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 unexpected finding that the complex [Au(PPh3)2]PF6 (C1) catalyses the specific hydration of 1‐octyne, (p‐phenoxyphenyl)acetylene, phenylacetylene, (p‐chlorophenyl)acetylene and benzylacetylene at 100 °C in the presence of H2SO4 and THF or methanol as solvents, specially using microwave radiation, led to the first gold(I) recyclable catalysts for this reaction. The phosphazene polymeric framework of idealised formula {[NP(O2C12H8)]0.85[NP(OC6H4PPh2)2 (AuPF6)0.5]0.15}n (C2), and the newly synthesised cyclomatrix material of idealised formula {[N3P3(OC6H4PPh2)6](AuPF6)3.5}n (C3), both having cationic [–Ph2P–Au+–PPh2–] cross‐linking sites, catalysed the complete hydration of terminal alkynes at 100 °C and 150 °C and could be used six and four times respectively without significant loss of activity. The mechanism of the catalytic system is based on the initial reversible displacement of one anchoring O–C6H5–PPh2 group from the [–Ph2P–Au+–PPh2–] cross‐linking sites by an alkyne molecule. Using microwave radiation, the hydration of (p‐phenoxyphenyl)acetylene, phenylacetylene, (p‐chlorophenyl)acetylene and benzylacetylene can be completed in 5 min to 2 h in the absence of any gold(I) catalyst.

Determination of stoichiometries between engineered nanoparticles and species attached to their surface after chemical functionalization or interaction with biological media has been a hotspot during the last years, still unsatisfactory solved. Herein we propose a new approach only requiring for a simple mass spectrometric sulfur isotope ratio measurement in the final solution. Of course, enriched 34 S isotope has to be previously introduced in the engineered nanoparticle structure. Conversely to existing methodologies, mostly based on relative analyte measurements, proposed method does not require any previous knowledge of the molecule concentration in the starting solution. Such rather generic approach can be applied to study physical and/or chemical interactions between any sulfur-containing molecule and a wide variety of engineered nanoparticles containing sulfur as well, either in their own core-shell structure or in the ligand used for their surface functionalization (e.g. any thiol-derivative). In this paper, an inexpensive standard synthetic procedure was carried out to incorporate the required stable isotopic 34 S into the ZnS shell of CdSe quantum dots (QDs). Such isotopically enriched nanoparticles were then successfully applied to the quantitative assessment of stoichiometries between QDs and different target biomolecules, such as surface-functionalizing molecules (e.g. biotin) and proteins (e.g. bovine serum albumin). Of course, any biological conclusion and/or optimized bioconjugation conditions obtained using such isotopically enriched QDs analogues could be easily translated to nanoassemblies obtained using regular non-enriched QDs since they are chemically and physically identical.

In each of the crystal structures of the two title compounds, two mol­ecules are found in the asymmetric unit. Individual mol­ecules are linked by inter­molecular O—H⋯O hydrogen bonding and show significant differences in the torsions about the N=N bond and the dihedral angle between the benzene rings.

A random phosphazene copolymer {[N = P((CH2)7-Br)Ph]0.5[N = PMePh]0.5}n (2) and a block copolyphosphazene {[N = P((CH2)7-Br)Ph]0.5[N = PMePh]0.5}45-b-[N = P(O2C12H8)]55 (5), having a branch with two randomly distributed units, have been synthesized and used as precursors for the stannyl derivatives {[N = P((CH2)7-SnBu2An)Ph]0.5[N = PMePh]0.5}n (3) and {[N = P((CH2)7-SnBu2An)Ph]0.5[N = PMePh]0.5}45-b-[N = P(O2C12H8)]55 (6, An = p-MeOC6H4). Polymers 3 and 6 were tested as recyclable tin reagents in the Stille cross-coupling reaction with ArI, using various Pd catalysts and different experimental conditions. Polymer 6 can be recycled without a significant release of tin, but its efficiency decreased after three consecutive cycles. This effect was explained by studying the self-assembly of the polymer under the same conditions used for the catalytic experiments, which evidenced the progressive coalescence of the polymeric vesicles (polymersomes) leading to stable and bigger core-shell aggregates by the attraction of the [N = P(O2C12H8)] rich membranes, thus decreasing the accessibility of the tin active centers.