Photo-induced thiol-ene reactions for late-stage functionalization of unsaturated polyether macrocycles: regio and diastereoselective access to macrocyclic dithiol derivatives.

Double hydrothiolation of bis enol ether macrocycles was achieved under photo-mediated conditions. The thiol-ene reactions afford a fully regioselective anti-Markovnikov post-functionalization. Thanks to the use of ethanedithiol as reagent, moderate to excellent diastereoselectivity was accomplished leading to macrocycles containing four defined stereocenters in only three steps from 1,4-dioxane, tetrahydrofuran (THF) or tetrahydropyran (THP).

Circularly-Polarized Electrochemiluminescence from a Chiral Bispyrene Organic Macrocycle.

The first observation of circular polarization of electrochemiluminescence (ECL) from a purely organic derivative is reported. A bispyrene scaffold mounted on a constrained polyether macrocycle displaying intense excimer fluorescence and highly circularly-polarized (CP) photoluminescence has been selected for this purpose. The compound displays an ECL dissymmetry factor of about |8×10-3 |, which is in good agreement with the corresponding photoluminescence value. This observation is the first step towards the molecular engineering of tailored dyes that can act as both ECL and CP-ECL reporters for (bio)analysis by bringing a new level of information when dealing with chiral environments. Additionally, it provides an extra dimension to the ECL phenomenon and opens the way to chiral detection and discrimination.

Diastereoselective synthesis of trifluoromethylated 1,3-dioxanes by intramolecular oxa-Michael reaction.

A highly diastereoselective synthesis of trifluoromethylated 1,3-dioxanes is described. The reaction proceeds by an addition/oxa-Michael sequence and works efficiently under mild reaction conditions, with a good substrate scope and acceptable to good yields.

Synthesis of the Acyclic Carbon Skeleton of Filipin III.

The synthesis of the carbon skeleton of filipin III, a polyenic macrolactone possessing 11 stereogenic centers, was achieved using a convergent strategy with the longest linear sequence of 19 steps starting from hexanal. Construction of the polyene was realized using two successive Heck couplings as the key steps. Control of the stereogenic centers of the polyol fragment was performed by utilizing an Evans aldolization, a 1,3-syn aldolization, enantio- and diastereoselective allylations, a hemiacetalization/oxa-Michael sequence, and a 1,3-syn reduction. The polyol and polyenic fragments were coupled using a 1,5-anti diastereoselective aldolization followed by a 1,3-anti reduction.

Total Synthesis of (+)-Cryptocaryol A Using a Prins Cyclization/Reductive Cleavage Sequence.

The total synthesis of (+)-cryptocaryol A was achieved in 20 steps from (R)-glycidol. The key steps were a Prins cyclization/reductive cleavage sequence to construct the C5-C11 polyol fragment, a diastereoselective aldol reaction to control the stereogenic center at C13, and a stereocontrolled reduction to introduce the stereogenic center at C15.

Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions.

We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

UV-induced bursting of cell-sized multicomponent lipid vesicles in a photosensitive surfactant solution.

We study the behavior of multicomponent giant unilamellar vesicles (GUVs) in the presence of AzoTAB, a photosensitive surfactant. GUVs are made of an equimolar ratio of dioleoylphosphatidylcholine (DOPC) and dipalmitoylphosphatidylcholine (DPPC) and various amounts of cholesterol (Chol), where the lipid membrane shows a phase separation into a DPPC-rich liquid-ordered (L(o)) phase and a DOPC-rich liquid-disordered (L(d)) phase. We find that UV illumination at 365 nm for 1 s induces the bursting of a significant fraction of the GUV population. The percentage of UV-induced disrupted vesicles, called bursting rate (Y(burst)), increases with an increase in [AzoTAB] and depends on [Chol] in a non-monotonous manner. Y(burst) decreases when [Chol] increases from 0 to 10 mol % and then increases with a further increase in [Chol], which can be correlated with the phase composition of the membrane. We show that Y(burst) increases with the appearance of solid domains ([Chol] = 0) or with an increase in area fraction of L(o) phase (with increasing [Chol] ≥ 10 mol %). Under our conditions (UV illumination at 365 nm for 1 s), maximal bursting efficiency (Y(burst) = 53%) is obtained for [AzoTAB] = 1 mM and [Chol] = 40 mol %. Finally, by restricting the illumination area, we demonstrate the first selective UV-induced bursting of individual target GUVs. These results show a new method to probe biomembrane mechanical properties using light as well as pave the way for novel strategies of light-induced drug delivery.

Metatranscriptomics of cheese microbial communities: Efficiency of RNA extraction from various cheese types and of mRNA enrichment.

Microbial communities from cheeses contribute to the development of typical organoleptic properties. Metatranscriptomic analyses can be used to provide a global picture of the functioning of these communities. Our objective was to evaluate the efficiency of RNA extraction from various cheese types and to evaluate mRNA enrichment procedures for metatranscriptomic analyses. For the 32 tested cheese brands, corresponding to five cheese types, the extraction yield varied from 1 µg to 363 µg RNA per gram of cheese and, overall, the yield was lower for fresh cheeses and for the core of pressed cooked cheeses than for the other cheese types. Pressed cooked cheeses also had a lower RNA integrity than the other cheese types. For total RNA extracts from four cheeses, approximately 99% of the sequencing reads corresponded to ribosomal RNA, and mRNA enrichment by RiboPOOL and FastSelect kits decreased this percentage to a range of 75 to 97% and of 53 to 76%, respectively. Comparison of RNA libraries after mRNA enrichment with libraries of undepleted total RNA showed that the FastSelect mRNA enrichment had a lower impact on the gene expression profiles of five target cheese species than the riboPOOL kit and the oligo (dT) selection method. The procedures that we describe in the present study may be useful for metatranscriptomic analysis of various cheese types.

Combined spectroscopic studies on post-functionalized Au25 cluster as an ATR-FTIR sensor for cations.

Recently, significant research activity has been devoted to thiolate-protected gold clusters due to their attractive optical and electronic properties. These properties as well as solubility and stability can be controlled by post-synthetic modification strategies. Herein, the ligand exchange reaction between Au25(2-PET)18 cluster (where 2-PET is 2-phenylethanethiol) and di-thiolated crown ether (t-CE) ligands bearing two chromophores was studied. The post-functionalization aimed to endow the cluster with ion binding properties. The exchange reaction was followed in situ by UV-vis, 1H NMR and HPLC. MALDI mass analysis revealed the incorporation of up to 5 t-CE ligands into the ligand shell. Once functionalized MALDI furthermore showed complexation of sodium ions to the cluster. ATR-FTIR spectroscopic studies using aqueous solutions of K+, Ba2+, Gd3+ and Eu3+ showed noticeable spectral shifts of the C-O stretching band around 1100 cm-1 upon complexation. Further spectral changes point towards a conformational change of the two chromophores that are attached to the crown ether. Density functional theory calculations indicate that the di-thiol ligand bridges two staple units on the cluster. The calculations furthermore reproduce the spectral shift of the C-O stretching vibrations upon complex formation and reveal a conformational change that involves the two chromophores attached to the crown ether. The functionalized clusters have therefore attractive ion sensing properties due to the combination of binding properties, mainly due to the crown ether, and the possibility for signal transduction via an induced conformational change involving chromophore units.

Tuning symmetry breaking charge separation in perylene bichromophores by conformational control.

Understanding structure-property relationships in multichromophoric molecular architectures is a crucial step in establishing new design principles in organic electronics as well as to fully understand how nature exploits solar energy. Here, we study the excited state dynamics of three bichromophores consisting of two perylene chromophores linked to three different crown-ether backbones, using stationary and ultrafast electronic spectroscopy combined with molecular dynamics simulations. The conformational space available to the bichromophores depends on the structure and geometry of the crown-ether and can be significantly changed upon cation binding, strongly affecting the excited-state dynamics. We show that, depending on the conformational restrictions and the local environment, the nature of the excited state varies greatly, going from an excimer to a symmetry-broken charge separated state. These results can be rationalised in terms of a structure-property relationship that includes the effect of the local environment.

Combined reversible switching of ECD and quenching of CPL with chiral fluorescent macrocycles.

Straightforward synthesis and resolution of a series of chiral fluorescent macrocycles are presented, together with their electronic circular dichroism (ECD), strong excimer fluorescence (EF, λ 300 to 650 nm) and allied highly circularly polarized luminescence (CPL, g lum up to 1.7 × 10-2). The ECD, EF and CPL responses are strongly affected by the presence of metal ions (Na+, Ba2+) thanks to deep conformational changes. While ECD signals can be almost completely reversibly inverted upon the complexation/decomplexation of metal ions in a typical binary response, CPL signals are reversibly quenched concomitantly. The designed macrocycles display thus a remarkable combination of both +/- ECD and on/off CPL reversible switching.

Diastereo- and enantioselective synthesis of 1,3,5,7-tetraol structural units using a Prins cyclisation-reductive cleavage sequence.

Stereocontrolled and efficient access to all the diastereomers of 1,3,5,7-tetraol structural units was developed using a Prins cyclisation-reductive cleavage sequence applied to tetrahydropyran aldehydes. Furthermore, these tetraols can be selectively functionalized.