Prominence of the Instability of a Stabilizing Agent in the Changes in Physical State of a Hybrid Nanomaterial.

Shaping ability of hybrid nanomaterials is a key point for their further use in devices. It is therefore crucial to control it. To this end, it is necessary that the macroscopic properties of the material remain constant over time. Here, we evidence by multinuclear Magic-Angle Spinning Nuclear Magnetic Resonance spectroscopic study including 17 O isotope exchange that for a ZnO-alkylamine hybrid material, the partial carbonation of amine into ammonium carbamate molecules is behind the conversion from highly viscous liquid to a powdery solid when exposed to air. This carbonation induces modification and reorganization of the organic shell around the nanocrystals and affects significantly the macroscopic properties of the material such as it physical state, its solubility and colloidal stability. This study, straightforwardly extendable, highlights that the nature of the functional chemical group allowing connecting the stabilizing agent (SA) to the surface of the nanoparticles is of tremendous importance especially if the SA is reactive with molecules present in the environment.

Multinuclear solid-state NMR study: a powerful tool for understanding the structure of ZnO hybrid nanoparticles.

Characterization of hybrid materials is crucial for gaining an in-depth understanding of nano-objects. Here, it is evidenced that the use of multinuclear 1H, 2H, 13C, 15N, 67Zn and 17O MAS NMR spectroscopy is a very powerful approach to acquire both structural and dynamic information on hybrid ZnO nanomaterials prepared from an organometallic approach. Not only is the coordination mode of the organic part onto the inorganic surface evidenced but also important information about the dynamics of the organic capping molecules and some particularities of the nanocrystal structure itself are obtained.

Full characterization of colloidal solutions of long-alkyl-chain-amine-stabilized ZnO nanoparticles by NMR spectroscopy: surface state, equilibria, and affinity.

Full NMR characterization of ZnO nanoparticles (NPs) stabilized by various amines (hexadecylamine, dodecylamine, and octylamine) in C(7)D(8) demonstrated that the surface of this apparently simple system was very complex. Using different NMR spectroscopic techniques ((1)H, PGSE-NMR, diffusion-filtered (1)H NMR, NOESY, ROESY), we observed at least three different modes of interaction of the amines at the surface of the NPs, in thermodynamic equilibrium with the free amines, the relative populations of which varied with their concentration. The first mode corresponded to a strong interaction between a small amount of amine and the ZnO NPs (k(desorp)≈13 s(-1)). The second mode corresponded to a weak interaction between the amines and the surface of the ZnO NPs (k(off(2))≈50-60 s(-1)). The third, and weakest, mode of interaction corresponded to the formation of a second ligand shell by the amine around the NPs that was held together through van der Waals interactions (k(off(1))≈25×10(5) s(-1)). The second and third modes were in fast exchange on the NMR timescales with the free amines. The strongly interacting amines at the NPs surface (first mode) were in slow exchange with the other modes. A complex hydrogen-bonding network at the NPs surface was also observed, which did not only involve the coordinated amine but also THF and water molecules that remained from the synthesis.

Nanocrystal-ligand interactions deciphered: the influence of HSAB and pK a in the case of luminescent ZnO.

Despite all the efforts made by the scientific community to rationalize the interaction of organic molecules with nanocrystals (Ncs), we are still at the level of the empirical recipe when the material behavior in solution is concerned. In an effort to address this issue, the analysis of the luminescence measurements of ZnO Ncs in the presence of various organic substrates using a Langmuir adsorption model was carried out to determine for the first time the affinity constants and the number of binding sites as well as to rank the interaction strengths of these substrates with regard to ZnO Ncs. The results were confirmed by NMR spectroscopic studies, which, besides, provided a deep understanding of the substrate-ZnO Nc interactions. Analysis of the results using pK a and HSAB theory demonstrates that the interaction of a given substrate can be determined by its pK a versus the pK a of the organic molecules present at the surface of pristine Ncs and that the hard or soft character of the substrates can govern the emission intensity of the ZnO Ncs.

Phosphonate terminated PPH dendrimers: influence of pendant alkyl chains on the in vitro anti-HIV-1 properties.

The synthesis, characterization and in vitro anti-HIV activity of a series of generation one dendrimers having phosphonate groups with pendant alkyl chains are described. The influence of the lateral alkyl chains on the biological properties was correlated to (1)H-(1)H NOESY experiments.

Designing dendrimers for ocular drug delivery.

New series of phosphorus-containing dendrimers, having one quaternary ammonium salt as core and carboxylic acid terminal groups have been synthesized from generation 0 (3 carboxylic acid terminal groups) to generation 2 (12 carboxylic acid terminal groups). These dendrimers react with the neutral form of carteolol (an ocular anti-hypertensive drug used to treat glaucoma) to afford ion pair (saline) species. The solubility in water of these charged dendrimers depends on the generation considered: generation 0 (3 carteolol) is well soluble, whereas generation 1 (6 carteolol) and generation 2 (12 carteolol) are poorly soluble. These dendrimers have been tested in vivo, as vehicle for ocular drug delivery of carteolol to rabbits.