SuFEx on the Surface: A Flexible Platform for Postpolymerization Modification of Polymer Brushes

Polymer brushes present a unique architecture for tailoring surface functionalities due to their distinctive physicochemical properties. However, the polymerization chemistries used to grow brushes place limitations on the monomers that can be grown directly from the surface. Several forms of click chemistry have previously been used to modify polymer brushes by postpolymerization modification with high efficiency, however, it is usually difficult to include the unprotected moieties in the original monomer. We present the use of a new form of click chemistry known as SuFEx (sulfur(VI) fluoride exchange), which allows a silyl ether to be rapidly and quantitatively clicked to a polymer brush grown by free‐radical polymerization containing native ‐SO₂F groups with rapid pseudo‐first‐order rates as high as 0.04 s^?1. Furthermore, we demonstrate the use of SuFEx to facilely add a variety of other chemical functional groups to brush substrates that have highly useful and orthogonal reactivity, including alkynes, thiols, and dienes.     

Freezing of polymer thin films and surfaces: The small molecular weight puzzle

Experimental observations (ellipsometry, scanning force microscopy, and nuclear magnetic recsonance (NMR)) of the freezing behavior of thin supported films as well as the free surface of atactic polystyrene are reported, taken at a particularly small molecular weight of 2 kg/mol. Remarkably, we find the same effect of reduction of the glass transition temperature, T_g, as observed earlier with much longer molecules. Furthermore, surface melting is observed by NMR, with the molten layer thickness similar to what has been observed with larger molecular weight. We conclude that molecular geometry effects cannot account for these observations, and that a consistent explanation must be presentable in a continuum picture. On the basis of the capillary mode spectrum of the free surface and of the supported films, we present such a model and find that it accounts very consistently with all observations made so far, at least with polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2968–2979, 2006     

Two-Dimensional Conjugated Polymer Synthesized by Interfacial Suzuki Reaction: Towards Electronic Device Applications

Preparing two-dimensional conjugated polymers (2DCPs) with desirable structures and semiconducting properties is promising but remains a great challenge. Presented here is a new 2DCP, named 2D polytriethyltriindole (2DPTTI), which is efficiently synthesized by a modified interfacial Suzuki reaction from 2,7,12-tribromo-5,10,15-triethyltriindole (2-BrTTI) and 1,4-benzenediboronic acid dipinacol ester (BADE) precursors at room temperature. Wafer-scale free-standing 2DPTTI films with controllable thicknesses between 2.5 and 46.0 nm were obtained by adjusting the experimental conditions. The resulting 2DPTTI films, used as an active layer in organic field effect transistors (OFETs), exhibited typical p-type semiconducting properties and superior UV optoelectronic performance with a photosensitivity of 3.7×10³ and responsivity of 1.4×10³ A W⁻¹, as well as a light-blue fluorescence character. This report provides a general approach for constructing various semiconducting 2DCPs, by an interfacial Suzuki reaction, towards multifunctional organic electronics.     

Two‐Dimensional Conjugated Polymer Synthesized by Interfacial Suzuki Reaction: Towards Electronic Device Applications

Preparing two‐dimensional conjugated polymers (2DCPs) with desirable structures and semiconducting properties is promising but remains a great challenge. Presented here is a new 2DCP, named 2D polytriethyltriindole (2DPTTI), which is efficiently synthesized by a modified interfacial Suzuki reaction from 2,7,12‐tribromo‐5,10,15‐triethyltriindole (2‐BrTTI) and 1,4‐benzenediboronic acid dipinacol ester (BADE) precursors at room temperature. Wafer‐scale free‐standing 2DPTTI films with controllable thicknesses between 2.5 and 46.0 nm were obtained by adjusting the experimental conditions. The resulting 2DPTTI films, used as an active layer in organic field effect transistors (OFETs), exhibited typical p‐type semiconducting properties and superior UV optoelectronic performance with a photosensitivity of 3.7×10³ and responsivity of 1.4×10³ A W^?1, as well as a light‐blue fluorescence character. This report provides a general approach for constructing various semiconducting 2DCPs, by an interfacial Suzuki reaction, towards multifunctional organic electronics.     

Salt‐Driven Deposition of Thermoresponsive Polymer‐Coated Metal Nanoparticles on Solid Substrates

Here we report on a simple, generally applicable method for depositing metal nanoparticles on a wide variety of solid surfaces under all aqueous conditions. Noble‐metal nanoparticles obtained by citrate reduction followed by coating with thermoresponsive polymers spontaneously form a monolayer‐like structure on a wide variety of substrates in presence of sodium chloride whereas this phenomenon does not occur in salt‐free medium. Interestingly, this phenomenon occurs below the cloud point temperature of the polymers and we hypothesize that salt ion‐induced screening of electrostatic charges on the nanoparticle surface entropically favors hydrophobic association between the polymer‐coated nanoparticles and a hydrophobic substrate.     

Topological Polymer Chemistry Enters Surface Science: Linear versus Cyclic Polymer Brushes

The cyclic polymer topology strongly alters the interfacial, physico‐chemical properties of polymer brushes, when compared to the linear counterparts. In this study, we especially concentrated on poly‐2‐ethyl‐2‐oxazoline (PEOXA) cyclic and linear grafts assembled on titanium oxide surfaces by the “grafting‐to” technique. The smaller hydrodynamic radius of ring PEOXAs favors the formation of denser brushes with respect to linear analogs. Denser and more compact cyclic brushes generate a steric barrier that surpasses the typical entropic shield by a linear brush. This phenomenon, translates into an improved resistance towards biological contamination from different protein mixtures. Moreover, the enhancement of steric stabilization coupled to the intrinsic absence of chain ends by cyclic brushes, produce surfaces displaying a super‐lubricating character when they are sheared against each other. All these topological effects pave the way for the application of cyclic brushes for surface functionalization, enabling the modulation of physico‐chemical properties that could be just marginally tuned by applying linear grafts.     

Formation Mechanism of a Silane‐PVA/PVAc Complex Film on a Glass Fiber Surface

Mechanical properties of glass fiber reinforced composite materials are affected by fiber sizing. A complex film formation, based on a silane film and PVA/PVAc (polyvinyl alcohol/polyvinyl acetate) microspheres on a glass fiber surface is determined at 1) the nanoscale by using atomic force microscopy (AFM), and 2) the macroscale by using the zeta potential. Silane groups strongly bind through the Si? O? Si bond to the glass surface, which provides the attachment mechanism as a coupling agent. The silane groups form islands, a homogeneous film, as well as empty sites. The average roughness of the silanized surface is 6.5 nm, whereas it is only 0.6 nm for the non‐silanized surface. The silane film vertically penetrates in a honeycomb fashion from the glass surface through the deposited PVA/PVAc microspheres to form a hexagonal close pack structure. The silane film not only penetrates, but also deforms the PVA/PVAc microspheres from the spherical shape in a dispersion to a ellipsoidal shape on the surface with average dimensions of 300/600 nm. The surface area value S_a represents an area of PVA/PVAc microspheres that are not affected by the silane penetration. The areas are found to be 0.2, 0.08, and 0.03 μm² if the ellipsoid sizes are 320/570, 300/610, and 270/620 nm for silane concentrations of 0, 3.8, and 7.2 μg mL^?1, respectively. The silane film also moves PVA/PVAc microspheres in the process of complex film formation, from the low silane concentration areas to the complex film area providing enough silane groups to stabilize the structure. The values for the residual silane honeycomb structure heights (H_a) are 6.5, 7, and 12 nm for silane concentrations of 3.8, 7.2, and 14.3 μg mL^?1, respectively. The pH‐dependent zeta‐potential results suggest a specific role of the silane groups with effects on the glass fiber surface and also on the PVA/PVAc microspheres. The non‐silanized glass fiber surface and the silane film have similar zeta potentials ranging from ?64 to ?12 mV at pH’s of 10.5 and 3, respectively. The zeta potentials for the PVA/PVAc microspheres on the glass fiber surface and within the silane film significantly decrease and range from ?25 to ?5 mV. The shapes of the pH‐dependent zeta potentials are different in the cases of silane groups over a pH range from 7 to 4. A triple‐layer model is used to fit the non‐silanized glass surface and the silane film. The value of the surface‐site density for Γ_Xglass and Γ_Xsilane, in which X denotes the Al? O? Si group, differs by a factor of 10^?4, which suggests an effective coupling of the silane film. A soft‐layer model is used to fit the silane‐PVA/PVAc complex film, which is approximated as four layers. Such a simplification and compensation of the microsphere shape gives an approximation of the relevant widths of the layers as the follows: 1) the layer of the silane groups makes up 10 % of the total length (27 nm), 2) the layer of the first PVA shell contributes 30 % to the total length (81 nm), 3) the layer of the PVAc core contributes 30 % to the total length (81 nm), and finally 4) the layer of the second PVA shell provides 30 % of the total length (81 nm). The coverage simulation resulted in a value of 0.4, which corresponds with the assumption of low‐order coverage, and is supported by the AFM scans. Correlating the results of the AFM scans, and the zeta potentials sheds some light on the formation mechanism of the silane‐PVA/PVAc complex film.     

Advances in the development of molecularly imprinted polymers for the separation and analysis of proteins with liquid chromatography

This review documents recent advances in the design, synthesis, characterization, and application of molecularly imprinted polymers in the form of monoliths and particles/beads for the use in the separation and analysis of proteins with solid‐phase extraction or liquid chromatography. The merits of three‐dimensional molecular imprinting, whereby the molecular template is randomly embedded in the polymer, and two‐dimensional imprinting, in which the template is confined to the surface, are described. Target protein binding can be achieved by either using the entire protein as a template or by using a protein substructure as template, that is, a peptide, as in the "epitope" approach. The intended approach and strategy then determine the choice of polymerization method. A synopsis has been provided on methods used for the physical, chemical, and functional characterizations and associated performance evaluations of molecularly imprinted and nonimprinted control polymers, involving a diverse range of analytical techniques commonly used for low and high molecular mass analytes. Examples of recent applications demonstrate that, due to the versatility of imprinting methods, molecularly imprinted monoliths or particles/beads can be adapted to protein extraction/depletion and separation procedures relevant to, for example, protein biomarker detection and quantification in biomedical diagnostics and targeted proteomics.     

From cloudy to transparent: chain rearrangement in hydrogen-bonded layer-by-layer assembled films.

The cloudiness of hydrogen-bonded LBL films assembled from polyvinylpyrrolidone (PVPON) and poly(acrylic acid) (PAA) is studied in detail by two approaches: spectroscopy (Fabry-Pérot fringes) and microscopy (AFM). Fabrication parameters such as temperature, molecular weight, pH value, and rinsing time, have notable influences on film cloudiness. The buildup of the PVPON/ PAA film is a two-stage process of adsorption and chain rearrangement. Generally, adsorption is fast, while chain rearrangement is slow. The fast adsorption process traps defects, whereas the relatively slow chain-rearrangement process can not heal the defects in time; therefore; the number of defects continuously increases as LBL assembly proceeds, and a cloudy, heterogeneous film is produced. However, the as-prepared cloudy films become transparent and homogeneous on subsequent annealing in acidic water. UV/Vis spectroscopy and fluid AFM were applied to monitor this transition ex situ and in situ, respectively. It is found that increasing the annealing temperature accelerates the transition from cloudy to transparent, and the transition of the film made from higher molecular weight polymer is slower.     

Silicate-Phenolic Networks: Coordination-Mediated Deposition of Bioinspired Tannic Acid Coatings

Surface modification with polyphenolic molecules has been pursued in biomedical materials owing to their antioxidant, anti-inflammatory, and antimicrobial characteristics. Recently, the use of silicic acid (Si_aq) as a mediator for efficient surface deposition of tannic acid (TA) was reported, but the postulated Si-TA polymeric networks were not characterized. Herein, we present unambiguous evidence for silicate-TA networks that involve Si−O−C motifs by using solid-state NMR spectroscopy, further supported by XPS and ToF-SIMS. By using QCM-D we demonstrate the advantages of Si_aq, compared to using transition-metal ions, to improve the coating efficiency under mildly acidic conditions. The presented homogenous coating buildup and validated applicability in inorganic buffers broadens the use of TA for surface modifications in technological and biomedical applications.