Photoinduced Formation of Cubyl Aryl Thioethers and Synthesis of Monocubyl Analogue of Dapsone.

1,4-Disubstituted cubyl aryl thioethers were generated from the corresponding iodocubanes and aryl thiolates upon UV irradiation in dimethyl sulfoxide at room temperature. This simple procedure was found to be compatible with a variety of substituted aryl thiolates. This finding paved the way to a synthesis of the monocubyl analogue of dapsone, a key molecule in the treatment of leprosy, also known as Hansen's disease, and of acne.

Theoretical, Semiempirical, and Experimental Solvatochromic Comparison Methods for the Construction of the α1 Scale of Hydrogen-Bond Donation of Solvents.

Today, the hydrogen bonding donation (HBD) ability parameter of new solvents, α, is generally determined either by the Kamlet-Taft solvatochromic comparison of two probes, Reichardt betaine dye B(30) and 4-nitroanisole, or by the measurement of a single probe (e.g., solvatochromism of an iron coordination complex). This work highlights the shortcomings of these probes and recommends three replacement methods: (a) the theoretical comparison of the experimental and PCM-TD-DFT calculated transition energies ET(30) of B(30), (b) the semiempirical comparison of the experimental and McRae calculated ET(30), and, (c) for ionic liquids, the experimental comparison of ET(30) and ET(33) lying on the lower basicity of the betaine dye B(33) compared to B(30). These methods yield a new HBD parameter, α1, for 101 molecular solvents and 30 ionic liquids. The novelty is emblematic for water, with α1 = 1.54 instead of α (Kamlet-Taft) = 1.17. The solvent parameter α1 is not equivalent to the solute hydrogen-bond acidity parameter α2H, partly because of the self-association of HBD solvents.

Hydrogen-Bond Acceptance of Solvents: A 19F Solvatomagnetic ß1 Database to Replace Solvatochromic and Solvatovibrational Scales.

A variety of physicochemical properties and several hydrogen-bond donors have been used to define methods and to build scales aiming at measuring the hydrogen-bond acceptance of solvents. There is a great deal of confusion in these scales and methods. Solvatochromic, solvatocalorimetric, solvatovibrational, and 19F solvatomagnetic comparison methods are critically reviewed. Only two methods, the solvatomagnetic and the solvatocalorimetric ones, are able to yield reliable solvent hydrogen-bond acceptance scales. The solvatomagnetic ß1 scale defined from the 19F chemical shift of 4-fluorophenol is extended to many solvents including ionic liquids and green solvents. The results for about 240 hydrogen-bond acceptor solvents are organized in a numerical ß1 database. The comparison of ß1 with solvatochromic scales highlights their shortcomings, in particular for the important class of amphiprotic solvents. Therefore, the use of the 19F solvatomagnetic comparison method and of the solvatomagnetic ß1 scale is recommended in solvent effect studies.

In Vitro Evaluation of Biocompatibility of Uncoated Thermally Reduced Graphene and Carbon Nanotube-Loaded PVDF Membranes with Adult Neural Stem Cell-Derived Neurons and Glia.

Graphene, graphene-based nanomaterials (GBNs), and carbon nanotubes (CNTs) are being investigated as potential substrates for the growth of neural cells. However, in most in vitro studies, the cells were seeded on these materials coated with various proteins implying that the observed effects on the cells could not solely be attributed to the GBN and CNT properties. Here, we studied the biocompatibility of uncoated thermally reduced graphene (TRG) and poly(vinylidene fluoride) (PVDF) membranes loaded with multi-walled CNTs (MWCNTs) using neural stem cells isolated from the adult mouse olfactory bulb (termed aOBSCs). When aOBSCs were induced to differentiate on coverslips treated with TRG or control materials (polyethyleneimine-PEI and polyornithine plus fibronectin-PLO/F) in a serum-free medium, neurons, astrocytes, and oligodendrocytes were generated in all conditions, indicating that TRG permits the multi-lineage differentiation of aOBSCs. However, the total number of cells was reduced on both PEI and TRG. In a serum-containing medium, aOBSC-derived neurons and oligodendrocytes grown on TRG were more numerous than in controls; the neurons developed synaptic boutons and oligodendrocytes were more branched. In contrast, neurons growing on PVDF membranes had reduced neurite branching, and on MWCNTs-loaded membranes oligodendrocytes were lower in numbers than in controls. Overall, these findings indicate that uncoated TRG may be biocompatible with the generation, differentiation, and maturation of aOBSC-derived neurons and glial cells, implying a potential use for TRG to study functional neuronal networks.

Solvatomagnetic Comparison Method: A Proper Quantification of Solvent Hydrogen-Bond Basicity.

The hydrogen-bond-acceptor basicity of an important class of solvents, the amphiprotic solvents (water, alcohols, primary and secondary amides, and carboxylic acids), has not yet been properly parametrized. In this work, the first scale of solvent hydrogen-bond basicity applicable to amphiprotic solvents is established by means of a new method that compares the 19F NMR chemical shifts of 4-fluorophenol and 4-fluoroanisole in hydrogen-bond-acceptor solvents. This so-called solvatomagnetic comparison method is free of the shortcomings of the solvatochromic comparison method used so far and is easier to carry out than the pure base calorimetric method. The validity of the new scale is assessed by good linear correlations with spectroscopic, thermodynamic, and kinetic solute properties depending on the solvent hydrogen-bond basicity. In such correlation analysis of solvent effects on physicochemical properties, solvent and solute hydrogen-bond basicity scales must not be mixed, since it is shown here that solute and solvent scales are not equivalent. A comprehensive collection of parameters quantifying the hydrogen-bond basicity is presented for 168 solvents.

Straightforward synthesis of conductive graphene/polymer nanocomposites from graphite oxide.

The reduction of graphite oxide (GO) in the presence of reactive poly(methyl methacrylate) (PMMA), under mild biphasic conditions, directly affords graphene grafted with PMMA. The resulting nanocomposite shows excellent electrical conductivities resulting from the optimal dispersion and exfoliation of graphene in the polymer matrix.

Influence of the structure of polyfluorinated alcohols on Brønsted acidity/hydrogen-bond donor ability and consequences on the promoter effect.

The influence of substituents on the properties of tri- and hexafluorinated alcohols derived from 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was examined. Measurements of specific solvent-solute interactions revealed that H-bond donation (HBD) of fluorinated alcohols is sensitive to the steric hindrance of the OH group, whereas their Brønsted acidity is dependent only on the number of fluorine atoms. For hexafluorinated alcohols (HFAs), their association with amines characterized by X-ray diffraction showed that the balance between HBD and acidity is influenced by their structure. Moreover, the ability of HFAs to donate H-bonds is exerted in synclinal (sc), synperiplanar (sp), and also antiperiplanar (ap) conformations along the C-O bond. Comparison of the effects of fluorinated alcohols as promoting solvents in three reactions is reported. The positive correlation between rate constants and H-bonding donation ability for sulfide oxidation and imino Diels-Alder reaction brings to light the role of this property, while acidity might have a minor influence. In the third reaction, epoxide opening by piperidine, none of these properties can clearly be put forward at this stage.

Solubility switch of gold nanoparticles through hydrogen bond association.

Gold nanoparticles (AuNPs) coated with hexafluoroisopropanol moieties were prepared, and their surface was changed through simple hydrogen bond association with various amines, which allow orientation of the solubility of these AuNPs in determined organic solvents.