We wished to compile a data set of results from the experimental literature to support the development and validation of accurate computational models (force fields) for an important class of micelle-forming nonionic surfactant compounds, the poly(ethylene oxide) alkyl ethers, usually denoted C n E m . However, careful examination of the experimental literature exposed a striking degree of variation in values reported for critical micelle concentrations (cmc) and mean aggregation numbers (N agg ). This variation was so large that it masked important trends known to exist within this family of molecules, thereby rendering most of the literature data to be of limited utility for force field development. In this work, we describe some reasons for the wide variability in the experimental literature, and we present a set of cmc and aggregation number data for 12 C n E m compounds that we feel is appropriate to use for the construction of and validation of computational models. The cmc values we selected are from the existing experimental literature and represent a carefully chosen and consistent subset that conveys important trends seen by many of the experimental studies. However, for a corresponding and consistent set of weight-averaged aggregation numbers, we needed to perform new dynamic light scattering (DLS) experiments. The results of these experiments were carefully analyzed to obtain not just mean aggregation numbers but also the underlying micelle size distribution functions. Several trends observed in the cmc and N agg observables are highlighted and serve as challenges for developers of force field and simulation methodology. The analysis of the DLS experiments accounts for the fact that a broad distribution of micelle sizes exists for many of these compounds and that one must be careful to use the appropriate weighted averages (e.g., mass-weighted vs number-weighted averages) in comparing results from different types of experiments and in comparing results from experiments with those from simulations.

Assembly from ultrasmall solution droplets follows a different dynamic from that of larger scales. Using an independently controlled microfluidic probe in an atomic force microscope, subfemtoliter aqueous droplets containing polymers produce well-defined features with dimensions as small as tens of nanometers. The initial shape of the droplet and the concentration of solute within the droplet play significant roles in the final assembly of polymers due to the ultrafast evaporation rate and spatial confinement by the small droplets. These effects are used to control the final molecular assembly in terms of feature geometry and distribution and packing of individual molecules within the features. This work introduces new means of control over molecular assembly, bringing us closer to programmable synthesis for chemistry and materials science. The outcomes pave the way for three-dimensional (3D) nanoprinting in additive manufacturing.

Branched and linear nonmigratory internal plasticizers attached to PVC by a pendant triazole linkage were synthesized and investigated. Copper‐free azide‐alkyne thermal cycloaddition was employed to covalently bind triazole‐based phthalate mimics to PVC. To systematically investigate the effect of plasticizer structure on glass transition temperature, several architectural motifs were explored. Free volume theory was considered when designing many of these internal plasticizers: hexyl‐tethers were utilized to generate additional space between the triazole‐phthalate mimic and the polymer backbone. Miscibility of these triazole‐plasticizers in PVC is important: variation of the ester moieties on the triazole possessing alkyl and/or poly(ethylene oxide) chains produced a wide range of glass transition temperatures (Tg): from anti‐plasticizing 96 °C, to highly efficient plasticized materials exhibiting Tg values as low as −42 °C. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2397–2411

The area selective growth of polymers and their use as inhibiting layers for inorganic film depositions may provide a valuable self-aligned process for fabrication. Polynorbornene (PNB) thin films were grown from surface-bound initiators and show inhibitory properties against the atomic layer deposition (ALD) of ZnO and TiO2. Area selective control of the polymerization was achieved through the synthesis of initiators that incorporate surface-binding ligands, enabling their selective attachment to metal oxide features versus silicon dielectrics, which were then used to initiate surface polymerizations. The subsequent use of these films in an ALD process enabled the area selective deposition (ASD) of up to 39 nm of ZnO. In addition, polymer thickness was found to play a key role, where films that underwent longer polymerization times were more effective at inhibiting higher numbers of ALD cycles. Finally, while the ASD of a TiO2 film was not achieved despite blanket studies showing inhibition, the ALD deposition on polymer regions of a patterned film produced a different quality metal oxide and therefore altered its etch resistance. This property was exploited in the area selective etch of a metal feature. This demonstration of an area selective surface-grown polymer to enable ASD and selective etch has implications for the fabrication of both micro- and nanoscale features and surfaces.