Effects of the dispersion methods in Pluronic F108 on the size and the surface composition of MWCNTs and their implications in toxicology assessment

Multi-walled carbon nanotubes (MWCNTs) were dispersed in water and in a Pluronic F108 solution by four different dispersion methods (stirring, bath sonication, stirring followed by bath sonication, and sonication probe). The effect of the dispersion methods were evaluated in terms of the particle size distribution, the agglomerates size, and the exfoliated fraction produced, as well as in terms of the surface and bulk chemical composition. Energy dispersive X-ray, X-ray photoelectron spectroscopy, and centrifugal liquid sedimentation techniques were used to characterize pristine MWCNTs and their dispersion. It is shown that, irrespective of the dispersion methods used, the MWCNTs are strongly wrapped with the biocompatible surfactant Pluronic F108, thereby modifying the external surface of the MWCNTs. Some shortening of MWCNTs and more wrapping are also observed when sonication methods are used. These observations raise questions as to the validity of results obtained in toxicology tests, in vitro and in vivo, were such methods of dispersion procedures are used.     

Stable (amino)(phosphino)carbenes: difunctional molecules

(Amino)(phosphino)carbenes are stable due to the donation of the nitrogen lone pair, the phosphino group remains strongly pyramidalized. Reactions can be performed selectively at the carbene center, but also at the phosphorus center leading to new stable carbenes. These difunctional molecules can be considered as hybrid ligands.     

1H, (19)F, and (31)P PGSE NMR diffusion studies on chiral organic salts: ion pairing and the dependence of a diffusion value on diastereomeric structure

1H, (19)F and (31)P pulsed field gradient spin-echo (PGSE) diffusion studies on chiral organic salts that contain hexacoordinate phosphate anions, namely tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) and bis(tetrachlorobenzenediolato)mono([1,1']binaphthalenyl-2,2'diolato)-phosphate(V) (BINPHAT), are reported. The first example of the dependence of a diffusion value on diastereomeric structure is presented. Marked solvent and concentration effects on the diffusion constants (D) of these salts are noted and the question of ion pairing is discussed.     

Theoretical study of rhodium(I) carbene complexes: the structural versatility of phosphino- compared with aminocarbenes

Density functional calculations are reported for complexes of general formula [(carbene)RhClL(2)] featuring model phosphino- and aminocarbenes. Both the cis and trans isomers of the rhodium(I) eta(1)-complexes (1-9) were investigated, and the influence of the rhodium co-ligands (L=ethylene, phosphine, or carbon monoxide) was evaluated. In the case of phosphinocarbenes and carbon monoxide as a ligand, a somewhat unusual coordination mode was observed, in which a significant intramolecular Cl-->C(carbene) interaction is present. The propensity of phosphino- and aminocarbenes to behave as four electron donors was also investigated both structurally and energetically on the related eta(2)-complexes 10-18. These results as a whole emphasize the structural versatility of phosphino- compared with aminocarbene complexes.     

Copper phosphoramidite-catalyzed enantioselective desymmetrization of meso-cyclic allylic bisdiethyl phosphates

[reaction: see text] A highly regio-, diastereo-, and enantioselective desymmetrization of five-, six-, and seven-membered meso-cyclic allylic bis-diethyl phosphates (2a, 2b, and 2c, respectively) was obtained with diethylzinc, using catalytic amounts of [Cu(OTf)](2).C(6)H(6) and phosphoramidite ligands 5. Enantiomeric excesses of up to 87, 94, and >98% were obtained for the addition of diethylzinc to cyclopentene, cyclohexene, and cycloheptene bis-diethyl phosphates, respectively.     

Gas-Phase Generation and Photoelectron Spectra of Reactive Unsubstituted Cycloalkenethiones

The flash vacuum thermolysis of cycloalkenyl allyl sulfides, potential precursors of unsubstituted cycloalkenethiones, has been investigated by photoelectron spectroscopy. This technique allowed us to characterize in the gas phase very reactive species of this series, the conjugated and nonconjugated cyclopentene and cyclohexenethiones, and to compare the reactivity of these compounds. The assignment of the PE spectra is supported by electronic structure calculations, particularly by the HF method at the MP2 level and the density functional theory (DFT) using the B3LYP and BP86 functionals with the 6-311G(d, p) basis set. Copyright 2001 Academic Press.     

Precision synthesis and characterization of thymine‐functionalized polyisobutylene

A new two‐step synthesis of polyisobutylene (PIB) with precisely one thymine functionality per chain (PIB‐T) is reported. The primary hydroxyl‐functionalized PIB (PIB‐OH) precursor was prepared by direct functionalization via living carbocationic polymerization of isobutylene initiated by the α‐methylstyrene epoxide/TiCl₄ system. Matrix assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐ToF MS) of a low molecular weight PIB‐OH precursor demonstrated the effectiveness of direct functionalization by this method. A PIB‐acrylate precursor (PIB‐Ac) was obtained from such a PIB‐OH, and the PIB‐T was subsequently prepared by Michael addition of thymine across the acrylate double bond. MALDI‐ToF MS of the products verified that all polymer chains carried precisely one thymine group. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3501–3506, 2010