RESUMO
Small-angle X-ray scattering (SAXS) was performed on dispersions of ultrasmall (d < 10 nm) fluorescent organic-inorganic hybrid core-shell silica nanoparticles synthesized in aqueous solutions (C' dots) by using an oscillating flow cell to overcome beam induced particle degradation. Form factor analysis and fitting was used to determine the size and size dispersity of the internal silica core containing covalently encapsulated fluorophores. The structure of the organic poly(ethylene glycol) (PEG) shell was modelled as a monodisperse corona containing concentrated and semi-dilute regimes of decaying density and as a simple polydisperse shell to determine the bounds of dispersity in the overall hybrid particle. C' dots containing single growth step silica cores have dispersities of 0.19-0.21; growth of additional silica shells onto the core produces a thin, dense silica layer, and increases the dispersity to 0.22-0.23. Comparison to FCS and DLS measures of size shows good agreement with SAXS measured and modelled sizes and size dispersities. Finally, comparison of a set of same sized and purified particles demonstrates that SAXS is sensitive to the skewness of the gel permeation chromatography elugrams of the original as-made materials. These and other insights provided by quantitative SAXS assessments may become useful for generation of robust nanoparticle design criteria necessary for their successful and safe use, for example in nanomedicine and oncology applications.
RESUMO
X-ray scattering of biological macromolecules in solution is an increasingly popular tool for structural biology and benefits greatly from modern high-brightness synchrotron sources. The upgraded MacCHESS BioSAXS station is now located at the 49-pole wiggler beamline G1. The 20-fold improved flux over the previous beamline F2 provides higher sample throughput and autonomous X-ray scattering data collection using a unique SAXS/WAXS dual detectors configuration. This setup achieves a combined q-range from 0.007 to 0.7 Å(-1), enabling better characterization of smaller molecules, while opening opportunities for emerging wide-angle scattering methods. In addition, a facility upgrade of the positron storage ring to continuous top-up mode has improved beam stability and eliminated beam drift over the course of typical BioSAXS experiments. Single exposure times have been reduced to 2 s for 3.560 mg ml(-1) lysozyme with an average quality factor I/σ of 20 in the Guinier region. A novel disposable plastic sample cell design that incorporates lower background X-ray window material provides users with a more pristine sample environment than previously available. Systematic comparisons of common X-ray window materials bonded to the cell have also been extended to the wide-angle regime, offering new insight into best choices for various q-space ranges. In addition, a quantitative assessment of signal-to-noise levels has been performed on the station to allow users to estimate necessary exposure times for obtaining usable signals in the Guinier regime. Users also have access to a new BioSAXS sample preparation laboratory which houses essential wet-chemistry equipment and biophysical instrumentation. User experiments at the upgraded BioSAXS station have been on-going since commissioning of the beamline in Summer 2013. A planned upgrade of the G1 insertion device to an undulator for the Winter 2014 cycle is expected to further improve flux by an order of magnitude.
