TY - JOUR A1 - Funk, C. A1 - Dietrich, Paul A1 - Gross, Thomas A1 - Min, Hyegeun A1 - Unger, Wolfgang A1 - Weigel, W. T1 - Epoxy-functionalized surfaces for microarray applications: surface chemical analysis and fluorescence labeling of surface species N2 - Methods for characterization of epoxy-functionalized substrates used for microarray applications, prepared by silanization with 3-glycidoxypropyltrimethoxysilane, have been developed. Contact angle measurements, X-ray photoelectron spectroscopy, time of flight secondary ion mass spectrometry and fluorescence based methods have been applied to investigate these epoxy-functionalized microarray substrates. The surface density of epoxy-functionalized glass slides was investigated by fluorescence labeling of surface species utilizing Rhodamine 110 as fluorescence probe. KW - Epoxy silane KW - Microarrays KW - Fluorescence KW - XPS KW - ToF-SIMS KW - Surface analysis PY - 2012 U6 - https://doi.org/10.1002/sia.3856 SN - 0142-2421 SN - 1096-9918 VL - 44 IS - 8 SP - 890 EP - 894 PB - Wiley CY - Chichester AN - OPUS4-26342 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Poppenberg, J. A1 - Richter, S. A1 - Darlatt, Erik A1 - Traulsen, C.H.-H. A1 - Min, Hyegeun A1 - Unger, Wolfgang A1 - Schalley, C.A. T1 - Successive coordination of palladium(II)-ions and terpyridine-ligands to a pyridyl-terminated self-assembled monolayer on gold N2 - The deposition of palladium on a novel, reversibly protonatable, pyridyl-terminated self-assembled monolayer on gold substrates has been studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS spectroscopy) and time of flight-secondary ion mass spectrometry (ToF-SIMS). For this purpose, 12-(pyridin-4-yl)dodecane-1-thiol, consisting of a surface-active head group, an unfunctionalized hydrocarbon backbone and a terminal pyridyl group, has been synthesized and deposited on gold surfaces. Coordination of Pd(II) ions to the pyridyl group was examined. Furthermore, a reversible protonation/deprotonation cycle has been applied, and the relation between protonation and the amount of complexed palladium was studied. Investigation of the SAM by angle-resolved NEXAFS spectroscopy revealed the aliphatic backbone to be preferentially upright oriented with the aromatic head group being not preferentially oriented. The palladium layer was further coordinated with a CF3-labeled terpyridine ligand in order to prove the accessibility of the Pd(II) ions to further complexation and the platform useful for deposition of further layers toward a multi-layered system. KW - Supramolecular surface chemistry KW - Pyridine terminated monolayer KW - NEXAFS spectroscopy KW - ToF-SIMS KW - Pyridine-metal coordination PY - 2012 U6 - https://doi.org/10.1016/j.susc.2011.10.020 SN - 0039-6028 VL - 606 IS - 3-4 SP - 367 EP - 377 PB - Elsevier CY - Amsterdam AN - OPUS4-25282 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dietrich, Paul A1 - Horlacher, T. A1 - Girard-Lauriault, Pierre-Luc A1 - Gross, Thomas A1 - Lippitz, Andreas A1 - Min, Hyegeun A1 - Wirth, Thomas A1 - Castelli, R. A1 - Seeberger, P. A1 - Unger, Wolfgang T1 - Multimethod chemical characterization of carbohydrate-functionalized surfaces N2 - A combined XPS, NEXAFS, and ToF-SIMS chemical surface characterization of carbohydrate-functionalized gold and glass surfaces is presented. Spot shape and chemical composition across a spot surface are provided by surface-sensitive methods as ToF-SIMS and XPS, used in their imaging modes. Moreover, the feasibility of this multimethod approach to control relevant production steps of a carbohydrate microarray prototype is demonstrated. KW - Carbohydrates KW - Microarrays KW - Self-assembled monolayers KW - XPS KW - NEXAFS KW - ToF-SIMS PY - 2011 U6 - https://doi.org/10.1080/07328303.2011.615181 SN - 0732-8303 VL - 30 IS - 4-6 SP - 361 EP - 372 PB - Taylor & Francis CY - London [u.a.] AN - OPUS4-24874 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dietrich, Paul A1 - Horlacher, T. A1 - Girard-Lauriault, Pierre-Luc A1 - Gross, Thomas A1 - Lippitz, Andreas A1 - Min, Hyegeun A1 - Wirth, Thomas A1 - Castelli, R. A1 - Seeberger, P.H. A1 - Unger, Wolfgang T1 - Adlayers of dimannoside thiols on gold: surface chemical analysis N2 - Carbohydrate films on gold based on dimannoside thiols (DMT) were prepared, and a complementary surface chemical analysis was performed in detail by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), near-edge X-ray absorption fine structure (NEXAFS), FT-IR, and contact angle measurements in order to verify formation of ω-carbohydrate-functionalized alkylthiol films. XPS (C 1s, O 1s, and S 2p) reveals information on carbohydrate specific alkoxy (C–O) and acetal moieties (O–C–O) as well as thiolate species attached to gold. Angle-resolved synchrotron XPS was used for chemical speciation at ultimate surface sensitivity. Angle-resolved XPS analysis suggests the presence of an excess top layer composed of unbound sulfur components combined with alkyl moieties. Further support for DMT attachment on Au is given by ToF-SIMS and FT-IR analysis. Carbon and oxygen K-edge NEXAFS spectra were interpreted by applying the building block model supported by comparison to data of 1-undecanethiol, poly(vinyl alcohol), and polyoxymethylene. No linear dichroism effect was observed in the angle-resolved C K-edge NEXAFS. KW - Carbohydrates KW - Self-assembled monolayer KW - XPS KW - NEXAFS KW - ToF-SIMS KW - Surface chemical analysis PY - 2011 U6 - https://doi.org/10.1021/la104038q SN - 0743-7463 SN - 1520-5827 VL - 27 IS - 8 SP - 4808 EP - 4815 PB - American Chemical Society CY - Washington, DC AN - OPUS4-23554 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Min, Hyegeun A1 - Girard-Lauriault, Pierre-Luc A1 - Gross, Thomas A1 - Lippitz, Andreas A1 - Dietrich, Paul A1 - Unger, Wolfgang T1 - Ambient-ageing processes in amine self-assembled monolayers on microarray slides as studied by ToF-SIMS with principal component analysis, XPS, and NEXAFS spectroscopy N2 - We investigated the ageing of amine-terminated self-assembled monolayers (amine-SAMs) on different silica substrates due to exposure to different ambient gases, pressures, and/or temperatures using time-of-flight secondary ion mass spectrometry (ToF-SIMS) with principal component analysis and complementary methods of surface analysis as X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS). The goal of this study is to examine the durability of primary amine groups of amine-SAMs stored in a user laboratory prior to being used as supports for biomolecule immobilization and other applications. We prepared amine-SAMs on the native oxides of silicon wafers and glass slides using 3- aminopropyl triethoxysilane, by using optimized conditions such as anhydrous organic solvent and reaction time scale of hours to avoid multilayer growth. Selected commercial amine-SAM slides have been investigated, too. When the amine-SAMs are exposed to air, oxygen incorporation occurs, followed by formation of amide groups. The formation of oxygen species due to ageing was proved by ToFSIMS, XPS, and NEXAFS findings such as CNO- secondary ion emission at m/z 42, observation of the N 1s HNC=O component peak at 400.2–400.3 eV in XPS, and, last but not least, by formation of a π*(HNC=O) resonance at 401 eV in the N K-edge X-ray absorption spectrum. It is concluded that the used multi-method approach comprising complementary ToF-SIMS, XPS, and NEXAFS analyses is well suited for a thorough study of chemical aspects of ageing phenomena of amine-SAM surfaces. KW - Amine-SAM KW - Ageing process KW - ToF-SIMS KW - NEXAFS KW - XPS PY - 2012 U6 - https://doi.org/10.1007/s00216-012-5862-5 SN - 1618-2642 SN - 1618-2650 VL - 403 IS - 2 SP - 613 EP - 623 PB - Springer CY - Berlin AN - OPUS4-25829 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Min, Hyegeun A1 - Wettmarshausen, Sascha A1 - Friedrich, Jörg F. A1 - Unger, Wolfgang T1 - A ToF-SIMS Study of the Deuterium-Hydrogen Exchange Induced by Ammonia Plasma Treatment of Simple Polyolefines T2 - SIMS Europe 2010 - 7th European Workshop on Secondary Ion Mass Spectrometry CY - Münster, Germany DA - 2010-09-19 PY - 2010 AN - OPUS4-21987 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Min, Hyegeun A1 - Oran, Umut A1 - Girard-Lauriault, Pierre-Luc A1 - Unger, Wolfgang T1 - ToF-SIMS/Principle Component Analysis (PCA) Study on Ageing of Plasma-Deposited Allylamine Polymer and Styrene/Ethylene-Allylamine Copolymer Films T2 - 12th International Conference on Plasma Surface Engineering CY - Garmisch-Partenkirchen, Germany DA - 2010-09-13 PY - 2010 AN - OPUS4-23068 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wettmarshausen, Sascha A1 - Min, Hyegeun A1 - Unger, Wolfgang A1 - Jäger, Christian A1 - Hidde, Gundula A1 - Friedrich, Jörg Florian T1 - Significance of hydrogen-deuterium exchange at polyolefin surfaces on exposure to ammonia low-pressure plasma N2 - Since more than 40 years ammonia plasma exposure of polyolefins is used for introduction of primary amino groups. The selectivity of this reaction and the yield in primary amino groups was found to be low. Here, a prominent side-reactions of this process was investigated, the hydrogenation by NH3 plasma. For identification of hydrogenation ammonia (NH3) and deuterated ammonia (ND3) were exposed to Polyethylene (h-PE) and fully deuterated polyethylene (d-PE) as well as hexatriacontane (h-HTC) and fully deuterated hexatriacontane (d-HTC) as low-molecular weight model for PE. H–D exchange was assumed and detected by Time-of-Flight Secondary Ion Mass Spectrometry (ToF–SIMS), X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance (ATR-FTIR) and 1H and 2H Nuclear magnetic Resonance. Results show a significant H–D exchange within the sampling depth of ATR (2.5 µm). However, N- and NH2 introduction was limited to the topmost surface as shown by SIMS and XPS (a few nanometers). KW - Deuterated ammonia KW - Ammonia plasma KW - Deuterated polyolefins KW - Hexatriacontane KW - H-D exchange PY - 2011 U6 - https://doi.org/10.1007/s11090-011-9304-5 SN - 0272-4324 VL - 31 IS - 4 SP - 551 EP - 572 PB - Plenum Publ. Corp. CY - New York, NY, USA AN - OPUS4-24178 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Min, Hyegeun A1 - Wettmarshausen, Sascha A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang T1 - A ToF-SIMS study of the deuterium-hydrogen exchange induced by ammonia plasma treatment of polyolefins N2 - ToF-SIMS has been used to study the surface functionalization of polypropylene and polyethylene samples by exposure to low-pressure ammonia plasma. Static secondary ion mass spectrometry is an appropriate tool to determine hydrogen isotopes as elements and in fragment ions with high sensitivity and selectivity. Specifically the exchange of hydrogen isotopes and the incorporation of N-containing moieties in the near-surface layer of the polyolefins have been studied in ND3 plasma experiments with conventional polypropylene (h-PP) and polyethylene (h-PE) and NH3 plasma experiments with deuterated polyethylene (d-PE). Considering the exchange of hydrogen between the plasma and the polymer surface studied by using deuterated ammonia and polyolefin samples the conclusion has been derived that polypropylene with its side chain methyl groups is more susceptible to hydrogen exchange reactions. For ND3 plasma treatment of polyethylene and polypropylene similar N-containing fragments were obtained and the measured semi-quantitative ToF-SIMS N-uptake data are rather similar. The observation of a wide range of characteristic mixed CkNlHmDn+ secondary fragment ions suggests complex and manifold reaction pathways at the polymer–plasma interface besides simple grafting of –ND2 or –NH2 moieties formed by ammonia fragmentation in the plasma. Finally, indications of an isotopic effect for hydrogen isotopes in the plasma process have been observed by comparison of ND3/h-PE results with those of NH3/d-PE. KW - ToF-SIMS KW - Hydrogen-deuterium exchange KW - Ammonia plasma treatment KW - Amine-functionalized polymer KW - Polyolefins PY - 2011 U6 - https://doi.org/10.1039/c1ja10043b SN - 0267-9477 SN - 1364-5544 VL - 26 SP - 1157 EP - 1165 PB - Royal Society of Chemistry CY - London AN - OPUS4-23754 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -