Self-structuring of lamellar bridged silsesquioxanes with long side spacers

Diurea cross-linked bridged silsesquioxanes (BSs) C(10)C(11)C(10) derived from organosilane precursors, including decylene chains as side spacers and alkylene chains with variable length as central spacers (EtO)(3)Si- (CH(2))(10)-Y(CH(2))(n)-Y-(CH(2))(10)-Si(OEt)(3) (n = 7, 9-12; Y = urea group and Et = ethyl), have been synthesized through the combination of self-directed assembly and an acid-catalyzed sol gel route involving the addition of dimethylsulfoxide (DMSO) and a large excess of water. This new family of hybrids has enabled us to conclude that the length of the side spacers plays a unique role in the structuring of alkylene-based BSs, although their morphology remains unaffected. All the samples adopt a lamellar structure. While the alkylene chains are totally disordered in the case of the C(10)C(7)C(10) sample, a variable proportion of all-trans and gauche conformers exists in the materials with longer central spacers. The highest degree of structuring occurs for n = 9. The inclusion of decylene instead of propylene chains as side spacers leads to the formation of a stronger hydrogen-bonded urea-urea array as evidenced by two dimensional correlation Fourier transform infrared spectroscopic analysis. The emission spectra and emission quantum yields of the C(10)C(n)C(10) Cm materials are similar to those reported for diurea cross-linked alkylene-based BSs incorporating propylene chains as side spacers and prepared under different experimental conditions. The emission of the C(10)C(n)C(10) hybrids is ascribed to the overlap of two distinct components that occur within the urea cross-linkages and within the siliceous nanodomains. Time-resolved photoluminescence spectroscopy has provided evidence that the average distance between the siliceous domains and the urea cross-links is similar in the C(10)C(n)C(10) BSs and in oxyethylene-based hybrid analogues incorporating propylene chains as side spacers (diureasils), an indication that the longer side chains in the former materials adopt gauche conformations. It has also allowed us to demonstrate for the first time that the emission features of the urea-related component of the emission of alkylene-based BSs depend critically on the length of the side spacers

Tailoring the Hydrophilic/Lipophilic Balance of Clickable Mesoporous Organosilicas by the Copper-Catalyzed Azide−Alkyne Cycloaddition Click-Functionalization

International audienceWe have designed and synthesized a clickable bridgedsilsesquioxane material featuring pendant alkyne chains as an aggregate ofgolf-ball-like nanoparticles, as evidenced by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and small- and wide-angle X-ray scattering (SWAXS). Using the copper-catalyzed azide−alkyne cycloaddition reaction with a range of organic azides of variable characteristics, we transformed this parent bridged silsesquioxane into new materials with tunable hydrophilic/lipophilic balance in high conversions while preserving the original morphology. N2, cyclohexane, and water sorption experiments were used to quantify the affinity of these materials toward the sorbates through the determination of their Henry’s constants. This resulted in the following hydrophilic scale: M-OH > M-PEG > M-C6 > M-Ph > M-F > M-C16, which was mostly confirmed by SWAXS measurements

Syntheses and applications of periodic mesoporous organosilica nanoparticles

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Tailoring the Hydrophilic/Lipophilic Balance of Clickable Mesoporous Organosilicas by the Copper-Catalyzed Azide–Alkyne Cycloaddition Click-Functionalization

We have designed and synthesized a clickable bridged silsesquioxane material featuring pendant alkyne chains as an aggregate of golf-ball-like nanoparticles, as evidenced by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and small- and wide-angle X-ray scattering (SWAXS). Using the copper-catalyzed azide–alkyne cycloaddition reaction with a range of organic azides of variable characteristics, we transformed this parent bridged silsesquioxane into new materials with tunable hydrophilic/lipophilic balance in high conversions while preserving the original morphology. N₂, cyclohexane, and water sorption experiments were used to quantify the affinity of these materials toward the sorbates through the determination of their Henry’s constants. This resulted in the following hydrophilic scale: M-OH > M-PEG > M-C6 > M-Ph > M-F > M-C16, which was mostly confirmed by SWAXS measurements

Enhanced Collective Magnetic Properties in 2D Monolayers of Iron Oxide Nanoparticles Favored by Local Order and Local 1D Shape Anisotropy

Magnetic nanoparticle arrays represent a very attractive research field because their collective properties can be efficiently modulated as a function of the structure of the assembly. Nevertheless, understanding the way dipolar interactions influence the intrinsic magnetic properties of nanoparticles still remains a great challenge. In this study, we report on the preparation of 2D assemblies of iron oxide nanoparticles as monolayers deposited onto substrates. Assemblies have been prepared by using the Langmuir–Blodgett technique and the SAM assisted assembling technique combined to CuAAC “click” reaction. These techniques afford to control the formation of well-defined monolayers of nanoparticles on large areas. The LB technique controls local ordering of nanoparticles, while adjusting the kinetics of CuAAC “click” reaction strongly affects the spatial arrangement of nanoparticles in monolayers. Fast kinetics favor disordered assemblies while slow kinetics favor the formation of chain-like structures. Such anisotropic assemblies are induced by dipolar interactions between nanoparticles as no magnetic field is applied and no solvent evaporation is performed. The collective magnetic properties of monolayers are studied as a function of average interparticle distance, local order and local shape anisotropy. We demonstrate that local control on spatial arrangement of nanoparticles in monolayers significantly strengthens dipolar interactions which enhances collective properties and results in possible super ferromagnetic order

Fast Assembling of Magnetic Iron Oxide Nanoparticles by Microwave-Assisted Copper(I) Catalyzed Alkyne–Azide Cycloaddition (CuAAC)

Two dimensional (2D) nanoparticles (NP) assemblies have become very attractive due to their original collective properties, which can be modulated as a function of the nanostructure. Beyond precise control on nanostructure and easy way to perform, fast assembling processes are highly desirable to develop efficient and popular strategies to prepare systems with tunable collective properties. In this article, we report on the highly efficient and fast 2D assembling of iron oxide nanoparticles on a self-assembled monolayer (SAM) of organic molecules by the microwave (MW)-assisted copper­(I) catalyzed alkyne–azide cycloaddition (CuAAC) click reaction. Microwave irradiation favors a dramatic enhancement of the assembling reaction, which was completed with maximum density in NPs within one hour, much faster than the conventional CuAAC click reactions that require up to 48 h. Moreover, the MW-assisted click reaction presents the great advantage to preserve specific reactions between alkyne and azide groups at SAM and NP surfaces, respectively, and also to avoid undesired reactions. To the best of our knowledge, this is the first time this approach is performed to nanoparticles assembled on surfaces

Mixed Periodic Mesoporous Organosilica Nanoparticles and Core−Shell Systems, Application to in Vitro Two-Photon Imaging, Therapy, and Drug Delivery

International audienceIn this work, we describe the synthesis of new Mixed Periodic Mesoporous Organosilica Nanoparticles (MPMO NPs), combining the co-condensation of a tetra-trialkoxysilylated twophoton photosensitizer with bis-(triethoxysilyl)phenylene or ethylene. Novel gold core-MPMO shell systems are also described. The MPMO NPs are analyzed and characterized by multiple techniques, and are very efficient for anti-cancer drug delivery combined with two-photon therapy in MCF-7 breast cancer cells, leading down to 76% cancer cell death. MPMO NPs are thus very promising for nanomedicine applications