Structural investigations of metal clusters by HREM

Silver clusters grown by the inert gas aggregation technique have been investigated by HREM. Undistorted cuboctahedra and icosahedra together with twinned particles have been observed. Three types of nucleation and growth mechanisms are proposed which can explain the observed particle structures. The untwinned large particles are created by the coalescence of liquid- like small clusters. The twins are produced by the coalescence of solid subunits.     

1-Arylsulfonylamino-1,2,3-triazole derivatives from functionalyzed 1,2-cyclohexanediones

The heterocyclization reaction of arylsulfonylhydrazones from alkyl substituted 1,2-cyclohexanediones is sensitive to the steric requirements of the alkyl groups. A mechanism for the cyclization in acidic medium is also reported.     

Thermal reactions of tributyltin hydride with alpha-azido esters: unexpected intervention of tin triazene adducts under both nonradical and radical conditions

Thermal reaction of various alpha-azido esters with Bu(3)SnH in refluxing benzene results in smooth production of 3-(tributylstannyl)-1-triazene adducts affording cyclized 1,2,3-triazol-4-ones in preference to reduced amines and thence provides a new useful method for the preparation of these triazole derivatives. In the presence of AIBN the occurrence of triazene products still remains important or even exclusive and, consequently, generation of the expected stannylaminyl radicals is seriously limited. With 2-azidomalonates and alpha-azido-beta-keto esters stannyltriazenes can similarly occur in the absence of the radical initiator, but in the latter cases the ensuing triazenes undergo preferential cyclization onto the ketone moiety to give reactive hydroxytriazolines. Contrary to alpha-azido esters, in the presence of AIBN alpha-azido-beta-keto esters as well as azidomalonates give rise only to the usual stannylaminyl radicals. A possible explanation for the different behavior of the mono- and dicarbonyl azides in the presence of AIBN is put forward.     

Ion-carrier controlled precipitation of calcium phosphate in giant ABA triblock copolymer vesicles

An ionophore assisted metal-ion transport across block copolymer membranes has been used to control the local Ca2+ concentration during precipitation of calcium phosphate in giant block copolymer vesicles.     

Mechanically responsive films of variable hydrophobicity made of polyelectrolyte multilayers

Mechanically responsive surfaces that allow to switch reversibly from a hydrophobic to a hydrophilic substrate are reported. The surfaces are constituted of polyelectrolyte multilayers deposited on modified charged silicone sheets. n bilayers of poly(allylamine)-Nafion (PAH-Naf) and m bilayers of poly(allylamine)-poly(acrylic acid) (PAH-PAA) composed the multilayers. A (PAH-Naf)(n) film possesses a water contact angle of around 105 degrees, whereas the contact angle of a (PAH-Naf)(4)-(PAH-PAA)(m) multilayer is around 50 degrees. When such a film with m < 5 and terminated by PAA is stretched out, its water contact angle increases up to around 100 degrees. Successive elongation/retraction cycles allow the water contact angle to alternate reversibly between 100 and 57 degrees indicating the reversible mechanical responsive nature of the film.     

FTIR and WAXS analysis of periodate oxycellulose: Evidence for a cluster mechanism of oxidation

Cellulose paper (Whatman no.1, chromatographic grade) was oxidised with 0.1 M sodium metaperiodate at different oxidation levels (0–11 days at room temperature), and analysed with FTIR before and after chemical treatments (reduction, further oxidation, alkaline hydrolysis). The deconvolution of infrared data allowed us to verify that periodate oxidises cellulose in isolated domains, leading to the decrease of crystallinity, in agreement with the results of wide angle X-ray scattering (WAXS). In particular, the alkaline hydrolysis (β-alkoxy fragmentation) followed by mild acid treatment removed the oxidised groups and recovered most of the crystallinity of cellulose, as determined by the FTIR crystallinity index.     

Is styrene planar in liquid phases?

The proton NMR spectra of two (13)C-labeled isotopomers of styrene dissolved in two liquid crystalline solvents have been obtained and analyzed to yield four sets each of 24 dipolar couplings. These couplings were then used to investigate the structure of the ring and the ene fragments of the molecule, and the position of the maximum, phi(0), in the ring-ene bond rotational probability distribution. To do this, the effect on the dipolar couplings of small-amplitude vibrational motion was taken into account using vibrational wave functions calculated by molecular orbital and density functional methods. It is concluded that the NMR data are consistent with the ring fragment, averaged over the ring-ene rotation, planar, while the ene fragment is not. The value of phi(0) is found to be 18.0 degrees +/-0.2 degrees for the two solutions, compared with a value of 27 degrees calculated by the molecular method MP2/6-31G(*).