Surface-Grafted Polymeric Ionic Liquids with Tunable Morphology via In/Ex Situ Cross-linking Methods.

Surface-grafted poly(ionic liquid) (PIL) films were prepared by both in and ex situ cross-linking methods with reversible addition-fragmentation chain transfer (RAFT) polymerization. Cross-linked brushes are more stable than linear brushes without sacrificing the surface functionality and, therefore, have increased potential for applications in biomedicine and materials chemistry. The two methods, in situ via a bifunctional cross-linker and ex situ via thermal cross-linking, were systematically compared on silicon-wafer substrates. Films obtained through in situ cross-linking were superior to films derived from our ex situ cross-linking technique with respect to responsive behavior and controlling the formation of polymer brushes on the surface. Alternatively, more stable layers were obtained by the ex situ cross-linking method using a cross-linker based on Meldrum's acid, where the film structure could be changed from a brush to collapsed film morphologies with an increasing cross-linker ratio.

Morphology evolution of Janus dumbbell nanoparticles in seeded emulsion polymerization.

Emulsion polymerization is a versatile approach to produce different polymeric nanoparticle morphologies, which can be useful in a variety of applications. However, the detailed mechanism of the morphology formation is not entirely clear. We study the kinetics of nanoparticle morphology evolution during a seeded emulsion polymerization using both experimental and computational tools. Lightly crosslinked polystyrene seeds were first synthesized using dispersion polymerization. Then the seed particles were swollen in tert-butyl acrylate and styrene monomers, and subsequently polymerized into nanoparticles of dumbbell and multilobe morphologies. It was discovered that both the seed and final particle morphology were affected by the methanol concentration during the seed synthesis. Systematically adjusting the methanol amount will not only yield spherical seed particles of different size, but also dumbbell particles even without the second monomer polymerization. In addition to methanol concentration, morphology can be controlled by crosslinking density. The kinetics studies revealed an interesting transition from multilobe to dumbbell geometries during the secondary polymerization. Based on the results, a nucleation-growth model has been proposed to describe the morphology evolution and verification was offered by computer simulation. The key discovery is that nanoparticle morphology can be kinetically controlled by diffusion of the protrusions on the seed particles. The condition of seed synthesis and crosslinking density will drastically change the seed and final nanoparticle morphology.

Crosslinked-Polymer Brushes with Switchable Capture and Release Capabilities.

Crosslinked-polymer brushes give rise to new opportunities for functionalizing, protecting, and structuring both organic and inorganic materials. In this study, pH- and temperature-switchable crosslinked-polymer brushes were easily prepared by combining the in situ method with reversible addition⁻fragmentation chain transfer (RAFT) polymerization. Initially, the RAFT agent was immobilized on an amine-terminated silicon wafer surface and utilized in the surface-initiated RAFT polymerization of 2-N-morpholinoethyl methacrylate (MEMA) as a monomer, and ß-cyclodextrin methacrylate (CDMA) was used as a crosslinker on the silicon substrate. Measurements of film thickness, water contact angle, surface morphology, and structural characteristics of the resulting surfaces confirmed the poly(2-N-morpholinoethyl methacrylate) (PMEMA) brush-gels. Reversible capture and release measurements of methylene blue as a model molecule were also performed by UV⁻vis analysis. The switchable properties of the PMEMA brush-gels were maintained over five cycles. The results indicate that these PMEMA brush-gels with reversible capture and release properties might have widespread potential applications, including improved diagnostic tools as well as bioseparation.

A switchable polymer brush system for antifouling and controlled detection.

A stimuli-responsive polymer brush system is designed to switch on and off surface functionality and prevent functional groups from fouling by grafting together two polymer brushes with precisely controlled lengths. The polymer brush with functional groups has a fixed length, while the other brush extends and collapses as the environment changes.

Surface modification of electrospun cellulose acetate nanofibers via RAFT polymerization for DNA adsorption.

We report on a facile and robust method by which surface of electrospun cellulose acetate (CA) nanofibers can be chemically modified with cationic polymer brushes for DNA adsorption. The surface of CA nanofibers was functionalized by growing poly[(ar-vinylbenzyl)trimethylammonium chloride)] [poly(VBTAC)] brushes through a multi-step chemical sequence that ensures retention of mechanically robust nanofibers. Initially, the surface of the CA nanofibers was modified with RAFT chain transfer agent. Poly(VBTAC) brushes were then prepared via RAFT-mediated polymerization from the nanofiber surface. DNA adsorption capacity of CA nanofibrous web surface functionalized with cationic poly(VBTAC) brushes was demonstrated. The reusability of these webs was investigated by measuring the adsorption capacity for target DNA in a cyclic manner. In brief, CA nanofibers surface-modified with cationic polymer brushes can be suitable as membrane materials for filtration, purification, and/or separation processes for DNA.

Synthesis, structure characterization and antimicrobial evaluation of 4-(substituted phenylazo)-3,5-diacetamido-1H-pyrazoles.

The present article deals with the synthesis, spectral characterization and antimicrobial activity of phenylazo dyes. All of the synthesized phenylazo dyes were characterized using ATR-FTIR, FT-Raman, (1)H NMR, (13)C NMR, elemental analysis and mass spectroscopic techniques. Solvent effects on the UV-Vis absorption spectra of these phenylazo dyes were studied. Acid and base effects on the visible absorption maxima of the phenylazo dyes were also reported. The structural and spectroscopic analysis of the molecules were carried out using Density Functional Theory (DFT) employing the standard 6-31G(d) basis set, and the optimized geometries and calculated vibrational frequencies were evaluated via comparison with experimental values. The antimicrobial activity of 4-(substituted phenylazo)-3,5-diacetamido-1H-pyrazoles was reported against bacteria, including B. cereus (RSKK 863), S. aureus (ATCC 259231), M. luteus (NRRL B-4375), E. coli (ATCC 11230) and the yeast C. albicans (ATCC 10239).

RAFT-mediated synthesis of cationic poly[(ar-vinylbenzyl)trimethylammonium chloride] brushes for quantitative DNA immobilization.

The synthesis of cationic poly[(ar-vinylbenzyl)trimethylammonium chloride)] [poly(VBTAC)] brushes was achieved via reversible addition-fragmentation chain transfer (RAFT) polymerization and used for quantitative DNA immobilization. Initially, silicon surfaces were modified with RAFT chain transfer agent by utilizing an amide reaction involving a silicon wafer modified with allylamine and 4-cyanopentanoic acid dithiobenzoate (CPAD). Poly(VBTAC) brushes were then prepared via RAFT-mediated polymerization from the surface immobilized CPAD. Various characterization techniques including ellipsometry, X-ray photoelectron spectroscopy, grazing angle-Fourier transform infrared spectroscopy, atomic force microscopy and contact-angle goniometer were used to characterize the immobilization of CPAD on the silicon wafer and the subsequent polymer formation. The addition of free CPAD was required for the formation of well-defined polymer brushes, which subsequently resulted in the presence of free polymer chains in solution. The free polymer chains were isolated and used to estimate the molecular weights and polydispersity index of chains attached to the surface. Moreover, from atomic force microscopy and ellipsometry measurements, it was also determined that the density of immobilized DNA on the cationic poly(VBTAC) brushes can be quantitatively controlled by adjusting the solution concentration.

Surface chemical conversion of 3-glycidoxypropyldimethylethoxysilane on hydroxylated silicon surface: FT-IR, contact angle and ellipsometry analysis.

The chemical conversion of the top surface of 3-glycidoxypropyldimethylethoxysilane (GPDMES) on hyroxylated silicon surface has been studied as a function of reaction time. A multiple-step procedure was applied in this study. At first, GPDMES molecules were self-assembled on the hydroxylated silicon surface. The second step was the modification of epoxy groups with 3,3'-iminodipropionitrile and the last step was the amidoximation reaction of nitrile groups. Existence of the monolayers covalently attached to silicon surfaces were revealed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy (FT-IR). Modification, conversion and thickness of surfaces were followed by FT-IR and ellipsometry analysis.