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Small-angle scattering (SAS) experiments are a powerful method for studying self-assembly phenomena in nanoscopic materials because of the sensitivity of the technique to structures formed by interactions on the nanoscale. Numerous out-of-the-box options exist for analysing structures measured by SAS but many of these are underpinned by assumptions about the underlying interactions that are not always relevant for a given system. Here, a numerical algorithm based on reverse Monte Carlo simulations is described to model the intensity observed on a SAS detector as a function of the scattering vector. The model simulates a two-dimensional detector image, accounting for magnetic scattering, instrument resolution, particle polydispersity and particle collisions, while making no further assumptions about the underlying particle interactions. By simulating a two-dimensional image that can be potentially anisotropic, the algorithm is particularly useful for studying systems driven by anisotropic interactions. The final output of the algorithm is a relative particle distribution, allowing visualization of particle structures that form over long-range length scales (i.e. several hundred nanometres), along with an orientational distribution of magnetic moments. The effectiveness of the algorithm is shown by modelling a SAS experimental data set studying finite-length chains consisting of magnetic nanoparticles, which assembled in the presence of a strong magnetic field due to dipole interactions.
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The softness of an object can be quantified by one of the fundamental elastic moduli. The bulk modulus of the particle is most appropriate in the presence of isotropic compressions. Here, we use small-angle neutron scattering with contrast variation to directly access the bulk modulus of polymeric nanocapsules - pNIPAM-based hollow nanogels. We show that the size of the cavity is the most important quantity that determines the softness of hollow nanogels. During initial compression, the polymer collapses into the cavity and leads to a large change in the particle volume, resulting in a very small initial bulk modulus. Once the cavity is partially occupied by the polymer, the hollow nanogels become significantly stiffer since now the highly crosslinked network has to be compressed. Furthermore, we show that the larger the cavity, the softer the nanogel.
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The bulk modulus, K, quantifies the elastic response of an object to an isotropic compression. For soft compressible colloids, knowing K is essential to accurately predict the suspension response to crowding. Most colloids have complex architectures characterized by different softness, which additionally depends on compression. Here, we determine the different values of K for the various morphological parts of individual nanogels and probe the changes of K with compression. Our method uses a partially deuterated polymer, which exerts the required isotropic stress, and small-angle neutron scattering with contrast matching to determine the form factor of the particles without any scattering contribution from the polymer. We show a clear difference in softness, compressibility, and evolution of K between the shell of the nanogel and the rest of the particle, depending on the amount of cross-linker used in their synthesis.
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Self-assembly of iron oxide nanoparticles (IONPs) into 1D chains is appealing, because of their biocompatibility and higher mobility compared to 2D/3D assemblies while traversing the circulatory passages and blood vessels for in vivo biomedical applications. In this work, parameters such as size, concentration, composition, and magnetic field, responsible for chain formation of IONPs in a dispersion as opposed to spatially confining substrates, are examined. In particular, the monodisperse 27 nm IONPs synthesized by an extended LaMer mechanism are shown to form chains at 4 mT, which are lengthened with applied field reaching 270 nm at 2.2 T. The chain lengths are completely reversible in field. Using a combination of scattering methods and reverse Monte Carlo simulations the formation of chains is directly visualized. The visualization of real-space IONPs assemblies formed in dispersions presents a novel tool for biomedical researchers. This allows for rapid exploration of the behavior of IONPs in solution in a broad parameter space and unambiguous extraction of âthe parameters of the equilibrium structures. Additionally, it can be extended to study novel assemblies formed by more complex geometries of IONPs.
Assuntos
Compostos Férricos , Nanopartículas de Magnetita , Tamanho da PartículaRESUMO
We present a platform for the encapsulation of superparamagnetic iron oxide nanocrystals (SPIONs) with a highly stable diblock copolymer shell allowing a homogeneous dispersion of the nanocrystals into a polymer matrix in the resulting nanocomposites. High polymer shell stability was achieved by crosslinking the inner polydiene shell for example in a persulfate based redox process. The advantage of this crosslinking reaction is the avoidance of heat and UV light for the initiation, making it suitable for heat or UV sensitive systems. In addition, we were able to minimize the ligand excess needed for the encapsulation and showcased a variation of molecular weight and composition as well as different ligands which lead to stable micelles. The encapsulated nanocrystals as well as the nanocomposite materials were characterized by transmission electron microscopy (TEM) and small angle scattering (SAXS and SANS).
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Core/shell quantum dots/quantum rods are nanocrystals with typical application scenarios as ensembles. Resonance energy transfer is a possible process between adjacent nanocrystals. Highly excited nanocrystals can also relax energy by multiexciton recombination, competing against the energy transfer. The two processes have different dependencies and can be convolved, resulting in collective properties different from the superposition of the individual nanocrystals. A platform to study the interplay of energy transfer and multiexciton recombination is presented. CdSe/CdS quantum dot/quantum rods encapsulated in amphiphilic micelles with an interparticle distance control by spacer ligands are used for time-resolved photoluminescence and transient absorption experiments. At exciton populations around one, the ensemble starts to be in a state where energy transfer can trigger multiexciton Auger recombination, altering the collective dynamics.
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Nanocomposite materials based on highly stable encapsulated superparamagnetic iron oxide nanocrystals (SPIONs) were synthesized and characterized by scattering methods and transmission electron microscopy (TEM). The combination of advanced synthesis and encapsulation techniques using different diblock copolymers and the thiol-ene click reaction for cross-linking the polymeric shell results in uniform hybrid SPIONs homogeneously dispersed in a poly(ethylene oxide) matrix. Small-angle X-ray scattering and TEM investigations demonstrate the presence of mostly single particles and a negligible amount of dyads. Consequently, an efficient control over the encapsulation and synthetic conditions is of paramount importance to minimize the fraction of agglomerates and to obtain uniform hybrid nanomaterials.