We herein report the formation of two complex nanostructures, toroidal micelles and bicontinuous nanospheres, by the self-assembly of the single structurally simple crystalline-b-coil diblock copolymer poly[bis(trifluoroethoxy)phosphazene]-b-poly(styrene), PTFEP-b-PS, in one solvent (THF) and without additives. The nature of these nanostructures in solution was confirmed by DLS and cryo-TEM experiments. The two morphologies are related by means of a new type of reversible morphological evolution, bicontinuous-to-toroidal, triggered by changes in the polymer concentration. WAXS experiments showed that the degree of crystallinity of the PTFEP chains located at the core of the toroids was higher than that in the bicontinuous nanospheres, thus indicating that the final morphology of the aggregates is mostly determined by the ordering of the PTFEP core-forming blocks.

The highly diastereo- and enantioselective Mannich addition/cyclisation reaction of α-substituted isocyanoacetate ester pronucleophiles and (hetero)aryl and alkyl methyl ketone-derived ketimines using a silver acetate and a cinchona-derived amino phosphine binary catalyst system is reported.

A catalytic asymmetric aldol addition/cyclization reaction of unactivated ketones with isocyanoacetate pronucleophiles has been developed. A quinine-derived aminophosphine precatalyst and silver oxide were found to be an effective binary catalyst system and promoted the reaction to afford chiral oxazolines possessing a fully substituted stereocenter with good diastereoselectivities and excellent enantioselectivities.

Nanostructured luminescent ZnO and SnO 2 materials are prepared by a solidstate method based on the pyrolysis of hybrid macromolecular precursors ZnCl 2 •Chitosan and SnCl 2 •Chitosan having different [polymer/MCl 2 ] (M = Zn or Sn) ratios (1:1, 1:5 and 1:10), under air at 800°C .The pyrolytic ZnO and SnO 2 nanomaterials show a dependence of the particle size, morphology and luminescent properties with the ratio [metal/polymer] in the MCl 2 •Chitosan precursors. Thus, ZnO semiconductor materials exhibit luminescence spectra with several emission peaks between 300 and 600 nm. The most intense emission at 440 nm corresponds to a radiative transition of an electron from the shallow donor level of oxygen vacancies, and the zinc interstitial, to the valence band. All the ZnO materials synthesized show a rather intense green emission at ca. 573 nm, which is characteristic of this synthetic methodology. On the other hand, the photoluminescence spectrum of the nanostructured SnO 2 shows an intense blue luminescence at a wavelength of 420 nm which may be attributed to oxygen-related defects that have been introduced during the growth process of the nanoparticles. In other hand, whereas SnO 2 was successfully incorporated into SiO 2 structure (SnO 2 //SiO 2) by pyrolysis of solid-state mixtures of the precursors SnCl 2 •Chitosan in the presence of SiO 2 , the same reaction carried out with ZnCl 2 •Chitosan precursors led to a mixture of Zn 2 SiO 4 and SiO 2 The absorption and photoluminescence properties of the nanostructured SnO 2 //SiO 2 were very similar than those of pure SnO 2. Thus, this new methodology yields nanostructured semiconductor materials, ZnO and SnO 2 , suitable for optoelectronic and sensor solid-state devices.

Ac atalytic asymmetric aldol addition/cyclization reaction of unactivated ketones with isocyanoacetate pronucleophiles has been developed. Aquinine-derived aminophosphine precatalyst and silver oxide were found to be an effective binary catalyst system and promoted the reaction to afford chiral oxazolines possessing af ully substituted stereocenter with good diastereoselectivities and excellent enantioselectivities.The aldol reaction is one of the most powerful methods for the construction of b-hydroxy carbonyl compounds.[1] The importance of these building blocks,c ontained in aw ide variety of biologically relevant compounds,has promoted the development of several catalytic asymmetric methods for their production.[2] However, despite enormous progress in the aldol addition arena, its application to the synthesis of tertiary alcohols still remains am ajor challenge,p rincipally owing to al ack of reactivity and the fact that the differentiation of the enantiotopic faces is more difficult with ketone electrophiles than with the corresponding aldehydes. Furthermore,d eleterious side reactions,s uch as retro-aldol reactions,c an predominate when ak etone moiety is involved.[3] Although af ew catalytic asymmetric aldol reactions with unactivated ketones have been reported, [4] the development of new and efficient catalytic asymmetric methods to access chiral tertiary alcohols remains an important goal in modern asymmetric catalysis. [5] Along these lines,w er ecognized that the catalytic asymmetric ketone aldol reaction of isocyanoacetate pronucleophiles [6] could be as ynthetically powerful approach.Isocyanoacetate ester addition reactions to carbonyl [7] or imine electrophiles [8,9] directly afford the respective oxazoline or imidazoline heterocycles,which can be ring-opened under mild hydrolytic conditions to yield b-substituted a-amino acids.A lthough the catalytic asymmetric version of this reaction has been widely studied using aldehydes, [7] to date, no enantioselective example using unactivated ketones has been reported despite its potential to provide an elegant asymmetric route to a-amino acid derivatives possessing ac hiral tertiary alcohol in the b-position (Scheme 1).[10] In ar elated study,t he asymmetric aldol addition reaction of isothiocyanato esters and unactivated ketones,w hich afforded oxazolidinethione products with af ully substituted b-stereocenter,w as described.[11]Forpromoting and controlling various addition reactions, our group has developed an effective binary catalyst system comprising a" soft" metal ion, such as as ilver (I) ion, and ac inchona-derived aminophosphine precatalyst of type 1. This system promotes the highly diastereo-and enantioselective aldol reaction of isocyanoacetates with aldehydes, [7l] and Mannich reactions of aldimines [8e] and ketimines.[9a] The precatalyst is equipped with Brønsted basic and Lewis basic sites and also possesses ahydrogen-bond donor group located in the proximity of the chiral pocket that is created by the cinchona scaffold (Scheme ...