Determination of aqueous inclusion complexation constants and stoichiometry of alkyl(methyl)-methylimidazolium-based ionic liquid cations and neutral cyclodextrins by affinity capillary electrophoresis

Affinity CE (ACE) method was developed to characterize the complex formation between seven alkyl(methyl)methylimidazolium-based ionic liquid (IL) cations and eight neutral cyclodextrins (CD). The effective mobility data of the IL cations were processed according to classical nonlinear and linear treatments to obtain the complex stoichiometry and formation constant K. The majority of systems followed a 1:1 complexation stoichiometry model but in four cases a 1:2 stoichiometry was better satisfied. The K values obtained for each IL were compared to elucidate the main influences of IL and CD nature. The availability of these data should lend support to various application areas, including the screening and tailoring of new interactions in the solution for CE.     

Thermodynamic and structural properties of Eu3+ complexes of a new 12-membered tetraaza macrocycle containing pyridine and N-glutaryl groups as pendant arms: characterization of three complexing successive phases

A new polyazamacrocyclic ligand (called pctga) containing pyridine and N-glutaryl arms has been synthesized as a potential agent for MRI (magnetic resonance imaging). Three series of successive complexes formed with Eu(3+) were characterized by at least two of the following methods: potentiometry, EXAFS or luminescence spectrometry. In the immediate complexes [EuH(h)(pctga)(H2O)6](h-3)+**, the metal ion is bound to the oxygen atoms of the three internal carboxylate groups and to six water molecules. As the lanthanide moves into the macrocyclic cavity, these species rapidly evolve into the intermediate metastable complexes [EuH(h)(pctga)(H2O)4](h-3)+*. The formation of two new bonds with the nitrogen atoms of the tetraazamacrocycle decreased the number of coordinated water molecules to four. In the final thermodynamically stable complexes [EuH(h)(pctga)(H2O)(2)](h-3)+, the pctga is bound to the europium(III) in a heptadentate manner, via the four nitrogen atoms of the tetraazamacrocycle and the three oxygen atoms of the internal carboxylate groups. The coordination number of the metal ion is completed to nine with two inner-sphere water molecules. The mean hydration numbers were calculated from the values of the bimolecular quenching constant k(q) of the luminescence species. The thermodynamic parameters corresponding to the protonation constants of the ligand and to the formation constants of the various intermediate and final complexes were determined from potentiometric measurements. They show that the complex species have some specific thermodynamic and structural properties inherent to the N-glutaryl groups and to the pyridine cycle. The insertion of this aromatic substructure rigidifies the ligand and sensibly diminishes the value of the overall formation constant (log beta(110) = 18.66(5)). This whole study allows us to propose a complexation mechanism for the system Eu(3+)/pctga in solution which is a mixture of the ones determined for the ligands dota and tced.     

The Hahn-Banach Property and the Axiom of Choice

We work in set theory ZF without axiom of choice. Though the Hahn-Banach theorem cannot be proved in ZF, we prove that every Gateaux-differentiable uniformly convex Banach space E satisfies the following continuous Hahn-Banach property: if p is a continuous sublinear functional on E, if F is a subspace of E, and if f: F → ? is a linear functional such that f ≤ p|F then there exists a linear functional g : E → ? such that g extends f and g ≤ p. We also prove that the continuous Hahn-Banach property on a topological vector space E is equivalent to the classical geometrical forms of the Hahn-Banach theorem on E. We then prove that the axiom of Dependent choices DC is equivalent to Ekeland's variational principle, and that it implies the continuous Hahn-Banach property on Gateaux-differentiable Banach spaces. Finally, we prove that, though separable normed spaces satisfy the continuous Hahn-Banach property, they do not satisfy the whole Hahn-Banach property in ZF+DC.     

Synthesis and Biological Activity of 3-(Heteroaryl)quinolin-2(1H)-ones Bis-Heterocycles as Potential Inhibitors of the Protein Folding Machinery Hsp90

In the context of our SAR study concerning 6BrCaQ analogues as C-terminal Hsp90 inhibitors, we designed and synthesized a novel series of 3-(heteroaryl)quinolin-2(1H), of types 3, 4, and 5, as a novel class of analogues. A Pd-catalyzed Liebeskind–Srogl cross-coupling was developed as a convenient approach for easy access to complex purine architectures. This series of analogues showed a promising biological effect against MDA-MB231 and PC-3 cancer cell lines. This study led to the identification of the best compounds, 3b (IC₅₀ = 28 µM) and 4e, which induce a significant decrease of CDK-1 client protein and stabilize the levels of Hsp90 and Hsp70 without triggering the HSR response.     

Self-assembled gel tubes,filaments and 3D-printing with in situ metal nanoparticle formation and enhanced stem cell growth

This paper reports simple strategies to fabricate self-assembled artificial tubular and filamentous systems from a low molecular weight gelator (LMWG). In the first strategy, tubular ‘core–shell’ gel structures based on the dibenzylidenesorbitol-based LMWG DBS-CONHNH₂ were made in combination with the polymer gelator (PG) calcium alginate. In the second approach, gel filaments based on DBS-CONHNH₂ alone were prepared by wet spinning at elevated concentrations using a ‘solvent-switch’ approach. The higher concentrations used in wet-spinning prevent the need for a supporting PG. Furthermore, this can be extended into a 3D-printing method, with the printed LMWG objects showing excellent stability for at least a week in water. The LMWG retains its unique ability for in situ precious metal reduction, yielding Au nanoparticles (AuNPs) within the tubes and filaments when they are exposed to AuCl₃ solutions. Since the gel filaments have a higher loading of DBS-CONHNH₂, they can be loaded with significantly more AuNPs. Cytotoxicity and viability studies on human mesenchymal stem cells show that the DBS-CONHNH₂ and DBS-CONHNH₂/alginate hybrid gels loaded with AuNPs are biocompatible, with the presence of AuNPs enhancing stem cell metabolism. Taken together, these results indicate that DBS-CONHNH₂ can be shaped and 3D-printed, and has considerable potential for use in tissue engineering applications.

Simple fabrication and 3D-printing methods are used to generate tubes and filaments from self-assembled gels, which can be loaded in situ with gold nanoparticles, with the resulting gels encouraging stem cell proliferation.     

Supercritical fluid chromatography coupled to mass spectrometry for lipidomics

Supercritical fluid chromatography (SFC) has experienced a particular revival in recent years thanks to the development of robust and efficient commercial systems. Because of its physico‐chemical properties, supercritical carbon dioxide (CO₂) mixed with cosolvents and additives is particularly suitable for SFC to allow the elution of compounds of different polarities and more particularly complex lipids. Hyphenation with mass spectrometry (MS) is increasingly described in the literature but still requires many further developments in order to be as user‐friendly as coupling with liquid chromatography. The basic concepts of SFC and MS hyphenation will be first considered. Then a representative example of method development in lipidomics will be introduced. In conclusion, the challenges and future needs in this field of research will be discussed.     

Transformation of n- hexane on PtAl/MCM-41 and PtAl/SBA-15

PtAl/MCM-41 and PtAl/SBA-15 materials were prepared by post-synthesis alumination followed by introduction of platinum by ion exchange. The samples were characterized by pyridine adsorption followed by FTIR and TPR of hydrogen. The catalytic behavior was explored in the transformation of n-hexane. This revised version was published online in August 2006 with corrections to the Cover Date.     

Xanthine Oxidase Inhibitors from Filipendula ulmaria (L.) Maxim. and Their Efficient Detections by HPTLC and HPLC Analyses

Filipendula ulmaria is a plant commonly used for the treatment of several pathologies, such as diarrhoea, ulcers, pain, stomach aches, fevers, and gout. Our study focused on the use of F. ulmaria for the treatment of gout disease. We first studied the chemical composition of a methanolic extract of the aerial parts and demonstrated its xanthine oxidase (XO) inhibitory activity. Then, we performed a fractionation and evaluated the most XO inhibitory active fractions by UV measurement. Purification of some fractions allowed the determination of the inhibitory activity of pure compounds. We demonstrated that spiraeoside, a glycosylated flavonoid, possesses an activity around 25 times higher than allopurinol, used as a reference in the treatment of gout disease. In order to easily and quickly identify potent inhibitors in complex matrix, we developed a complementary strategy based on an HPLC method and an Effect Directed Assay (EDA) method combining HPTLC and biochemical assays. The HPLC method, capable of determining compounds exhibiting interactions with the enzyme, could be an efficient strategy for evaluating potent enzyme inhibitors in a complex mixture. This strategy could be applied for quantitative assays using LC/MS experiments.