Glycine-betaine-derived ionic liquids: Synthesis, characterization and ecotoxicological evaluation.

Ionic Liquids (ILs) are generically regarded as environmentally "harmless" and thus, assumed as "non-toxic". However, due to the endless design possibilities, their ecotoxicological profile is still poorly known. An accurate knowledge on the toxicity of a substance is required, under the scope of environmental regulation worldwide, before their application and commercialization. Knowledge on the relationship between the chemical structure and toxic effects is essential for the future design of more biocompatible solvents. Focusing on the use of ILs as base lubricants, lubricant additives, or even as potential working fluids for absorption heat pumps, the knowledge on its environmental impact is of great importance, due to the possibility of spills. In this specific context, four analogues of glycine-betaine-based ILs (AGB-ILs) and four glycine-betaine based ILs (GB-ILs) were synthesized and characterized. Their ecotoxicity was assessed using representatives of two trophic levels in aquatic ecosystems, the bacteria Allivibrio fischeri (commonly used as a screening test organism) and the microalgae Raphidocelis subcapitata (as an alternative test organism that has been proven very sensitive to several IL families). The microalgae were more sensitive than the bacteria, hence, following a precautionary principle, we recommend considering the toxicity towards microalgae as an indicator in future studies regarding the focused ILs. Although four of the studied ILs were derived from a natural amino acid, all were considered hazardous for the aquatic environment, disproving the primary theory that all ILs derived from natural compounds are benign. Furthermore, the modification in the structure of anion and the cation can lead to the increase of toxicity.

Liquid crystal-based tunable photodetector operating in the telecom C-band.

Liquid crystal (LC) microcells monolithically integrated on the surface of InGaAs based photodiodes (PDs) are demonstrated. These LC microcells acting as tunable Fabry-Perot filters exhibit a wavelength tunability of more than 100 nm around 1550 nm with less than 10V applied voltage. Using a tunable laser operating in the S and C bands, photocurrent measurements are performed. On a 70 nm tuning range covered with a driving voltage lower than 7V, the average sensitivity for the PD is 0.4 A/W and the spectral linewidth of the LC filter remains constant, showing a FWHM of 1.5 nm. Finally, the emission spectrum from an Er-doped fiber is acquired by using this tunable PD as a micro-spectrometer.

Impact of the concentration in polymer on the dynamic behavior of Polymer Stabilized Ferroelectric Liquid Crystal using Snap-shot Mueller Matrix Polarimetry.

Experimental results are presented related to the dynamic behaviour of Polymer Stabilized Ferro-electric Liquid Crystal (PSFLC) samples under external applied electric field, using Snap-shot Mueller Matrix Polarimetry (SMMP) and Mueller Matrix (MM) formalism. Different polarimetric coefficients are simultaneously extracted from each channeled spectrum measured with this full-optical SMMP technique. The impact of the concentration of polymer present into the liquid crystal cell on this dynamic behaviour is studied, permitting a direct and quick characterisation of the material. The results obtained for PSFLC are compared with those already measured for pure Surface Stabilized Ferro-electric Liquid Crystal (SSFLC) samples, which correspond to a 0% concentration in polymer.

Ecotoxicity interspecies study of ionic liquids based on phosphonium and ammonium cations.

This work studies the effects of different bromide-based ionic liquids, with phosphonium and ammonium cations, towards several environmental biomodels: Daphnia magna, Allivibrio fischeri, Raphidocelis subcapitata. Results indicate that toxicity clearly depends on the biomodel, Allivibrio fischeri being the least sensitive one while Daphnia magna is more severely affected in the presence of the studied ionic liquids. In most of the cases, phosphonium moieties are less toxic than ammonium ionic liquids. Furthermore, a prediction about the oral toxicity and carcinogenicity of the studied ionic liquids has been also carried out, showing that these chemical structures may suggest significant toxicity but not present genotoxic or nongenotoxic carcinogenicity.

Time-resolved switching analysis of a ferroelectric liquid crystal by snapshot Mueller matrix polarimetry.

An experimental snapshot Mueller matrix polarimeter based on wavelength polarization coding is used to get a time-resolved description of electric-field-induced fast transition within a ferroelectric liquid-crystal cell. The parameters extracted from experimental Mueller matrices are linked to the molecule director distribution to further determine the average trajectory and the collective behavior of these molecules while they switch over to another state.

Study of Iron Piperazine-Based Chelators as Potential Siderophore Mimetics.

Gram-negative bacteria's resistance such as Pseudomonas aeruginosa and the Burkholderia group to conventional antibiotics leads to therapeutic failure. Use of siderophores as Trojan horses to internalize antibacterial agents or toxic metals within bacteria is a promising strategy to overcome resistance phenomenon. To combat the Pseudomonas sp, we have synthesized and studied two piperazine-based siderophore mimetics carrying either catecholate moieties (1) or hydroxypyridinone groups (2) as iron chelators. These siderophore-like molecules were prepared in no more than four steps with good global yields. The physicochemical study has highlighted a strong iron affinity since their pFe values were higher than 20. 1 possesses even a pFe value superior than those of pyoverdine, the P. aeruginosa endogenous siderophore, suggesting its potential ability to compete with it. At physiological pH, 1 forms mainly a 2:3 complex with iron, whereas two species are observed for 2. Unfortunately, the corresponding Ga(III)-1 and 2 complexes showed no antibacterial activity against P. aeruginosa DSM 1117 strain. The evaluation of their siderophore-like activity showed that 1 and 2 could be internalized by the bacteria.

Dispersions of Goethite Nanorods in Aprotic Polar Solvents.

Colloidal suspensions of anisotropic nanoparticles can spontaneously self-organize in liquid-crystalline phases beyond some concentration threshold. These phases often respond to electric and magnetic fields. At lower concentrations, usual isotropic liquids are observed but they can display very strong Kerr and Cotton-Mouton effects (i.e., field-induced particle orientation). For many examples of these colloidal suspensions, the solvent is water, which hinders most electro-optic applications. Here, for goethite (α-FeOOH) nanorod dispersions, we show that water can be replaced by polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO), without loss of colloidal stability. By polarized-light microscopy, small-angle X-ray scattering and electro-optic measurements, we found that the nematic phase, with its field-response properties, is retained. Moreover, a strong Kerr effect was also observed with isotropic goethite suspensions in these polar aprotic solvents. Furthermore, we found no significant difference in the behavior of both the nematic and isotropic phases between the aqueous and non-aqueous dispersions. Our work shows that goethite nanorod suspensions in polar aprotic solvents, suitable for electro-optic applications, can easily be produced and that they keep all their outstanding properties. It also suggests that this solvent replacement method could be extended to the aqueous colloidal suspensions of other kinds of charged anisotropic nanoparticles.

Synthesis, iron(III) complexation properties, molecular dynamics simulations and P. aeruginosa siderophore-like activity of two pyoverdine analogs.

P. aeruginosa ranks among the top five organisms causing nosocomial infections. Among the many novel strategies for developing new therapeutics against infection, targeting iron uptake mechanism seems promising as P. aeruginosa needs iron for its growth and survival. To scavenge iron, the bacterium produces siderophores possessing a very high affinity towards Fe(III) ions such as pyoverdines. In this work, we decided to study two pyoverdine analogs, aPvd2 and aPvd3, structurally close to the endogen pyoverdine. The pFe constants calculated with the values of formation showed a high affinity of aPvd3 towards Fe(III). Molecular dynamics calculations demonstrated that aPvd3-Fe forms with Fe(III) stable 1:1 complexes in water, whereas aPvd2 does not. Only aPvd3 is able to increase the bacterial growth and represents thus an alternative to pyoverdine for iron acquisition by the bacterium. The aPvd2-3 interaction studies with a lipid membrane indicated that they were unable to interact and to cross the plasma membrane of bacteria by passive diffusion. Consequently, the penetration of aPvd3 is ruled by a transport membrane protein. These results showed that aPvd3 may be used to inhibit pyoverdine uptake or to promote the accumulation and release of antibiotics into the cell following a Trojan horse strategy.

Isotropic Elastic Stress Induced Large Temperature Range Liquid Crystal Blue Phase at Room Temperature.

A thermodynamically stable blue phase (BP) based on the conventional rod like nematogen is demonstrated for the first time at room temperature by only diluting a chiral-nematic mixture with the help of some nonmesogenic isotropic liquid. It is observed that addition of this isotropic liquid does not only stabilize the BPs at room temperature, but also significantly improves the temperature range (reversible during heating and cooling) of the BPs to the level of more than 28 °C. Apart from that, we have observed its microsecond electro-optic response time and, external electric field induced wavelength tuning, which are the two indispensable requirements for next generation optical devices, photonic displays, lasers, and many more. Here we propose that the isotropic liquid plays two crucial roles simultaneously. On one hand, it reduces the effective elastic moduli (EEM) of the BP mixtures and stabilizes the BPs at room temperature, and on the other hand, it increases the symmetry of the mutual orientation ordering among the neighboring unit cells of the BP. Hence, the resultant mixture becomes better resistive to some microscopic change due to the change in temperature, even over a large range.

Thermodynamic and spectroscopic studies of copper (II) complexes with three bis(amide) ligands derived from L-tartaric acid.

The interactions of three bis(amide) ligands derived from tartaric acid with copper (II) were investigated in aqueous solution by a combination of potentiometry, UV-vis spectrophotometry, electron paramagnetic resonance (EPR), and mass spectrometry. The formation constants of the complexes were measured and their relative structures were reported. The sites of complexation of these ligands are investigated based mostly on their electronic and EPR spectra and on the comparison with the behaviour of some analog compounds.

Evidence of chitosan-mediated reduction of Au(III) to Au(0) nanoparticles under electron beam by using OH˙ and e⁻(aq) scavengers.

Selective scavengers of e(-)(aq) and OH˙ radicals were used to investigate the radiolytic synthesis of gold nanoparticles from Au(III) solutions in the presence of chitosan. This reaction does not exclusively follow the direct reduction by solvated electrons. Irradiation generates short-lived and long-lived reductive species derived from chitosan that efficiently convert Au(III) into Au(0) which aggregates to form clusters.

Use of analytical microscopy to analyze the speciation of copper and chromium ions onto a low-cost biomaterial.

In this paper, we present our study of the speciation of copper and hexavalent chromium sorbed onto a lignocellulosic substrate, using analytical microscopy. The lignocellulosic substrate constitutes a low-cost biomaterial that can be used in wastewater treatment. Transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDXS) was used to determine the speciation of the two metal ions on the constitutive moieties of the lignocellulosic substrate. The use of a staining agent sensitive to carbon unsaturation allowed us to differentiate between the microstructures rich in lignin entities and those rich in cellulose entities. The EDX analysis showed that metal ions are preferentially sorbed onto microstructures rich in lignin moieties. The energy electron loss spectroscopy (EELS) was used to determine the oxidation states of chromium in association with lignocellulosic moieties. We showed that the sorption process of hexavalent chromium requires the reduction of Cr(VI) into Cr(III) and the probable oxidation of lignin moieties.

Synthesis, Physicochemical Studies, Molecular Dynamics Simulations, and Metal-Ion-Dependent Antiproliferative and Antiangiogenic Properties of Cone ICL670-Substituted Calix[4]arenes.

Iron chelators, through their capacity to modulate the iron concentration in cells, are promising molecules for cancer chemotherapy. Chelators with high lipophilicity easily enter into cells and deplete the iron intracellular pool. Consequently, iron-dependent enzymes, such as ribonucleotide reductase, which is over-expressed in cancer cells, become nonfunctional. A series of calix[4]arene derivatives substituted at the lower rim by ICL670, a strong FeIII chelator, have been synthesized. Physicochemical properties and antiproliferative, angiogenesis, and tumorigenesis effects of two calix[4]arenes mono- (5a) or disubstituted (5b) with ICL670 have been studied. These compounds form metal complexes in a ratio of one to two ligands per FeIII atom as shown by combined analyses of the protometric titration curves and ESIMS spectra. The grafting of an ICL670 group on a calix[4]arene core does not significantly alter the acid-base properties, but improves the iron-chelating and lipophilicity properties. The best antiproliferative and anti-angiogenic results were obtained with calix[4]arene ligand 5a, which possesses the highest corresponding properties. Analyses of molecular dynamics simulations performed on the two calix[4]arenes provide three-dimensional structures of the complexes and proved 5a to be the most stable upon complexation.

Synthesis, physico-chemical properties and complexing abilities of new amphiphilic ligands from D-galacturonic acid.

This paper describes a convenient and efficient synthesis of new complexing surfactants from d-galacturonic acid and n-octanol as renewable raw materials in a two-step sequence. In the first step, simultaneous O-glycosidation-esterification under Fischer conditions was achieved. The anomeric ratio of the products was studied based on the main experimental parameters and the activation mode (thermal or microwave). In the second step, aminolysis of the n-octyl ester was achieved with various functionalized primary amines under standard thermal or microwave activation. The physico-chemical properties of these new amphiphilic ligands were measured and these compounds were found to exhibit interesting surface properties. Complexing abilities of one uronamide ligand functionalized with a pyridine moiety toward Cu(II) ions was investigated in solution by EPR titrations. A solid compound was also synthesized and characterized, its relative structure was deduced from spectroscopic data.

Thermodynamic and spectroscopic studies of Cu(II) and Ni(II) complexes with a new proline-threonine dipeptide ligand.

The interactions between a new proline-threonine dipeptide ligand with two metallic cations were investigated in aqueous solution. The metallic cations studied were the copper(II) and the nickel(II), which are involved in many biological processes. The combination of potentiometry, UV-visible spectrophotometry, EPR, and mass spectrometry was used to determine the formation constants of the complexes and their structure in solution. The complexation sites were identified using electronic absorption and EPR spectroscopies. Copper complexes were obtained as square planar or square pyramidal mononuclear species, whereas nickel complexes were obtained as dinuclear species with an octahedral geometry.

Synthesis, characterization and dioxygen reactivity of copper(I) complexes with glycoligands.

A new family of copper(I) complexes with "glycoligands" containing a central saccharide scaffold, with 2-picolyl ether groups or 2-picolylamine or N-imidazolylamine groups, has been prepared and characterized. For this purpose, the following tetradentate ligands have been synthesized: methyl 2,3-di-O-(2-picolyl)-alpha-D-lyxofuranoside (L1), 1,5-anhydro-2-deoxy-3,4-di-O-(2-picolyl)-d-galactitol (L2), 5-(amino-N-(2-salicyl))-5-deoxy-1,2-O-isopropylidene-3-O-(2-picolyl)-alpha-D-xylofuranose (L3), and 5-(amino-N-(2-salicyl))-5-deoxy-1,2-O-isopropylidene-3-O-(methylimidazol-2-yl)-alpha-D-xylofuranose (L4). The ligands and the complexes were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopies, ESI mass spectrometry, and cyclic voltammetry. Collaterally with the experimental work, HF-DFT(B3LYP/6-31G*) computations were performed to obtain additional structural information. The Cu(I) complexes are found to be pentacoordinated. The redox properties and the O2-reactivity of the Cu(I)Ln complexes have been studied. Reactions of Cu(I) complexes with dioxygen in ethanol yield stable Cu(II) complexes as confirmed by UV-visible spectrophotometry and EPR spectroscopy.

EXAFS and XANES studies of retention of copper and lead by a lignocellulosic biomaterial.

Lignocellulosic substrate (LS), which is a low cost biomaterial, has a strong complexing ability and can be used in the treatment of wastewaters as biosorbentto remove heavy metals. The speciation of copper and lead to this biomaterial has been studied by X-ray absorption spectroscopy. The copper(II) has a 6-coordinate structure with four oxygen atoms in the equatorial plane at 1.95 A and two in axial position at 2.35 A. In the case of lead a particularly low coordination number of about 3 has been obtained. The combination of extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) suggested that Cu and Pb are bound to the surface of LS through carboxylic moieties.