Quantitative Measure of the Size Dispersity in Ultrasmall Fluorescent Organic-Inorganic Hybrid Core-Shell Silica Nanoparticles by Small-angle X-ray Scattering.

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.

Exploiting Molecular Weight Distribution Shape to Tune Domain Spacing in Block Copolymer Thin Films.

We report a method for tuning the domain spacing ( Dsp) of self-assembled block copolymer thin films of poly(styrene- block-methyl methacrylate) (PS- b-PMMA) over a large range of lamellar periods. By modifying the molecular weight distribution (MWD) shape (including both the breadth and skew) of the PS block via temporal control of polymer chain initiation in anionic polymerization, we observe increases of up to 41% in Dsp for polymers with the same overall molecular weight ( Mn ≈ 125 kg mol-1) without significantly changing the overall morphology or chemical composition of the final material. In conjunction with our experimental efforts, we have utilized concepts from population statistics and least-squares analysis to develop a model for predicting Dsp based on the first three moments of the MWDs. This statistical model reproduces experimental Dsp values with high fidelity (with mean absolute errors of 1.2 nm or 1.8%) and provides novel physical insight into the individual and collective roles played by the MWD moments in determining this property of interest. This work demonstrates that both MWD breadth and skew have a profound influence over Dsp, thereby providing an experimental and conceptual platform for exploiting MWD shape as a simple and modular handle for fine-tuning Dsp in block copolymer thin films.

A general approach to controlling the surface composition of poly(ethylene oxide)-based block copolymers for antifouling coatings.

To control the surface properties of a polystyrene-block-poly(ethylene oxide) diblock copolymer, perfluorinated chemical moieties were specifically incorporated into the block copolymer backbone. A polystyrene-block-poly[(ethylene oxide)-stat-(allyl glycidyl ether)] [PS-b-P(EO-stat-AGE)] statistical diblock terpolymer was synthesized with varying incorporations of allyl glycidyl ether (AGE) in the poly(ethylene oxide) block from 0 to 17 mol %. The pendant alkenes of the AGE repeat units were subsequently functionalized by thiol-ene chemistry with 1H,1H,2H,2H-perfluorooctanethiol, yielding fluorocarbon-functionalized AGE (fAGE) repeat units. (1)H NMR spectroscopy and size-exclusion chromatography indicated well-defined structures with complete functionalization of the pendant alkenes. The surfaces of the polymer films were characterized after spray coating by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS), showing that the P(EO-stat-fAGE) block starts to compete with polystyrene to populate the surface after only 1 mol % incorporation of fAGE. Increasing the incorporation of fAGE led to an increased amount of perfluorocarbons on the surface and a decrease in the concentration of PS. At a fAGE incorporation of 8 mol %, PS was not detected at the surface, as measured by NEXAFS spectroscopy. Water contact angles measured by the captive-air-bubble technique showed the underwater surfaces to be dynamic, with advancing and receding contact angles varying by >20°. Protein adsorption studies demonstrated that the fluorinated surfaces effectively prevent nonspecific binding of proteins relative to an unmodified PS-b-PEO diblock copolymer. In biological systems, settlement of spores of the green macroalga Ulva was significantly lower for the fAGE-incorporated polymers compared to the unmodified diblock and a polydimethylsiloxane elastomer standard. Furthermore, the attachment strength of sporelings (young plants) of Ulva was also reduced for the fAGE-containing polymers, affirming their potential as fouling-release coatings.

Correlating the scattered intensities of P3HT and PCBM to the current densities of polymer solar cells.

Grazing-incidence X-ray diffraction and rocking scans have quantified the structure of poly(3-hexylthiophene) and [6,6]-phenyl-C(61)-butyric acid methyl ester in the active layers of organic solar cells. Our study reveals that the device J(SC) correlates with the local structural development of pure PCBM and, to second order, the extent of out-of-plane P3HT π-stacking.