Stamm, M. (1997). Grafting of polypeptides on solid substrates by initiation of N-carboxyanhydride polymerization by aminoterminated self-assembled monolayers. Langmuir, 13(4), 723-728. DOI: 10.1021/la960467g Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Volker Erb and Manfred StammMax-Plank-Institut fü r Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany Received May 13, 1996. In Final Form: December 9, 1996 A series of mixed self-assembled monolayers of functionalized (Br(CH2)11SiCl3) and unfunctionalized (CH3(CH2)10SiCl3) alkyltrichlorosilanes of different compositions have been prepared on bulk silicon substrates. By in situ modification of these monolayers the bromo end groups were transformed to amino end groups as shown by X-ray photoelectron spectroscopy measurements. The change of hydrophilicity was monitored by water contact angle measurements, showing the expected decrease of contact angles with increase amino group content on the surface. These substrates were used to initiate Ncarboxyanhydrides in dioxane to yield R-helical polypeptides grafted from the surface. The thicknesses of the obtained polymer layers were measured with ellipsometry and X-ray reflectometry. Fourier transform infrared measurements confirm that the grafted polymers are in the R-helical conformation.

Electromechanical properties of an ultrathin layer of directionally aligned helical polypeptides Jaworek, T.; Neher, D.; Wegner, G.; Wieringa, R.H.; Schouten, A.J.

In this paper the average helix orientation of surface-grafted poly(γ-benzyl L-glutamate) (PBLG), poly-(γ-methyl L-glutamate) (PMLG), and poly(γ-methyl L-glutamate)-co-(γ-n-stearyl L-glutamate) (PMLGSLG 70/30) was investigated by means of FT-IR transmission spectroscopy. The theoretical relation between the average tilt angle (θ) and the absorption peak areas of three different backbone amide bands could be calculated because their transition dipole moment directions with respect to the helix axis were known. From the normalized absorptions, the average tilt angles of grafted helices of PBLG, PMLG, and PMLGSLG 70/30 were determined. The somewhat larger average angle of PMLG helices of 35 ( 5°with respect to the substrate compared to the value of 32 ( 5°of PBLG was due to the higher grafting density of PMLG. Because of the smaller helix diameter as a result of the smaller size of the methyl side group, more PMLG helices grew on the same surface area. Sterical hindrance and unfavorable polar interactions between unidirectional aligned helices forced the PMLG helices in a more upright arrangement. The even more perpendicular orientation of PMLGSLG 70/30 (48 ( 6°) could be the result of incorporation of mainly γ-methyl L-glutamate N-carboxyanhydride (MLG-NCA) monomers during the initiation step. Incorporation of the much larger γ-n-stearyl L-glutamate N-carboxyanhydride (SLG-NCA) monomers afterward lead to enlarged angles with respect to the substrate. Due to swelling, a pronounced change in helix orientation of grafted PMLGSLG 70/30 in n-hexadecane was observed, resulting in an almost perpendicular helix orientation.

The ring-opening polymerization of N-carboxyanhydrides (NCA) of γ-benzyl L-glutamate and γ-methyl L-glutamate from (γ-aminopropyl)triethoxysilane (APS) pretreated substrates such as silicon wafers and quartz slides was investigated. FT-IR transmission spectroscopy, circular dichroism measurements, and UV/vis spectroscopy confirmed the pure R-helix conformation of the grafted polypeptide layers. FT-IR spectroscopy also showed that the most important part of the polymer growth took place in the first 5 h of the polymerization. The average orientation of the rather rigid R-helical polypeptides, grown during a short period of time, was more perpendicular with respect to the substrate than the orientation of the polymers grown over a longer reaction time. For concentrations up to 2.0 M, the polymer growth from both NCA monomers showed a pronounced dependence on the monomer concentration. Moreover, it appeared that the higher the monomer concentration, the more perpendicular the average orientation of the helices with respect to the substrate. The thickness of the grafted polypeptide layers up to 400 Å was determined with ellipsometry and small-angle X-ray reflection measurements. The absence of chemical chain termination was demonstrated by additional polymer growth in a renewed polymerization.