Nitroxyl radicals and nitroxylethers beyond stabilization: radical generators for efficient polymer modification

Beyond traditional polymer stabilization, sterically hindered piperidine derivatives move into new application areas where radical functions are key elements. Recent achievements in using nitroxyl derivatives in degradation, polymerization and grafting processes are discussed together with the involved chemical reactions and the resulting material properties. The examples shown cover selected nitroxylethers (NORs) performing as flame retardants and flame retardant synergists or replacing peroxides in manufacturing controlled rheology polypropylene (PP). Furthermore, NORs and nitroxyl radicals mediate radical polymerization processes resulting in tailor-made intermediates for polymer modification via radical and condensation steps and offer access to complex polymer architecture. To cite this article: R. Pfaendner, C.R. Chimie 9 (2006).     

Polyacetylenes and Cumulenes,Potential Elements for Molecular Machines and Precursors of Carbon Clusters: A Theoretical Study

A recently described very simple procedure for estimating Hartree–Fock (H. F.) energy and accurate nonrelativistic energy has been used with simple hydrocarbons possessing C?C or C?C bonds and for the acetylene dimer. Experimental characteristics (heats of formation, ionization potentials, electron affinities), structural features, and reactivity have been discussed in terms of quantum‐chemistry characteristics at the H. F. level and also at a level including a part of electron correlation. Deviations from linearity with derivatives of long polyacetylenes and cumulenes are ascribed to the lowest‐energy deformation vibrations, which decrease rapidly when passing from short to long acetylenic and cumulenic chains. The role of derivatives and heteroanalogues of hydrocarbons under study in atmospheric and interstellar chemistry is briefly mentioned. Derivatives with enhanced stability represent potentially promising construction materials for molecular devices and also resources for the preparation of defined clusters of C‐atoms.     

S(N)1-like reactions of bicyclic alpha-amino ethers with sulfur,nitrogen, and carbon nucleophiles. Synthesis of 1-azabicyclo[3.2.2]nonanes functionalized at carbon C2 and C6 with complete stereocontrol

[reaction: see text] In the presence of nucleophiles, Lewis acid mediated cleavage of alpha-amino ethers derived from quincorine and quincoridine affords a variety of C2-substituted and C6-vinylated 1-azabicyclo[3.2.2]nonanes. These are enantiopure and are formed in S(N)1-like reactions with complete stereocontrol. There is no leakage into 2-Nu en route to product 1-Nu or vice versa. Me(3)SiCN provides new Strecker-type alpha-amino nitriles. In the presence of TTMPP-BF(3).OEt(2), the ketene acetal Me(2)C=C(OMe)OSiMe(3) delivers enantiopure bicyclic beta-amino acid esters.     

Experimental and theoretical study of the adsorption of fumaramide [2]rotaxane on Au(111) and Ag(111) surfaces

Thin films of fumaramide [2]rotaxane, a mechanically interlocked molecule composed of a macrocycle and a thread in a "bead and thread" configuration, were prepared by vapor deposition on both Ag(111) and Au(111) substrates. X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy were used to characterize monolayer and bulklike multilayer films. XPS determination of the relative amounts of carbon, nitrogen, and oxygen indicates that the molecule adsorbs intact. On both metal surfaces, molecules in the first adsorbed layer show an additional component in the C 1s XPS line attributed to chemisorption via amide groups. Molecular-dynamics simulation indicates that the molecule orients two of its eight phenyl rings, one from the macrocycle and one from the thread, in a parallel bonding geometry with respect to the metal surfaces, leaving three amide groups very close to the substrate. In the case of fumaramide [2]rotaxane adsorption on Au(111), the presence of certain out-of-plane phenyl ring and Au-O vibrational modes points to such bonding and a preferential molecular orientation. The theoretical and experimental results imply that the three-dimensional intermolecular configuration permits chemisorption at low coverage to be driven by interactions between the three amide functions of fumaramide [2]rotaxane and the Ag(111) or Au(111) surface.     

Antioxidant Activity of Ruthenium Cyclopentadienyl Complexes Bearing Succinimidato and Phthalimidato Ligands

In these studies, we investigated the antioxidant activity of three ruthenium cyclopentadienyl complexes bearing different imidato ligands: (η⁵-cyclopentadienyl)Ru(CO)₂-N-methoxysuccinimidato (1), (η⁵-cyclopentadienyl)Ru(CO)₂-N-ethoxysuccinimidato (2), and (η⁵-cyclopentadienyl)Ru(CO)₂-N-phthalimidato (3). We studied the effects of ruthenium complexes 1–3 at a low concentration of 50 µM on the viability and the cell cycle of peripheral blood mononuclear cells (PBMCs) and HL-60 leukemic cells exposed to oxidative stress induced by hydrogen peroxide (H₂O₂). Moreover, we examined the influence of these complexes on DNA oxidative damage, the level of reactive oxygen species (ROS), and superoxide dismutase (SOD) activity. We have observed that ruthenium complexes 1–3 increase the viability of both normal and cancer cells decreased by H₂O₂ and also alter the HL-60 cell cycle arrested by H₂O₂ in the sub-G1 phase. In addition, we have shown that ruthenium complexes reduce the levels of ROS and oxidative DNA damage in both cell types. They also restore SOD activity reduced by H₂O₂. Our results indicate that ruthenium complexes 1–3 bearing succinimidato and phthalimidato ligands have antioxidant activity without cytotoxic effect at low concentrations. For this reason, the ruthenium complexes studied by us should be considered interesting molecules with clinical potential that require further detailed research.     

Novel Dithiolene Complexes and Tetrathiafulvalenes

Abstract

Novel dithiolene metal complexes, some of which absorb in the near infrared, and tetrathiafulvalenes, in particular tetraiodotetrathia- fulvalene, have been prepared, and their magnetic properties studied.     

Self Organization and Redox Behavior of Poly(vinylferrocene)-block-Poly(isobutylene)-block-Poly(vinylferrocene) Triblock Copolymer †

Self organization and redox behavior of a ferrocene containing triblock copolymer, poly(vinylferrocene)-block-poly(isobutylene)-block-poly(vinylferrocene), with narrow molecular weight distribution in solutions and in thin films were investigated. Dynamic light scattering studies of the block copolymer in dilute solutions indicated that the polymer chains aggregated at relatively low concentrations. The aggregations of polymer chains were observed in toluene, as well as in tetrahydrofuran at concentrations as low as 0.014 mg/mL and 0.0045 mg/mL, respectively. Thin films of the copolymer showed reversible single electron redox behavior, similar to that of ferrocene. Morphology and micro-phase separation of the copolymer was analyzed by transmission electron microscopy.     

Polyisobutylene-Based Thermoplastic Elastomers. I. Synthesis and Characterization of Polystyrene-Polyisobutylene-Polystyrene Triblock Copolymers

Abstract

Polystyrene-polyisobutylene-polystyrene triblock copolymer thermoplastic elastomers have been synthesized by living carbocationic sequential copolymerization using the tert-butyl dicumyl chloride/TiCl₄/methylcyclohexane:methyl chloride (60:40 v:v)/ ?80°C system in the presence of the proton trap 2,6-di-tert-butylpyridine. Structure-property relationships have been examined by varying the M_n of the PIB middle block (39,000 to 156,000) and that of the PSt end-segment (1,000 to 19,000). The tensile strength is controlled by the molecular weight of the PSt segment and independent of the PIB middle block length in the studied range. Phase separation starts when the M_n of the PSt segment reaches ～ 5,000, and it is complete when the M_n reaches ～ 15,000. These triblocks exhibited 23-25 MPa tensile strength, similar to that of styrenic thermoplastic elastomers obtained by anionic polymerization.     

Quality assurance in immunoassay performance—comparison of different enzyme immunoassays for the determination of caffeine in consumer products

Enzyme immunoassays with optical detection are amongst the most widely used bioanalytical tools. We defined seven parameters for the quality assessment of immunoassays that were addressed in a systematic study of direct and indirect immunoassays, using the enzymes horseradish peroxidase (HRP) and alkaline phosphatase (AP), the chromogenic substrates 3,3′,5,5′-tetramethylbenzidine (TMB) and para-nitrophenyl phosphate, and the fluorescent substrates 3-(4-hydroxyphenyl)propionic acid and 4-methylumbelliferyl phosphate. The same monoclonal antibody against caffeine was used throughout the study. The four quality parameters regarding the standard curve were the test midpoint (sensitivity), the measurement range, the relative dynamic range of the signal, and the goodness of fit of the adjusted four-parameter logistic function. All HRP immunoassays showed a higher sensitivity compared to the AP assays. On the basis of all four criteria, it was established that the direct assay format is superior to the indirect format, the immunoassay using HRP TMB fulfilling all requirements best. In a second step, caffeine concentrations in 24 beverage and cosmetics samples were determined and three more quality parameters were assessed with this application. The direct HRP TMB assay showed one of the best intra- and inter-plate precisions and the best accuracy, defined by the correlation of results with those from the chosen reference method liquid chromatography tandem mass spectrometry (LC-MS/MS). Considering all criteria, HRP TMB seems to be the enzyme substrate system of choice preferably used in the direct assay format.

Pinacol Rearrangement of 3,4‐Dihydro‐3,4‐dihydroxyquinolin‐2(1H)‐ones: An Alternative Pathway to Viridicatin Alkaloids and Their Analogs

3‐Alkyl/aryl‐3‐hydroxyquinoline‐2,4‐diones were reduced with NaBH₄ to give cis‐3‐alkyl/aryl‐3,4‐dihydro‐3,4‐dihydroxyquinolin‐2(1H)‐ones. These compounds were subjected to pinacol rearrangement by treatment with concentrated H₂SO₄, resulting in 4‐alkyl/aryl‐3‐hydroxyquinolin‐2(1H)‐ones. When a benzyl (Bn) group was present in position 3 of the starting compound, its elimination occurred during the rearrangement, and the corresponding 3‐hydroxyquinolin‐2(1H)‐one was formed. The reaction mechanisms are discussed for all transformations. All compounds were characterized by IR, ¹H‐ and ¹³C‐NMR spectroscopy, as well as mass spectrometry.