Formation, structure, and reactivity of amino-terminated organic films on silicon substrates.

Amino-functionalized organic films were prepared by self-assembling 3-aminopropyltriethoxysilane (APTES) on silicon wafers in either anhydrous toluene or phosphate-buffered saline (PBS) for varied deposition times. Fourier transform infrared spectroscopy (FTIR) and ellipsometry have shown that the structure and thickness of APTES films are governed by the deposition time and reaction solution. Deposition from an anhydrous toluene solution produces APTES films ranging from 10 to 144 A in thickness, depending on the reaction time. FTIR spectra indicate that film growth initially proceeds by adsorption of APTES to the silicon surface followed by siloxane condensation, and after an extended period of time APTES molecules accumulate on the underlying APTES film by either covalent or noncovalent interactions. In contrast, spectroscopically indistinguishable APTES films in thickness ranging from 8 to 13 A were formed when deposition was conducted in aqueous solutions. Measured water contact angles indicate that APTES films deposited in aqueous solutions are more hydrophilic compared to those prepared in toluene solutions. Fluorescence measurements revealed that APTES films prepared in toluene solutions contain more reactive surface amino groups by ca. 3 to 10 times than those prepared in aqueous solutions for the identical reaction time.

[1]  P. Braun,et al.  Patterned poly(N-isopropylacrylamide) brushes on silica surfaces by microcontact printing followed by surface-initiated polymerization. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[2]  D. Reinhoudt,et al.  Molecular Printboards: Monolayers of β-Cyclodextrins on Silicon Oxide Surfaces , 2004 .

[3]  Brian L. Frey,et al.  Characterization of poly-L-lysine adsorption onto alkanethiol-modified gold surfaces with polarization-modulation Fourier transform infrared spectroscopy and surface plasmon resonance measurements , 1994 .

[4]  P. Soltys,et al.  Equilibrium adsorption of LDL and gold immunoconjugates to affinity membranes containing PEG spacers. , 2000, Biomaterials.

[5]  Bo Liedberg,et al.  Functionalized Self-Assembled Monolayers on Gold as Binding Matrices for the Screening of Antibody-Antigen Interactions , 2003 .

[6]  Qinlin Gu,et al.  Tribological behaviors of self-assembled 3-aminopropyltriethoxysilane films on silicon , 2008 .

[7]  David N Reinhoudt,et al.  Engineering silicon oxide surfaces using self-assembled monolayers. , 2005, Angewandte Chemie.

[8]  Paul Heremans,et al.  Static solvent contact angle measurements, surface free energy and wettability determination of various self-assembled monolayers on silicon dioxide , 2006 .

[9]  P. Stenius,et al.  ESCA and contact angle studies of the adsorption of aminosilanes on mica , 1988 .

[10]  S. High,et al.  Membrane integration of Sec61alpha: a core component of the endoplasmic reticulum translocation complex. , 1998, The Biochemical journal.

[11]  Min Zhu,et al.  Preparation and nano/microtribological properties of perfluorododecanoic acid (PFDA)–3-aminopropyltriethoxysilane (APS) self-assembled dual-layer film deposited on silicon , 2008 .

[12]  S. Margel,et al.  Functionalized thin films : synthesis, characterization, and potential use , 1991 .

[13]  Névine Rochat,et al.  Attenuated total reflection spectroscopy for infrared analysis of thin layers on a semiconductor substrate , 2002 .

[14]  J. Lenhard,et al.  Chemically Modified Electrodes. IX. X-Ray Photoelectron Spectroscopy of Alkylaminesilanes Bound to Metal Oxide Electrodes. , 1978 .

[15]  H. Hoffmann,et al.  Reflection-absorption infrared spectroscopy of self-assembled monolayers on gold and silicon surfaces , 1995 .

[16]  J. Koenig,et al.  FT—IR characterization of the reaction at the silane/matrix resin interphase of composite materials , 1986 .

[17]  Single-Reflection Attenuated Total Reflection of Organic Monolayers on Silicon , 2003, Applied spectroscopy.

[18]  R. Kellner,et al.  FTIR-ATR-spectroscopic investigation of the silanization of germanium surfaces with 3-aminopropyltriethoxysilane , 1989 .

[19]  K. Hattori,et al.  Synthesis of chitosan derivatives bearing cyclodextrin and adsorption of p-nonylphenol and bisphenol A , 2003 .

[20]  Lesile Glasser The chemistry of silica: By Ralph K. Iller. Pp. vii+ 866. Wiley, Chichester. 1979, £39.50 , 1980 .

[21]  Andreas Ebner,et al.  Comparison of different aminofunctionalization strategies for attachment of single antibodies to AFM cantilevers. , 2007, Ultramicroscopy.

[22]  J. Koenig,et al.  The structure of γ-aminopropyltriethoxysilane on glass surfaces , 1980 .

[23]  F. Shimura,et al.  Infrared spectroscopy of thin silicon dioxide on silicon , 1988 .

[24]  T. Hopson,et al.  Evaluation of amine‐ and amide‐terminated self‐assembled monolayers as ‘Molecular glues’ for Au and SiO2 substrates , 2001 .

[25]  Robert M. Corn,et al.  Covalent Attachment and Derivatization of Poly(l-lysine) Monolayers on Gold Surfaces As Characterized by Polarization−Modulation FT-IR Spectroscopy , 1996 .

[26]  J. Youngblood,et al.  Optimization of silica silanization by 3-aminopropyltriethoxysilane. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[27]  C. Freire,et al.  Copper acetylacetonate anchored onto amine-functionalised clays. , 2007, Journal of colloid and interface science.

[28]  H. Hoffmann,et al.  Stepwise growth of ultrathin SiOx films on Si(100) surfaces through sequential adsorption/oxidation cycles of alkylsiloxane monolayers , 1996 .

[29]  Joonyeong Kim,et al.  Investigations of the effect of curing conditions on the structure and stability of amino-functionalized organic films on silicon substrates by Fourier transform infrared spectroscopy, ellipsometry, and fluorescence microscopy , 2008 .

[30]  Marc D. Porter,et al.  Investigation of Approaches for the Fabrication of Protein Patterns by Scanning Probe Lithography , 2001 .

[31]  F. Rubio,et al.  Study of the hydrolysis and condensation of γ-Aminopropyltriethoxysilane by FT-IR spectroscopy , 2007 .

[32]  S. M. Hu,et al.  Infrared absorption spectra of SiO2 precipitates of various shapes in silicon: calculated and experimental , 1980 .

[33]  H. Hoffmann,et al.  Monolayers at solid–solid interfaces probed with infrared spectroscopy , 2007, Analytical and bioanalytical chemistry.

[34]  V. Gun'ko,et al.  Influence of the Partial Hydrophobization of Fumed Silica by Hexamethyldisilazane on Interactions with Water , 2003 .

[35]  T. Bein,et al.  Surface reactions on thin layers of silane coupling agents , 1993 .

[36]  J. Koenig,et al.  Structure of silane coupling agents adsorbed on silicon powder , 1985 .

[37]  M. Delamar,et al.  Adsorption of aminopropyltriethoxy silane on quartz: an XPS and contact angle measurements study , 1996 .

[38]  H. Hoffmann,et al.  Structure of Alkylsiloxane Monolayers on Silicon Surfaces Investigated by External Reflection Infrared Spectroscopy , 1995 .

[39]  Jan D. Miller,et al.  Carboxyl Stretching Vibrations of Spontaneously Adsorbed and LB-Transferred Calcium Carboxylates as Determined by FTIR Internal Reflection Spectroscopy , 2002 .

[40]  D. Reinhoudt,et al.  Cation sensing by patterned self-assembled monolayers on gold , 2000 .

[41]  Linus Pauling,et al.  Molecular Models of Amino Acids, Peptides, and Proteins , 1953 .

[42]  B. Newby,et al.  Suppress polystyrene thin film dewetting by modifying substrate surface with aminopropyltriethoxysilane , 2006 .

[43]  Stuart L. Schreiber,et al.  Printing Small Molecules as Microarrays and Detecting Protein−Ligand Interactions en Masse , 1999 .

[44]  Ingemar Lundström,et al.  Structure of 3-aminopropyl triethoxy silane on silicon oxide , 1991 .

[45]  H. Möhwald,et al.  Hydrogen-bonded multilayers of self-assembling silanes: structure elucidation by combined Fourier transform infra-red spectroscopy and X-ray scattering techniques , 1995 .

[46]  S. Pack,et al.  Development of an efficient amine-functionalized glass platform by additional silanization treatment with alkylsilane , 2006, Analytical and bioanalytical chemistry.

[47]  Specific recognition of antibody-oligonucleotide conjugates by radiolabeled antisense nucleotides: a novel approach for two-step radioimmunotherapy of cancer. , 1993, Bioconjugate chemistry.

[48]  Charles R. Kurkjian,et al.  Effects of surface hydration on the deposition of silane monolayers on silica , 1993 .

[49]  R. Boukherroub,et al.  Formation, characterization, and chemistry of undecanoic acid-terminated silicon surfaces: patterning and immobilization of DNA. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[50]  D. Petri,et al.  An Improved Method for the Assembly of Amino-Terminated Monolayers on SiO2 and the Vapor Deposition of Gold Layers , 1999 .

[51]  J. Koenig,et al.  Magic-angle cross-polarization carbon 13 NMR study of aminosilane coupling agents on silica surfaces , 1982 .

[52]  A. Horgan,et al.  Reaction of N-phenyl maleimide with aminosilane monolayers. , 2004, Colloids and surfaces. B, Biointerfaces.

[53]  A. Ulman,et al.  Formation and Structure of Self-Assembled Monolayers. , 1996, Chemical reviews.

[54]  S. Schreiber,et al.  Printing proteins as microarrays for high-throughput function determination. , 2000, Science.

[55]  J. Sagiv,et al.  Organized monolayers by adsorption. 1. Formation and structure of oleophobic mixed monolayers on solid surfaces , 1980 .

[56]  Nikin Patel,et al.  Immobilization of Protein Molecules onto Homogeneous and Mixed Carboxylate-Terminated Self-Assembled Monolayers , 1997 .

[57]  D. Stenger,et al.  Fabrication and Surface Characterization of DNA Microarrays Using Amine- and Thiol-Terminated Oligonucleotide Probes† , 2003 .

[58]  H. Hoffmann,et al.  Investigation of the Formation and Structure of Self-assembled Alkylsiloxane Monolayers on Silicon Using In Situ Attenuated Total Reflection Infrared Spectroscopy , 1999 .

[59]  R. Gallavan,et al.  Investigation of trialkoxysilane hydrolysis kinetics using liquid chromatography with inductively coupled plasma atomic emission spectrometric detection and non-linear regression modeling , 2003 .

[60]  I. Haller Covalently attached organic monolayers on semiconductor surfaces , 1978 .

[61]  M. Porter,et al.  Deposition of metal overlayers at end-group-functionalized thiolate monolayers adsorbed at gold. 1. Surface and interfacial chemical characterization of deposited copper overlayers at carboxylic acid-terminated structures , 1992 .

[62]  K. Mikoshiba,et al.  Calmodulin inhibits inositol 1,4,5‐trisphosphate‐induced calcium release through the purified and reconstituted inositol 1,4,5‐trisphosphate receptor type 1 , 1999, FEBS letters.

[63]  V. Yadavalli,et al.  Investigations of chemical modifications of amino-terminated organic films on silicon substrates and controlled protein immobilization. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[64]  Roger Woodward,et al.  An evaluation of methods for contact angle measurement. , 2005, Colloids and surfaces. B, Biointerfaces.

[65]  D. Reinhoudt,et al.  Functionalization of self‐assembled monolayers on glass and oxidized silicon wafers by surface reactions , 2001 .

[66]  Gil U. Lee,et al.  Covalent attachment of synthetic DNA to self-assembled monolayer films. , 1996, Nucleic acids research.

[67]  J. Koenig,et al.  Analytical and spectroscopic investigation of the interaction of CO2 with amine functional silane coupling agents on glass fibers , 1983 .

[68]  J. Kirkham,et al.  Formation of aminosilane-functionalized mica for atomic force microscopy imaging of DNA. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[69]  Extended length heterobifunctional coupling agents for protein conjugations. , 1996 .

[70]  M. Wilchek,et al.  Immobilization of glycoconjugates by their oligosaccharides: use of hydrazido-derivatized matrices. , 1990, Analytical biochemistry.

[71]  White,et al.  Reaction of (3-Aminopropyl)dimethylethoxysilane with Amine Catalysts on Silica Surfaces. , 2000, Journal of colloid and interface science.

[72]  Jing Li,et al.  Electrochemical and electrochemiluminescence study of Ru(bpy)(2+)3-doped silica nanoparticles with covalently grafted biomacromolecules. , 2008, Journal of colloid and interface science.

[73]  D. S. Hage,et al.  Development of sulfhydryl-reactive silica for protein immobilization in high-performance affinity chromatography. , 2007, Analytical chemistry.

[74]  J. M. Chalmers,et al.  Specular reflectance: A convenient tool for polymer characterization by FTIR-microscopy? , 1996 .

[75]  V. Zaitsev,et al.  Preparation, structure and thermal stability of onium- and amino-functionalized silicas for the use as catalysts supports. , 2006, Journal of colloid and interface science.

[76]  J. McIntosh,et al.  Patterning of functional antibodies and other proteins by photolithography of silane monolayers. , 1996, Proceedings of the National Academy of Sciences of the United States of America.

[77]  Juan Li,et al.  Functionalization of syndiotactic polystyrene with succinic anhydride in the presence of aluminum chloride , 2005 .