We present a method to combine the functional features of poly(diethyl vinylphosphonate) (PDEVP) and photoluminescent silicon nanocrystals. The polymer-particle hybrids were synthesized in three steps through surfaceinitiated group transfer polymerization using Cp 2 YCH 2 TMS-(thf) as a catalyst. This pathway of particle modification renders the nanoparticle surface stable against oxidation. Although SiNC properties are known to be sensitive toward transition metals, the hybrid particles exhibit red photoluminescence in water. The temperature-dependent coiling of PDEVP results in a change of the hydrodynamic radius of the hybrid particles in water. To the best of our knowledge, this is the first example of controlled catalytic polymerization reactions on a silicon nanocrystal surface.
Flow field-flow fractionation is a powerful method for the analysis of nanoparticle size distributions, but its widespread use has been hampered by large analyte losses, especially of metal nanoparticles. Here, we report on the colloidal mechanisms underlying the losses. We systematically studied gold nanoparticles (AuNPs) during asymmetrical flow field-flow fractionation (AF4) by systematic variation of the particle properties and the eluent composition. Recoveries of AuNPs (core diameter 12 nm) stabilized by citrate or polyethylene glycol (PEG) at different ionic strengths were determined. We used online UV-vis detection and off-line elementary analysis to follow particle losses during full analysis runs, runs without cross-flow, and runs with parts of the instrument bypassed. The combination allowed us to calculate relative and absolute analyte losses at different stages of the analytic protocol. We found different loss mechanisms depending on the ligand. Citrate-stabilized particles degraded during analysis and suffered large losses (up to 74%). PEG-stabilized particles had smaller relative losses at moderate ionic strengths (1-20%) that depended on PEG length. Long PEGs at higher ionic strengths (≥5 mM) caused particle loss due to bridging adsorption at the membrane. Bulk agglomeration was not a relevant loss mechanism at low ionic strengths ≤5 mM for any of the studied particles. An unexpectedly large fraction of particles was lost at tubing and other internal surfaces. We propose that the colloidal mechanisms observed here are relevant loss mechanisms in many particle analysis protocols and discuss strategies to avoid them.
We present a method to combine the functional features of poly(diethyl vinylphosphonate) (PDEVP) and photoluminescent silicon nanocrystals. The polymer-particle hybrids were synthesized in three steps through surface-initiated group transfer polymerization using Cp2 YCH2 TMS(thf) as a catalyst. This pathway of particle modification renders the nanoparticle surface stable against oxidation. Although SiNC properties are known to be sensitive toward transition metals, the hybrid particles exhibit red photoluminescence in water. The temperature-dependent coiling of PDEVP results in a change of the hydrodynamic radius of the hybrid particles in water. To the best of our knowledge, this is the first example of controlled catalytic polymerization reactions on a silicon nanocrystal surface.
Different colloidal particle characterization methods are examined for their suitability to determine the particle size distribution of particles extracted from steels. Microalloyed steels are dissolved to extract niobium and titanium carbonitride particles that are important for the mechanical properties of these steels. Such particles have sizes ranging from several nanometers to hundreds of nanometers depending on the precipitation stage during the thermomechanically controlled rolling process. The size distribution of the particles is analyzed by dynamic light scattering (DLS), analytical ultracentrifugation (AUC), and hollow fiber flow field‐flow fractionation (HF5) and compared to data obtained for reference particles as well as data from electron microscopy, the standard sizing technique used in metallurgy today. AUC and HF5 provide high‐quality size distributions, average over large particle numbers that enables statistical analysis, and yield useful insights for alloy design; however, DLS fails due to a lack of resolution. Important aspects in the conversion and comparison of size distributions obtained for broadly distributed particle systems with different measurement principles and the role of surfactants used in sample preparation are discussed.
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