stabilized by fatty alcohol crystals. Below the melting temperature of the crystals, oleogel foams were stable for months. Upon heating, these ultrastable foams collapsed within a few minutes due to the melting of the crystal particles. The transition between crystal formation and melting was reversible, leading to thermoresponsive nonaqueous foams. The reversible switching between ultrastable and unstable foam depended solely on the temperature of the system. We demonstrate that these oleogel foams can be made to be photoresponsive by using internal heat sources such as carbon black particles, which can absorb UV light and dissipate the absorbed energy as heat. This simple approach for the formulation of responsive oil foams could be easily extended to other oleogel systems and could find a broad range of applications due to the availability of the components in large quantities and at low cost.

pH-responsive fatty acid self-assembly transition induced by UV light.

Fatty acids are natural, pH-responsive surfactants. Their properties can be tuned by adding CO2 or by applying light which modify solution pH. We investigated photoresponsive systems based on fatty acids with different chain lengths in the presence of a photoacid generator (PAG). Under UV irradiation, photolysis of the PAG in aqueous solution resulted in a decrease in pH, triggering a change in fatty acid assembly. Using a multi-scale approach before and after UV irradiation, we characterized the effect of this pH decrease on the nature of the fatty acid self-assemblies. At the molecular scale, pH and infrared spectroscopy measurements were used to determine the fatty acid ionization state. At the microscopic scale, the self-assembled structure was characterized using small-angle neutron scattering and microscopy. We showed that UV irradiation tuned the ionization state of the fatty acid molecules which in turn triggered a transition from spherical micelles to vesicles or lamellar phases, depending on fatty acid chain length. We studied the foaming properties of these systems before and after UV irradiation. We showed that after UV irradiation, foam stability was drastically enhanced as a result of a change in self-assembly. Our approach can be easily extended to various pH-responsive surfactants.

In vitro digestion of emulsions: high spatiotemporal resolution using synchrotron SAXS.

Although the biochemical processes of lipid digestion are well-known, the biophysical ones, responsible for the assembly of molecules into functional structures, lack studies resolving both time and space scales. About 35 years ago, the seminal microscopy study of Patton and Carey constituted a major advance to reach this goal. Nowadays, new perspectives arise from the availability of large facilities scattering techniques, able to monitor the dynamics of multi-scale assemblies with unprecedented resolutions. The present small angle X-ray scattering (SAXS) study focused on the roles of the emulsifier and triglyceride in the formation of lipid assemblies during emulsion digestion in vitro. By developing several interpretations of the data in the whole space range (qualitative, shape-dependent and shape-independent models), the characteristic size of the assemblies and their transition times were obtained, which depended on the triglyceride, but not on the emulsifier. The major assembly formed was found to be a spherical mixed micelle, but vesicle was also found to coexist throughout the digestion, although in a lower proportion. The quantitative determination of the sizes and proportions of these assemblies, as well as the evolution of these characteristics during digestion are precious information for nutritional sciences, as these assemblies are the vehicles of lipophilic nutrients and micronutrients towards their absorption site.