Multiple Surface Functionalities through Step-by-Step Hydrolysis of Self-Assembled Monolayers

Bhat, Rahila; Sell, Stephan; Trimbach, David C.; Zankovych, S.; Zhang, Jiantao; Bossert, Jörg; Klemm, Elisabeth

doi:10.1021/cm800326w

Cited by 6 publications

(6 citation statements)

References 62 publications

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“…19 Hydrolysis and X-ray-induced chemical modification have been used to produce chemical changes in monolayers on gold, but these techniques have not yet been employed in a gradient fashion. 20,21 Finally, a number of researchers have used polymer or copolymer brushes to create surface energy gradients for block copolymer thin film studies. These gradients can be generated by grafting or synthesizing two types of polymers on a surface in a gradient fashion or by synthesizing statistical copolymers on the surface with a gradient in composition.…”

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confidence: 99%

“…This technique has been used to study dewetting behavior of thin polymer films, to examine the effect of surface energy on block copolymer phase behavior, and to introduce alkyne functionalities suitable for “click chemistry” attachment of biologically relevant molecules . Hydrolysis and X-ray-induced chemical modification have been used to produce chemical changes in monolayers on gold, but these techniques have not yet been employed in a gradient fashion. , …”

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confidence: 99%

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Generation of Monolayer Gradients in Surface Energy and Surface Chemistry for Block Copolymer Thin Film Studies

et al. 2009

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We utilize a vapor deposition setup and cross-diffusion of functionalized chlorosilanes under dynamic vacuum to generate a nearly linear gradient in surface energy and composition on a silicon substrate. The gradient can be tuned by manipulating chlorosilane reservoir sizes and positions, and the gradient profile is independent of time as long as maximum coverage of the substrate is achieved. Our method is readily amenable to the creation of gradients on other substrate surfaces, due to the use of vapor deposition, and with other functionalities, due to our use of functionalized chlorosilanes. Our gradients were characterized using contact angle measurements and X-ray photoelectron spectroscopy. From these measurements, we were able to correlate composition, contact angle, and surface energy. We generated a nearly linear gradient with a range in mole fraction of one component from 0.15 to 0.85 (34 to 40 mJ/m(2) in surface energy) to demonstrate its utility in a block copolymer thin film morphology study. Examination of the copolymer thin film surface morphology with optical and atomic force microscopy revealed the expected morphological transitions across the gradient.

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Generation of Monolayer Gradients in Surface Energy and Surface Chemistry for Block Copolymer Thin Film Studies

et al. 2009

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“…In general, a substrate surface fully covered with a covalently bonded SAM composed of small molecules cannot be functionalized by further addition of other SAM-forming agents. The surfaces with multiple functionalities are usually obtained by transforming some of the functional groups in the tail of SAM molecules into a different chemical structure . In contrast, the PSAM-coated surface investigated here can accommodate additional SAM-forming surface-reactive agents because much of the surface underneath the PSAM is still available for covalent grafting.…”

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confidence: 99%

Surface-Grafted Rodlike Polymers: Adaptive Self-Assembled Monolayers and Rapid Photo-Patterning of Surfaces

et al. 2011

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We present a new concept of functionalizing solid surfaces using polymeric self-assembled monolayers (PSAM) that are obtained by grafting onto solid surfaces an asymmetric block copolymer composed of a long rodlike block and a short surface-reactive block. Poly(n-hexylisocyanate)-b-poly [3-(trimethoxysilyl) propyl methacrylate] (PHIC-b-PTMSM) is synthesized via a living anionic polymerization and an atom transfer radical polymerization. The new rodÀcoil block copolymer forms a polymeric self-assembled monolayer (PSAM) through covalent bonding of the sticky PTMSM block and planar adsorption of PHIC rodlike chains onto the substrate surface. The uniform PSAM with a thickness identical to the diameter of the rodlike chain is produced by the immersion coating method in a range of immersion solution concentrations and coating times. The PSAMs present unique properties thanks to the freedom of rotation of the end-grafted rodlike chains. The PSAMs exhibit nematic liquid crystalline ordering when the monolayer is fluidized by solvent vapor. A mixed SAM with a nanodot pattern is obtained by introducing a second coating agent of octadecyltrimethoxysilanes (ODTMS) onto the PSAM-coated substrate. The PSAM is micropatternable using photochemical cleavage of the anchoring blocks by brief exposure to UV. Use of the PSAMs as an additional dielectric layer in P3HT-based field effect transistors (FETs) is also demonstrated.

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“…Further details of the ellipsometry measurements can be found elsewhere. [37] Atomic Force Microscopy (AFM) Measurements…”

Section: Layer Thickness Measurementsmentioning

confidence: 99%

A Comparison of the Cell Compatibility of Poly(ethyleneimine) with that of other Cationic Biopolymers Used in Applications at Biointerfaces

et al. 2011

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Poly(ethyleneimine) (PEI) is used as an initiating base layer or intermediate layer for layer‐by‐layer (LBL) technology. Since PEI is potentially cytotoxic in solution, it is necessary to investigate the influence of the physical properties of PEI layers on osteoblast cells. Therefore, the first aim of this study was to test the hypothesis that there is no statistically significant difference of cell adhesion, proliferation, and viability in response to nanometer thin polymer layers of PEI compared to other well‐known polymers. The second aim of this study was to test the hypothesis that the amine‐substituted dextran (aminodextran (AMD)) adheres well on Ti and can be used as a polymer coating in biomaterials applications. Titanium samples were coated with PEI, poly‐L‐lysine (PLL), or AMD using dip coating. The polymer films were investigated with ellipsometry, atomic force microscopy, contact angle measurements, and X‐ray‐photoelectron spectroscopy (XPS). Cell adhesion, proliferation, and viability tests were carried out using osteoblast‐like cells (CAL‐72). Thin polymer layers below 10 nm layer thickness were found on the Ti surfaces. It was shown for the first time that base layers of PEI with nanometer thickness do not affect the bone cell reaction negatively. PEI, therefore, can be used as a functional base layer for LBL functionalization of metallic implants. AMD can be used in biomedical applications but does not adhere on titanium without an adhesion promoter.

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Multiple Surface Functionalities through Step-by-Step Hydrolysis of Self-Assembled Monolayers

Cited by 6 publications

References 62 publications

Generation of Monolayer Gradients in Surface Energy and Surface Chemistry for Block Copolymer Thin Film Studies

Generation of Monolayer Gradients in Surface Energy and Surface Chemistry for Block Copolymer Thin Film Studies

Surface-Grafted Rodlike Polymers: Adaptive Self-Assembled Monolayers and Rapid Photo-Patterning of Surfaces

A Comparison of the Cell Compatibility of Poly(ethyleneimine) with that of other Cationic Biopolymers Used in Applications at Biointerfaces

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