Dendrimers as scaffolds for multifunctional reversible addition–fragmentation chain transfer agents: Syntheses and polymerization

The synthesis and characterization of novel first‐ and second‐generation true dendritic reversible addition–fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3‐benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z‐group architecture based on 1,1,1‐hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 < polydispersity index < 1.1 for PBA and 1.5 < polydispersity index < 1.3 for PS) via bulk free‐radical polymerization at 60 °C. The novel dendrimer‐based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number‐average molecular weight (M_n) with the monomer–polymer conversion, yielding star polymers with molecular weights of up to M_n = 160,000 g mol^?1 for PBA (based on a linear PBA calibration) and up to M_n = 70,000 g mol^?1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1‐hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star‐shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star‐shaped polymeric materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5877–5890, 2004     

A complete active-space self-consistent-field study on cubic N8

Summary Complete Active-Space Self-Consistent-Field (CAS-SCF) calculations for cubic N₈ are presented. We studied the N₈↔4N₂ reaction inD _4h symmetry and found its energy release and activation barrier with three different atomic basis sets. The energy release for this reaction is predicted to be around 526 kcal/mol, while the energy barrier to dissociation is estimated about 159 kcal/mol. These results are in substantial agreement with previousab initio estimates. The authors of this paper have agreed to not receive the proofs for correction.     

Alkane oxygenation with H2O2 catalysed by FeCl3 and 2,2′-bipyridine

The H₂O₂-FeCl₃-bipy system in acetonitrile efficiently oxidises alkanes predominantly to alkyl hydroperoxides. Turnover numbers attain 400 after 1 h at 60 °C. It has been assumed that bipy facilitates proton abstraction from a H₂O₂ molecule coordinated to the iron ion (these reactions are stages in the catalytic cycle generating hydroxyl radicals from the hydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkyl hydroperoxide.     

Novel heterocycle-based two-photon absorbing dyes

[structure: see text]. The synthesis and nonlinear optical characterization of two novel heteroaromatic-based chromophores is described. The new dyes present an A-pi-D-pi-A general framework, where A is a pi-deficient heteroaromatic ring (pyridine, quinoline, benzothiazole) and D a pi-excessive pyrrolyl moiety. Both systems exhibit large two-photon absorption (TPA) values in the femtoseconds regime (TPA cross section as high as 150 x 10(-50) cm(4) s photon(-1) molecule(-1) with 150 fs laser pulses). Their TPA-based optical limiting activity is also shown.     

Solid-phase extraction and gas chromatographic-mass spectrometric identification of degradation products from enhanced environmentally degradable polyethylene

A solid-phase extraction (SPE) method using unbonded silica (Si) and silica bonded with octadecyl (C₁₈) or aminopropyl (NH₂) groups was developed to separate into five fractions the highly complex mixture of low-molecular-mass degradation products formed from degradable polymers. Application of the method to polyethylene modified with starch and/or a pro-oxidant system, degraded for 30 weeks in water at 95°C, enabled the identification by GC-MS of over three times as many products as when the sample was prepared by liquid-liquid extraction. Over 60 degradation products were identified in each sample; mainly dicarboxylic acids, monocarboxylic acids and n-alkanes. In addition, several lactones, aldehydes and alcohols were detected.     

Cyclopeptid-Antibiotika aus Aspergillus-Arten. Struktur der Echinocandine C und D

Cyclopeptide antibiotics from Aspergillus species. Structure of echinocandins C and D The echinocandins B, C and D are antifungal antibiotics produced by a strain of Aspergillus rugulosus. All three metabolites are closely related representing cyclic oligopeptides composed of six amino acids and a linolic acid residue in an amide linkage. The complete structure of echinocandin B ( 1 ) has recently been established by X-ray analysis. Structural assignments to the new minor metabolites C and D have now been made by hydrolytic and oxidative cleavage reactions, formation of N-acyl-α-aminoethers as well as by chemical correlations and extensive NMR. examinations. Echinocandin C ( 2 ), C₅₂H₈₁N₇O₁₅, contains 3-hydroxyhomotyrosine in the place of 3, 4-dihydroxyhomotyrosine present in 1 . Echinocandin D ( 3 ), C₅₂H₈₁N₇O₁₃, differs in two amino acids: 3, 4-dihyroxyhomotyrosine and 4, 5-dihydroxyornithine, unusual units of 1 being replaced by 3-hydroxyhomotyrosine and ornithine.     

Long-range dispersion coefficients for like centrosymmetric linear molecules and an application to H2-H2

The real spherical tensor theory of long-range intermolecular coefficients developed in previous papers is applied to derive explicit formulae for the first three dispersion coefficients for like centrosymmetric linear molecules. The expansion of angle-dependent coefficients in associated Legendre polynomials allows one to identify the isotropic and anisotropic components of the dispersion interaction in terms of London dispersion constants, the treatment of higher coefficients being simplified by the coupling of the elementary (l, l′)-polarizations to resultant angular momenta L_A and L_B onto each molecule. The contributions from all coupling schemes are given explicitly for C₆, C₈, C₁₀, and numerical results are presented for H₂-H₂ using two-term reduced spectra values from the Kaiserlautern group.     

Reaction of ketenes with N,N-disubstituted 2-aminomethylenecycloalkanones. V. Synthesis of N,N-disubstituted 4′-aminospiro [1,3-dithiane-2,3′-(5′,6′-polymethylene-3′,4′-dihydro-α-pyrones)]

The reaction of 2-carbonyl-1,3-dithiane, a sulfene prepared in situ from 2-chloroearbonyl-1,3-dithiane and triethylamine, with N,N-disubstituted 2-aminomethylvnecycloalkanones gave the 1,4-cycloadducts, namely N,N-disubstituted 4′-aminospiro[1,3-dithiane-2,3′-(5′,6′-poly-methylene-3′,4′-dihydro-α-pyrones)].     

Geographical traceability of West Liguria extravirgin olive oils by the analysis of volatile terpenoid hydrocarbons

This study aimed at evaluating if the volatile terpenoid hydrocarbons of extravirgin olive oils from West Liguria, a North Italy region, could trace their geographical origin. If terpenoid hydrocarbons were individually considered, three compounds, i.e. alpha-copaene, alpha-muurolene and alpha-farnesene, allowed building a simple decision tree and discriminating oils produced in West Liguria from oils produced in other Mediterranean regions. Moreover, the multivariate analysis allowed building West Liguria class-models with high predictive ability, confirming the fundamental role of the volatile terpenoid hydrocarbons for the geographical characterisation of West Liguria oils.