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The accelerated weathering of flax and miscanthus fibers possessing distinct chemical compositions was investigated. The chosen fibers included raw, extractive-free (EF) and delignified samples (x3), alone and used as fillers in a stabilized polypropylene blue matrix (PP). Modifications in both color and the chemical composition of the fibers throughout the weathering process under ultraviolet (UV) light were meticulously tracked and analyzed by spectrophotometry and attenuated total reflectance with Fourier-transform infrared spectroscopy (ATR-FTIR). The inherent nature and composition of the selected fibers led to varied color-change tendencies. Raw and EF flax fibers exhibited lightening effects, while raw and EF miscanthus fibers demonstrated darkening effects. Extractives exhibited negligible influence on the color alteration of both flax and miscanthus fibers. This disparity between the fibers correlates with their respective lignin content and type, and the significant formation of carbonyl (C=O) groups in miscanthus. Better stability was noted for delignified flax fibers. A comparative study was achieved by weathering the PP matrix containing these various fibers. Contrary to the weathering observations on individual fibers, it was noted that composites containing raw and EF flax fibers exhibited significant color degradation. The other fiber-containing formulations showed enhanced color stability when compared to the pure PP matrix. The study highlights that the UV stability of composites depends on their thermal history. As confirmed by thermogravimetric analysis (TGA), fiber degradation during extrusion may affect UV stability, a factor that is not apparent when fibers alone are subjected to UV aging.

Short flax fibers have been modified by radiation-induced grafting using methacrylate monomers containing phosphorus to give them a flame-retardant character. Two methodologies, namely pre-irradiation and simultaneous irradiation grafting, were examined. Certain parameters, notably the dose and the irradiation source (e-Beam and γ rays), were evaluated. The grafting efficiency, in terms of phosphorus content (mass percentage), was measured by X-ray fluorescence spectrometry (XRF). Using simultaneous irradiation, 2.39 wt% phosphorus could be obtained from 10 kGy, compared to 100 kGy in pre-irradiation. Furthermore, for similar phosphorus levels, the location of the grafted polymer chains was different for the two methodologies. The effect of phosphorus content on thermal properties and fire behavior was evaluated on a microscopic scale using a pyrolytic flow combustion calorimeter (PCFC) and on a laboratory scale using a cone calorimeter. It was then pointed out that flammability was linked to the phosphorus content and likely its location, which is associated with the radiation-induced grafting methodology, showing that the grafting conditions influence the final fire properties. Simultaneous irradiation, thus, proved to be more interesting in terms of efficiency and final properties.

It is shown that the presence of hundreds of ppm of water in 1,3-dimethylurea (DMU) powder led to the large depression of the transition temperature between the two enantiotropically related polymorphic forms of DMU (Form II → Form I) from 58 °C to 25 °C, thus explaining the reported discrepancies on this temperature of transition. Importantly, this case study shows that thermodynamics (through the construction of the DMU–water temperature-composition phase diagram) rather than kinetics is responsible for this significant temperature drop. Furthermore, this work also highlights the existence of a monohydrate of DMU that has never been reported before with a non-congruent fusion at 8 °C. Interestingly, its crystal structure, determined from X-ray powder diffraction data at sub-ambient temperature, consists of a DMU–water hydrogen bonded network totally excluding homo-molecular hydrogen bonds (whereas present in forms I and II of DMU).

Controlling flavor perception by analyzing volatile and taste compounds is a key challenge for food industries, as flavor is the result of a complex mix of components. Machine-learning methodologies are already used to predict odor perception, but they are used to a lesser extent to predict aroma perception. The objectives of this work were, for the processed cream cheese models studied, to (1) analyze the impact of the composition and process on the sensory perception and VOC release and (2) predict “fresh cream” aroma perception from the VOC characteristics. Sixteen processed cream cheese models were produced according to a three-factor experimental design: the texturing agent type (κ-carrageenan, agar-agar) and level and the heating time. A R-A-T-A test on 59 consumers was carried out to describe the sensory perception of the cheese models. VOC release from the cheese model boli during swallowing was investigated with an in vitro masticator (Oniris device patent), followed by HS-SPME-GC-(ToF)MS analysis. Regression trees and random forests were used to predict “fresh cream” aroma perception, i.e., one of the main drivers of liking of processed cheeses, from the VOC release during swallowing. Agar-agar cheese models were perceived as having a “milk” odor and favored the release of a greater number of VOCs; κ-carrageenan samples were perceived as having a “granular” and “brittle” texture and a “salty” and “sour” taste and displayed a VOC retention capacity. Heating induced firmer cheese models and promoted Maillard VOCs responsible for “cooked” and “chemical” aroma perceptions. Octa-3,5-dien-2-one and octane-2,3-dione were the two main VOCs that contributed positively to the “fresh cream” aroma perception. Thus, regression trees and random forests are powerful statistical tools to provide a first insight into predicting the aroma of cheese models based on VOC characteristics.

Preferential enrichment (PE) is a crystallization process, starting from either a racemic of slightly enantio-enriched solution (ca. +5%) that results in a high enantiomeric excess in the liquid phase (>+90%ee) and a slight opposite excess in the deposited crystals (−2 to −5%ee). The mechanism(s) of this symmetry-breaking phenomenon is (are) still a matter of debate since it eludes rationalization by phase diagram formalism. In this publication, we thoroughly reinvestigate the PE phenomenon of arginine fumarate by using a new approach: the process is monitored by introducing isotopically labeled arginine enantiomers into the crystallization medium to better understand the mass exchanges during crystallization. These experiments are supported by chiral HPLC-MS/MS. This study permits re-evaluating the criteria that were thought mandatory to perform PE. In particular, we show that PE occurs by a continuous exchange between the solution and the crystals and does not require the occurrence of a solvent-mediated solid–solid phase transition.

Dynamic covalent polymers (DCPs) offer opportunities as adaptive materials of particular interest for targeting, sensing and delivery of biological molecules. In this view, combining cationic units and fluorescent units along DCP chains is attractive for achieving optical probes for the recognition and delivery of nucleic acids. Here, we report on the design of acylhydrazone-based DCPs combining cationic arginine units with π-conjugated fluorescent moieties based on thiophene-ethynyl-fluorene cores. Two types of fluorescent building blocks bearing neutral or cationic side groups on the fluorene moiety are considered in order to assess the role of the number of cationic units on complexation with DNA. The (chir)optical properties of the building blocks, the DCPs, and their complexes with several types of DNA are explored, providing details on the formation of supramolecular complexes and on their stability in aqueous solutions. The DNA-templated formation of DCPs is demonstrated, which provides new perspectives on the assembly of fluorescent DCP based on the nucleic acid structure.

Atropisomers are fascinating objects of study by themselves for chemists but also find applications in various sub-fields of applied chemistry. Obtaining them in enantiopure form is far from being a solved challenge, and the past decades has seen a surge of methodological developments in that direction. Among these strategies, oxidative aromatization with central-to-axial conversion of chirality has gained increasing popularity. It consists of the oxidation of a cyclic non-aromatic precursors into the corresponding aromatic atropisomers. This review proposes a critical analysis of this research field by delineating it and discussing its historical background and its present state of the art to draw potential future development directions.

As an alternative to fossil volatile hydrocarbon solvents used nowadays in perfumery, investigation on essential oil of Commiphora wildii Merxm. oleo gum resin as a source of heptane is reported here. Heptane, representing up to 30 wt-% of this oleo gum resin, was successfully isolated from the C. wildii essential oil, using an innovative double distillation process. Isolated heptane was then used as a solvent in order to extract some noble plants of perfumery. It was found that extracts obtained with this solvent were more promising in terms of sensory analysis than those obtained from fossil-based heptane. In addition, in order to valorize the essential oil depleted from heptane, chemical composition of this oil was found to obtain, and potential biological activity properties were studied. A total of 172 different compounds were identified by GC-MS in the remaining oil. In vitro tests—including hyaluronidase, tyrosinase, antioxidant, elastase and lipoxygenase, as well as inhibitory tests against two yeasts and 21 bacterial strains commonly found on the skin—were carried out. Overall, bioassays results suggest this heptane-depleted essential oil is a promising active ingredient for cosmetic applications.

In vitro culture of flax (Linum usitatissimum L.) was exposed to chitosan oligosaccharides (COS) in order to investigate the effects on the growth and secondary metabolites content in roots and shoots. COS are fragments of chitosan released from the fungal cell wall during plant–pathogen interactions. They can be perceived by the plant as pathogen-associated signals, mediating local and systemic innate immune responses. In the present study, we report a novel COS oligosaccharide fraction with a degree of polymerization (DP) range of 2–10, which was produced from fungal chitosan by a thermal degradation method and purified by an alcohol-precipitation process. COS was dissolved in hydroponic medium at two different concentrations (250 and 500 mg/L) and applied to the roots of growing flax seedlings. Our observations indicated that the growth of roots and shoots decreased markedly in COS-treated flax seedlings compared to the control. In addition, the results of a metabolomics analysis showed that COS treatment induced the accumulation of (neo)lignans locally at roots, flavones luteolin C-glycosides, and chlorogenic acid in systemic responses in the shoots of flax seedlings. These phenolic compounds have been previously reported to exhibit a strong antioxidant and antimicrobial activities. COS oligosaccharides, under the conditions applied in this study (high dose treatment with a much longer exposure time), can be used to indirectly trigger metabolic response modifications in planta, especially secondary metabolism, because during fungal pathogen attack, COS oligosaccharides are among the signals exchanged between the pathogen and host plant.

We here report the synthesis of three new hybrid ligands built around the phenanthroline scaffold and encompassing two histidine-like moieties: phenHH, phenHGH and H’phenH’, where H correspond to histidine and H’ to histamine. These ligands were designed to capture Cu(I/II) from the amyloid-β peptide and to prevent the formation of reactive oxygen species produced by amyloid-β bound copper in presence of physiological reductant (e.g., ascorbate) and dioxygen. The amyloid-β peptide is a well-known key player in Alzheimer’s disease, a debilitating and devasting neurological disorder the mankind has to fight against. The Cu-Aβ complex does participate in the oxidative stress observed in the disease, due to the redox ability of the Cu(I/II) ions. The complete characterization of the copper complexes made with phenHH, phenHGH and H’phenH’ is reported, along with the ability of ligands to remove Cu from Aβ, and to prevent the formation of reactive oxygen species catalyzed by Cu and Cu-Aβ, including in presence of zinc, the second metal ions important in the etiology of Alzheimer’s disease. The importance of the reduced state of copper, Cu(I), in the prevention and arrest of ROS is mechanistically described with the help of cyclic voltammetry experiments.

Humankind is facing a climate and energy crisis which demands global and prompt actions to minimize the negative impacts on the environment and on the lives of millions of people. Among all the disciplines which have an important role to play, chemistry has a chance to rethink the way molecules are made and find innovations to decrease the overall anthropic footprint on the environment. In this paper, we will provide a review of the existing knowledge but also recent advances on the manufacturing and end uses of acrylamide-based polymers following the “green chemistry” concept and 100 years after the revolutionary publication of Staudinger on macromolecules. After a review of raw material sourcing options (fossil derivatives vs. biobased), we will discuss the improvements in monomer manufacturing followed by a second part dealing with polymer manufacturing processes and the paths followed to reduce energy consumption and CO2 emissions. In the following section, we will see how the polyacrylamides help reduce the environmental footprint of end users in various fields such as agriculture or wastewater treatment and discuss in more detail the fate of these molecules in the environment by looking at the existing literature, the regulations in place and the procedures used to assess the overall biodegradability. In the last section, we will review macromolecular engineering principles which could help enhance the degradability of said polymers when they reach the end of their life cycle.

Chlorophyll a derivatives were integrated in “all solid-state” dye sensitized solar cells (DSSCs) with a mesoporous TiO2 electrode and 2′,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene as the hole-transport material. Despite modest power conversion efficiencies (PCEs) between 0.26% and 0.55% achieved for these chlorin dyes, a systematic investigation was carried out in order to elucidate their main limitations. To provide a comprehensive understanding of the parameters (structure, nature of the anchoring group, adsorption …) and their relationship with the PCEs, density functional theory (DFT) calculations, optical and photovoltaic studies and electron paramagnetic resonance analysis exploiting the 4-carboxy-TEMPO spin probe were combined. The recombination kinetics, the frontier molecular orbitals of these DSSCs and the adsorption efficiency onto the TiO2 surface were found to be the key parameters that govern their photovoltaic response.

The development of hybrid materials based on polyoxometalates constitutes a strategy for the design of multifunctional materials. The slow evaporation of an aqueous solution of [NaP5W30O110]14− in the presence of γ-Cyclodextrin (γ-CD) led to the crystallization of a K6Na8{[NaP5W30O110]•(C48H80O40)}•23H2O (NaP5W30•1CD) supramolecular compound, which was characterized by single-crystal X-ray diffraction, IR-spectroscopy, thermogravimetric and elemental analyses. Structural analysis revealed the formation of 1:1 {[NaP5W30O110]•[γ-CD]}14− adduct in the solid state. Studies in solution by cyclic voltammetry, electrochemical impedance spectroscopy, 1H NMR spectroscopy, and 31P DOSY, have demonstrated weak interactions between the inorganic anion and the macrocyclic organic molecule.

Nicotinamide adenine dinucleotide (NAD) kinases are essential and ubiquitous enzymes involved in the tight regulation of NAD/nicotinamide adenine dinucleotide phosphate (NADP) levels in many metabolic pathways. Consequently, they represent promising therapeutic targets in cancer and antibacterial treatments. We previously reported diadenosine derivatives as NAD kinase inhibitors with bactericidal activities on Staphylococcus aureus. Among them, one compound (namely NKI1) was found effective in vivo in a mouse infection model. With the aim to gain detailed knowledge about the selectivity and mechanism of action of this lead compound, we planned to develop a chemical probe that could be used in affinity-based chemoproteomic approaches. Here, we describe the first functionalized chemical probe targeting a bacterial NAD kinase. Aminoalkyl functional groups were introduced on NKI1 for further covalent coupling to an activated SepharoseTM matrix. Inhibitory properties of functionalized NKI1 derivatives together with X-ray characterization of their complexes with the NAD kinase led to identify candidate compounds that are amenable to covalent coupling to a matrix.

Productivity of tropical lowland moist forests is often limited by availability and functional allocation of phosphorus (P) that drives competition among tree species and becomes a key factor in determining forestall community diversity. We used non-target 31P-NMR metabolic profiling to study the foliar P-metabolism of trees of a French Guiana rainforest. The objective was to test the hypotheses that P-use is species-specific, and that species diversity relates to species P-use and concentrations of P-containing compounds, including inorganic phosphates, orthophosphate monoesters and diesters, phosphonates and organic polyphosphates. We found that tree species explained the 59% of variance in 31P-NMR metabolite profiling of leaves. A principal component analysis showed that tree species were separated along PC 1 and PC 2 of detected P-containing compounds, which represented a continuum going from high concentrations of metabolites related to non-active P and P-storage, low total P concentrations and high N:P ratios, to high concentrations of P-containing metabolites related to energy and anabolic metabolism, high total P concentrations and low N:P ratios. These results highlight the species-specific use of P and the existence of species-specific P-use niches that are driven by the distinct species-specific position in a continuum in the P-allocation from P-storage compounds to P-containing molecules related to energy and anabolic metabolism.

Through this Special Issue, you will discover the potentiality of inorganic polymerization (sol-gel process) which is a unique and versatile way for the preparation of materials [...]

Alzheimer’s disease (AD) is one of the utmost chronic neurodegenerative disorders, which is characterized from a neuropathological point of view by the aggregates of amyloid beta (Aβ) peptides that are deposited as senile plaques and tau proteins which form neurofibrillary tangles (NFTs). Even though advancement has been observed in order to understand AD pathogenesis, currently available therapeutic methods can only deliver modest symptomatic relief. Interestingly, naturally occurring dietary flavonoids have gained substantial attention due to their antioxidative, anti-inflammatory, and anti-amyloidogenic properties as alternative candidates for AD therapy. Experimental proof provides support to the idea that some flavonoids might protect AD by interfering with the production and aggregation of Aβ peptides and/or decreasing the aggregation of tau. Flavonoids have the ability to promote clearance of Aβ peptides and inhibit tau phosphorylation by the mTOR/autophagy signaling pathway. Moreover, due to their cholinesterase inhibitory potential, flavonoids can represent promising symptomatic anti-Alzheimer agents. Several processes have been suggested for the aptitude of flavonoids to slow down the advancement or to avert the onset of Alzheimer’s pathogenesis. To enhance cognitive performance and to prevent the onset and progress of AD, the interaction of flavonoids with various signaling pathways is proposed to exert their therapeutic potential. Therefore, this review elaborates on the probable therapeutic approaches of flavonoids aimed at averting or slowing the progression of the AD pathogenesis.

α-Series gangliosides define a particular sub-class of glycosphingolipids containing sialic acid α2,6-linked to GalNAc residue that was isolated as a minor compound from the brain. The sialyltransferase ST6GalNAc V was cloned from mouse brain and showed α2,6-sialyltransferase activity almost exclusively for GM1b, to form GD1α and is considered as the main enzyme involved in the biosynthesis of α-series gangliosides. Recently, ST6GALNAC5 was identified as one of the genes over-expressed in breast cancer cell populations selected for their ability to produce brain metastasis. However, the capacity of human breast cancer cells to produce α-series gangliosides has never been clearly demonstrated. Here, we show by stable transfection and MS-MS analysis of total glycosphingolipids that ST6GALNAC5 expressing MDA-MB-231 breast cancer cells accumulate GD1α ganglioside (IV3Neu5Ac1, III6Neu5Ac1Gg4-Cer).

This manuscript reviews the possibilities offered by 2,5-dimethylfuran-protected maleimides. Suitably derivatized building blocks incorporating the exo Diels-Alder cycloadduct can be introduced at any position of oligonucleotides, peptide nucleic acids, peptides and peptoids, making use of standard solid-phase procedures. Maleimide deprotection takes place upon heating, which can be followed by either Michael-type or Diels-Alder click conjugation reactions. However, the one-pot procedure in which maleimide deprotection and conjugation are simultaneously carried out provides the target conjugate more quickly and, more importantly, in better yield. This procedure is compatible with conjugates involving oligonucleotides, peptides and peptide nucleic acids. A variety of cyclic peptides and oligonucleotides can be obtained from peptide and oligonucleotide precursors incorporating protected maleimides and thiols.

Alternative splicing of tau pre-mRNA is regulated by a 5′ splice site (5′ss) hairpin present at the exon 10−intron 10 junction. Single mutations within the hairpin sequence alter hairpin structural stability and/or the binding of splicing factors, resulting in disease-causing aberrant splicing of exon 10. The hairpin structure contains about seven stably formed base pairs and thus may be suitable for targeting through antisense strands. Here, we used antisense peptide nucleic acids (asPNAs) to probe and target the tau pre-mRNA exon 10 5′ss hairpin structure through strand invasion. We characterized by electrophoretic mobility shift assay the binding of the designed asPNAs to model tau splice site hairpins. The relatively short (10−15 mer) asPNAs showed nanomolar binding to wild-type hairpins as well as a disease-causing mutant hairpin C+19G, albeit with reduced binding strength. Thus, the structural stabilizing effect of C+19G mutation could be revealed by asPNA binding. In addition, our cell culture minigene splicing assay data revealed that application of an asPNA targeting the 3′ arm of the hairpin resulted in an increased exon 10 inclusion level for the disease-associated mutant C+19G, probably by exposing the 5′ss as well as inhibiting the binding of protein factors to the intronic spicing silencer. On the contrary, the application of asPNAs targeting the 5′ arm of the hairpin caused an increased exon 10 exclusion for a disease-associated mutant C+14U, mainly by blocking the 5′ss. PNAs could enter cells through conjugation with amino sugar neamine or by cotransfection with minigene plasmids using a commercially available transfection reagent.

A polyol method was used to obtain ultrasmall ZnO nanoparticles (NPs) doped with iron ions and coated with a low molecular weight fucoidan in order to perform in vivo MR and ex vivo fluorescence imaging of athrothrombosis. During the synthesis, the early elimination of water by azeotropic distillation with toluene allowed us to produce NPs which size, determined by XRD and TEM, decreased from 7 nm to 4 nm with the increase of iron/zinc ratios from 0.05 to 0.50 respectively. For the highest iron content (NP-0.50) NPs were evidenced as a mixture of nanocrystals made of wurtzite and cubic phase with a molar ratio of 2.57:1, although it was not possible to distinguish one from the other by TEM. NP-0.50 were superparamagnetic and exhibited a large emission spectrum at 470 nm when excited at 370 nm. After surface functionalization of NP-0.50 with fucoidan (fuco-0.50), the hydrodynamic size in the physiological medium was 162.0 ± 0.4 nm, with a corresponding negative zeta potential of −48.7 ± 0.4 mV, respectively. The coating was evidenced by FT-IR spectra and thermogravimetric analysis. Aqueous suspensions of fuco-0.50 revealed high transverse proton relaxivities (T2) with an r2 value of 173.5 mM−1 s−1 (300 K, 7.0 T) and remained stable for more than 3 months in water or in phosphate buffer saline without evolution of the hydrodynamic size and size distribution. No cytotoxic effect was observed on human endothelial cells up to 48 h with these NPs at a dose of 0.1 mg/mL. After injection into a rat model of atherothrombosis, MR imaging allowed the localization of diseased areas and the subsequent fluorescence imaging of thrombus on tissue slices.

2,3-Diphenylated quinoxaline, pyrido[2,3-b]pyrazine and 8-bromopyrido[3,4-b]pyrazine were halogenated in deprotometalation-trapping reactions using mixed 2,2,6,6-tetramethyl piperidino-based lithium-zinc combinations in tetrahydrofuran. The 2,3-diphenylated 5-iodo- quinoxaline, 8-iodopyrido[2,3-b]pyrazine and 8-bromo-7-iodopyrido[3,4-b]pyrazine thus obtained were subjected to palladium-catalyzed couplings with arylboronic acids or anilines, and possible subsequent cyclizations to afford the corresponding pyrazino[2,3-a]carbazole, pyrazino[2′,3′:5,6] pyrido[4,3-b]indole and pyrazino[2′,3′:4,5]pyrido[2,3-d]indole, respectively. 8-Iodopyrido[2,3-b] pyrazine was subjected either to a copper-catalyzed C-N bond formation with azoles, or to direct substitution to introduce alkylamino, benzylamino, hydrazine and aryloxy groups at the 8 position. The 8-hydrazino product was converted into aryl hydrazones. Most of the compounds were evaluated for their biological properties (antiproliferative activity in A2058 melanoma cells and disease-relevant kinase inhibition).

A new layered hybrid polythiophene-silica material was obtained directly by hydrolysis and polycondensation (sol-gel) of a silylated-thiophene bifunctional precursor, and its subsequent oxidative polymerization by FeCl3. This precursor was judiciously designed to guarantee its self-assembly and the formation of a lamellar polymer-silica structure, exploiting the cooperative effect between the hydrogen bonding interactions, originating from the ureido groups and the π-stacking interactions between the thiophene units. The lamellar structure of the polythiophene-silica composite was confirmed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) analyses. The solid-state nuclear magnetic resonance (NMR), UV-Vis, and photoluminescence spectra unambiguously indicate the incorporation of polythiophene into the silica matrix. Our work demonstrates that using a polymerizable silylated-thiophene precursor is an efficient approach towards the formation of nanostructured conjugated polymer-based hybrid materials.

The aim of our study is to improve the aluminium alloy corrosion resistance with Organic-Inorganic Hybrid (OIH) sol-gel coating. Coatings are obtained from unusual formulation with precursors mixing: glycidoxypropyltrimethoxysilane (GPTMS), zirconium (IV) propoxide (TPOZ) and aluminium tri-sec-butoxide (ASB). This formulation was characterized and compared with sol formulations GPTMS/TPOZ and GPTMS/ASB. In each formulation, a corrosion inhibitor, cerium (III) nitrate hexahydrate, is employed to improve the corrosion performance. Coatings obtained from sol based on GPTMS/TPOZ/ASB have good anti-corrosion performances with Natural Salt Spray (NSS) resistance of 500 h for a thickness lower than 4 µm. Contact angle measurement showed a coating hydrophobic behaviour. To understand these performances, nuclear magnetic resonance (NMR) analyses were performed, results make sol-gel coating condensation evident and are in very good agreement with previous results.

The synthesis and preliminary evaluation as donor material for organic photovoltaics of the poly(diketopyrrolopyrrole-spirobifluorene) (PDPPSBF) is reported herein. Prepared via homogeneous and heterogeneous direct (hetero)arylation polymerization (DHAP), through the use of different catalytic systems, conjugated polymers with comparable molecular weights were obtained. The polymers exhibited strong optical absorption out to 700 nm as thin-films and had appropriate electronic energy levels for use as a donor with PC70BM. Bulk heterojunction solar cells were fabricated giving power conversion efficiencies above 4%. These results reveal the potential of such polymers prepared in only three steps from affordable and commercially available starting materials.

Enriching oxygen content within nanosized zeolite X (as synthesized Na-X) by insertion of cerium (ion exchanged Ce-X) and functionalization with bromoperfluoro-n-octane (fluorinated F-X) is reported. The materials were fully characterized by powder X-ray diffraction (XRD), dynamic light scattering (DLS), zeta potential, thermogravimetric analysis (TGA), nitrogen adsorption, and nuclear magnetic resonance (19F NMR). The O2 adsorption in the zeolite samples at various concentrations (0 to 165 Torr) at −196 °C was studied by in situ FTIR. The modification of nanosized zeolites did not alter their colloidal stability, crystallinity, porosity, and particle size distribution. The inclusion of cerium and bromoperfluoro-n-octane considerably increase the oxygen capacity by 33% for samples Ce-X and F-X in comparison to the as-synthesized Na-X zeolite. Further, toxicity tests revealed that these materials are safe, which opens the door for their implementation in medical applications, where controlled delivery of oxygen is highly desirable.

A new resveratrol dimer (1) called labruscol, has been purified by centrifugal partition chromatography of a crude ethyl acetate stilbene extract obtained from elicited grapevine cell suspensions of Vitis labrusca L. cultured in a 14-liter stirred bioreactor. One dimensional (1D) and two dimensional (2D) nuclear magnetic resonance (NMR) analyses including 1H, 13C, heteronuclear single-quantum correlation (HSQC), heteronuclear multiple bond correlation (HMBC), and correlation spectroscopy (COSY) as well as high-resolution electrospray ionisation mass spectrometry (HR-ESI-MS) were used to characterize this compound and to unambiguously identify it as a new stilbene dimer, though its relative stereochemistry remained unsolved. Labruscol was recovered as a pure compound (>93%) in sufficient amounts (41 mg) to allow assessment of its biological activity (cell viability, cell invasion and apoptotic activity) on two different cell lines, including one human skin melanoma cancer cell line HT-144 and a healthy human dermal fibroblast (HDF) line. This compound induced almost 100% of cell viability inhibition in the cancer line at a dose of 100 μM within 72 h of treatment. However, at all tested concentrations and treatment times, resveratrol displayed an inhibition of the cancer line viability higher than that of labruscol in the presence of fetal bovine serum. Both compounds also showed differential activities on healthy and cancer cell lines. Finally, labruscol at a concentration of 1.2 μM was shown to reduce cell invasion by 40%, although no similar activity was observed with resveratrol. The cytotoxic activity of this newly-identified dimer is discussed.

Trifluoromethylselenylated compounds are emergent compounds with interesting physicochemical properties that still suffer from a lack of efficient synthetic methods. We recently developed an efficient one-pot strategy to generate in situ CF3SeCl and use it in various reactions. Herein, we continue our study of the reactivity scope of this preformed reagent. Cross-coupling reactions with aromatic and heteroaromatic boronic acids have been investigated. The expected products have been obtained, using a stoichiometric amount of copper, with moderate yields.

In the present study, resveratrol and various oligomeric derivatives were obtained from a 14 L bioreactor culture of elicited grapevine cell suspensions (Vitis labrusca L.). The crude ethyl acetate stilbene extract obtained from the culture medium was fractionated by centrifugal partition chromatography (CPC) using a gradient elution method and the major stilbenes contained in the fractions were subsequently identified by using a 13C-NMR-based dereplication procedure and further 2D NMR analyses including HSQC, HMBC, and COSY. Beside δ-viniferin (2), leachianol F (4) and G (4′), four stilbenes (resveratrol (1), ε-viniferin (5), pallidol (3) and a newly characterized dimer (6)) were recovered as pure compounds in sufficient amounts to allow assessment of their biological activity on the cell growth of three different cell lines, including two human skin malignant melanoma cancer cell lines (HT-144 and SKMEL-28) and a healthy human dermal fibroblast HDF line. Among the dimers obtained in this study, the newly characterized resveratrol dimer (6) has never been described in nature and its biological potential was evaluated here for the first time. ε-viniferin as well as dimer (6) showed IC50 values on the three tested cell lines lower than the ones exerted by resveratrol and pallidol. However, activities of the first two compounds were significantly decreased in the presence of fetal bovine serum although that of resveratrol and pallidol was not. The differential tumor activity exerted by resveratrol on healthy and cancer lines was also discussed.

Stilbenes are defense molecules produced by grapevine in response to stresses including various elicitors and signal molecules. Together with their prominent role in planta, stilbenes have been the center of much attention in recent decades due to their pharmaceutical properties. With the aim of setting up a cost-effective and high purity production of resveratrol derivatives, hairy root lines were established from Vitis vinifera cv Pinot Noir 40024 to study the organ-specific production of various stilbenes. Biomass increase and stilbene production by roots were monitored during flask experiments. Although there was a constitutive production of stilbenes in roots, an induction of stilbene synthesis by methyl jasmonate (MeJA) after 18 days of growth led to further accumulation of ε-viniferin, δ-viniferin, resveratrol and piceid. The use of 100 µM MeJA after 18 days of culture in the presence of methyl-β-cyclodextrins (MCDs) improved production levels, which reached 1034µg/g fresh weight (FW) in roots and 165 mg/L in the extracellular medium, corresponding to five-and 570-foldincrease in comparison to control. Whereas a low level of stilbene excretion was measured in controls, addition of MeJA induced excretion of up to 37% of total stilbenes. The use of MCDs increased the excretion phenomenon even more, reaching up to 98%. Our results demonstrate the ability of grapevine hairy roots to produce various stilbenes. This production was significantly improved in response to elicitation by methyl jasmonate and/or MCDs. This supports the interest of using hairy roots as a potentially valuable system for producing resveratrol derivatives.

α-Series gangliosides define a particular sub-class of glycosphingolipids containing sialic acid α2,6-linked to GalNAc residue that was isolated as a minor compound from the brain. The sialyltransferase ST6GalNAc V was cloned from mouse brain and showed α2,6-sialyltransferase activity almost exclusively for GM1b, to form GD1α and is considered as the main enzyme involved in the biosynthesis of α-series gangliosides. Recently, ST6GALNAC5 was identified as one of the genes over-expressed in breast cancer cell populations selected for their ability to produce brain metastasis. However, the capacity of human breast cancer cells to produce α-series gangliosides has never been clearly demonstrated. Here, we show by stable transfection and MS-MS analysis of total glycosphingolipids that ST6GALNAC5 expressing MDA-MB-231 breast cancer cells accumulate GD1α ganglioside (IV3Neu5Ac1, III6Neu5Ac1Gg4-Cer). [ABSTRACT FROM AUTHOR]