Magnetic-Field-Assisted Fabrication and Manipulation of Nonspherical Polymer Particles in Ferrofluid-Based Droplet Microfluidics.

We report a novel magnetic-field-assisted method for the fabrication and manipulation of nonspherical polymer particles within a ferrofluid-based droplet microfluidic device. Shape control and chain assembly of droplets with tunable lengths have been achieved.

π-Complexation in nickel-catalyzed cross-coupling reactions.

The kinetic isotope effect (KIE) is used to experimentally elucidate the first irreversible step in oxidative addition reactions of a zerovalent nickel catalyst to a set of haloarene substrates. Halogenated o-methylbenzene, dimethoxybenzene, and thiophene derivatives undergo intramolecular oxidative addition through irreversible π-complexation. Density functional theory computations at the B3LYP-D3/TZ2P-LANL2TZ(f)-LANL08d level predict η(2)-bound π-complexes are generally stable relative to a solvated catalyst plus free substrate and that ring-walking of the Ni(0) catalyst and intramolecular oxidative addition are facile in these intermediates.

Rate determination of azide click reactions onto alkyne polymer brush scaffolds: a comparison of conventional and catalyst-free cycloadditions for tunable surface modification.

The postpolymerization functionalization of poly(N-hydroxysuccinimide 4-vinylbenzoate) brushes with reactive alkynes that differ in relative rates of activity of alkyne-azide cycloaddition reactions is described. The alkyne-derived polymer brushes undergo "click"-type cycloadditions with azido-containing compounds by two mechanisms: a strain-promoted alkyne-azide cycloaddition (SPAAC) with dibenzocyclooctyne (DIBO) and azadibenzocyclooctyne (ADIBO) or a copper-catalyzed alkyne-azide cycloaddition (CuAAC) to a propargyl group (PPG). Using a pseudo-first-order limited rate equation, rate constants for DIBO, ADIBO, and PPG-derivatized polymer brushes functionalized with an azide-functionalized dye were calculated as 7.7 × 10(-4), 4.4 × 10(-3), and 2.0 × 10(-2) s(-1), respectively. The SPAAC click reactions of the surface bound layers were determined to be slower than the equivalent reactions in solution, but the relative ratio of the reaction rates for the DIBO and ADIBO SPAAC reactions was consistent between solution and the polymer layer. The rate of functionalization was not influenced by the diffusion of azide into the polymer scaffold as long as the concentration of azide in solution was sufficiently high. The PPG functionalization by CuAAC had an extremely fast rate, which was comparable to other surface click reaction rates. Preliminary studies of dilute solution azide functionalization indicate that the diffusion-limited regime of brush functionalization impacts a 50 nm polymer brush layer and decreases the pseudo-first-order rate by a constant diffusion-limited factor of 0.233.

Palladium-Mediated Surface-Initiated Kumada Catalyst Polycondensation: A Facile Route Towards Oriented Conjugated Polymers.

Palladium-mediated surface-initiated Kumada catalyst transfer polycondensation is used to generate poly(3-methyl thiophene) films with controlled thickness up to 100 nm. The palladium initiator density is measured using cyclic voltammetry and a ferrocene-capping agent, where the surface density is found to be 55% (1.1 × 10(14) molecules per cm(2)). UV-Vis spectroscopy and AFM show increased aggregation in palladium-initiated films due to the higher grafting density of palladium initiators on the surface. The anisotropy of the P3MT films is determined using polarized UV-Vis spectroscopy, which indicates a degree of orientation perpendicular to the substrate. Evidence that palladium can maintain π-complexation even at elevated temperatures, is also shown through the exclusive intramolecular coupling of both a phenyl and thiophene-based magnesium bromide with different dihaloarenes.

Fabrication of spiropyran-containing thin film sensors used for the simultaneous identification of multiple metal ions.

In this article, a methacrylate-based spiropyran-containing copolymer was used as a colorimetric sensor to identify multiple metal ions simultaneously. Through UV-vis absorption spectroscopy, the relative binding affinity of merocyanine to each metal ion was investigated by displacement studies of a bound metal ion with a second metal ion of a higher binding affinity. We also show that because each metal ion gives rise to a distinct spectral response, partial least-squares discriminant analysis (PLS-DA) can be used to analyze the UV-vis absorbance spectra to identify the two metal ions that are present in solution at varying concentrations simply by dipping a coated polymer substrate into solution after irradiation. Partial least-squares regression analysis (PLS) was used to determine the metal ions in solution for several binary mixtures quantitatively. We also demonstrate that the quantitative determination depends on the relative binding preference of merocyanine to each metal ion.

Surface-confined nickel mediated cross-coupling reactions: characterization of initiator environment in Kumada catalyst-transfer polycondensation.

Kumada catalyst-transfer polycondensation (KCTP) has proven to be an excellent strategy toward the synthesis of well-defined conjugated polymers. In this report, Ni(0) species are reacted with surface-bound aryl bromides to yield KCTP initiators of structure (aryl)Ni(II)-Br. Surface-confined Kumada reactions are carried out with a ferrocene functionalized Grignard reagent to quantify initiator coverage, ligand exchange, and Kumada reaction kinetics. In addition, surface-initiated Kumada catalyst-transfer polycondensation (SI-KCTP) is carried out from the fabricated initiators to modify SiO(2) and ITO surfaces. Uniform poly(3-methylthiophene) films with thicknesses between 40 and 65 nm were characterized using a variety of spectroscopic and electrochemical techniques.

High density scaffolding of functional polymer brushes: surface initiated atom transfer radical polymerization of active esters.

In this Article, we describe a method for the polymerization of active esters based on N-hydroxysuccinimide 4-vinyl benzoate (NHS4VB) using surface initiated atom transfer radical polymerization (SI-ATRP). Poly(NHS4VB) brushes have high grafting density and a uniform and smooth morphology, and film thickness increases linearly with reaction time. Block copolymer brushes with 2-hydroxyethyl acrylate, tert-butyl acrylate, and styrene were synthesized from surface bound poly(NHS4VB) macroinitiators. The active ester brushes show rapid and quantitative conversion under aminolysis conditions with primary amines, which was studied using grazing incidence attenuated total reflection Fourier transform infrared (GATR-FTIR) and UV-vis spectroscopy. UV-vis was also used to quantify the amount of reactive groups in polymer brush layers of differing thickness. Functionalization of the active ester pendant groups with chromophores containing primary amines showed a linear correlation between the amount of chromophore incorporated into the brush layer and brush thickness. Grafting densities as high as 25.7 nmol/cm(2) were observed for a 50 nm brush. Block copolymer brushes with buried active ester functional moieties also undergo quantitative conversion with primary amines as confirmed by GATR-FTIR. We discuss the potential of activated ester brushes as universal scaffolds for sensor and microarray surfaces, where the twofold control of functionalizable active ester polymer and block copolymers provides well-ordered, tunable microenvironments.