← Back to Search
Organosilane Chemical Gradients: Progress, Properties, And Promise.
M. Collinson, D. Higgins
Published 2017 · Chemistry, Medicine
Download PDFAnalyze on Scholarcy
Chemical gradients play an important role in nature, driving many different phenomena critical to life, including the transport of chemical species across membranes and the transport, attachment, and assembly of cells. Taking a cue from these natural processes, scientists and engineers are now working to develop synthetic chemical gradients for use in a broad range of applications, such as in high-throughput investigations of surface properties, as means to guide the motions and/or assembly of liquid droplets, vesicles, nanoparticles, and cells and as new media for stationary-phase-gradient chemical separations. Our groups have been working to develop new methods for preparing chemical gradients from organoalkoxysilane and organochlorosilane precursors and to obtain a better understanding of their properties on macroscopic to microscopic length scales. This review highlights our recent work on the development of controlled-rate infusion and infusion-withdrawal dip-coating methods for the preparation of gradients on planar glass and silicon substrates, on thin-layer chromatography plates, and in capillaries and monoliths for liquid chromatography. We also cover the new knowledge gained from the characterization of our gradients using sessile drop and Wilhelmy plate dynamic water contact angle measurements, X-ray photoelectron spectroscopy mapping, and single-molecule tracking and spectroscopy. Our studies reveal important evidence of phase separation and cooperative interactions occurring along multicomponent gradients. Emerging concepts and new directions in the preparation and characterization of organosilane-based chemical gradients are also discussed.
This paper references
Chemical imaging of protein adsorption and crystallization on a wettability gradient surface.
S. Glassford (2012)
Reactions of chlorosilanes with silica surfaces
M. Hair (1969)
Wetting-dewetting transition line in thin polymer films.
K. M. Ashley (2005)
Molecular Combing of λ-DNA using Self-Propelled Water Droplets on Wettability Gradient Surfaces.
Dipak Giri (2016)
Fluorescence Spectroscopy Studies of Silica Film Polarity Gradients Prepared by Infusion-Withdrawal Dip-Coating
F. Ye (2010)
Analytical instrumentation infrastructure for combinatorial and high-throughput development of formulated discrete and gradient polymeric sensor materials arrays
R. Potyrailo (2005)
Isoelectric focusing in immobilized pH gradients
P. G. Righetti (1989)
Reactive self-assembled monolayers: from surface functionalization to gradient formation
C. Nicosia (2014)
Measuring the spatial distribution of dielectric constants in polymers through quasi-single molecule microscopy.
Chelsea Hess Haupt (2013)
Moisture absorption characteristics of organosiloxane self-assembled monolayers
David L. Angst (1991)
Phase separation in class II organically modified silicate films as probed by phase-imaging atomic force microscopy.
J. Striová (2005)
Single-molecule probing of adsorption and diffusion on silica surfaces.
M. Wirth (2007)
High-Throughput Measurement of Polymer Blend Phase Behavior
J. Meredith (2000)
Fabricating Tunable Nanoparticle Density Gradients with the Contact Printing Based Approach
F. Song (2006)
Combinatorial Materials Science for Polymer Thin-Film Dewetting
J. Meredith (2000)
pH-tunable gradients of wettability and surface potential
A. Mierczynska (2012)
Submicrometer structure of surface-chemical gradients prepared by a two-step immersion method.
S. Morgenthaler (2006)
Study of adhesion and friction properties on a nanoparticle gradient surface: transition from JKR to DMT contact mechanics.
S. N. Ramakrishna (2013)
Role of solvent and base in the silanization reaction of silicas for reversed-phase high-performance liquid chromatography
J. Kinkel (1984)
Vesicles surfing on a lipid bilayer: Self-induced haptotactic motion
Jérôme Solon (2006)
Chemical force microscopy of mixed self-assembled monolayers of alkanethiols on gold: evidence for phase separation.
N. J. Brewer (2004)
Versatile wettability gradients prepared by chemical modification of polymer brushes on polymer foils.
S. Neuhaus (2011)
Universal Gradient Substrates for “Click” Biofunctionalization
N. Gallant (2007)
Single-Molecule Spectroscopic Imaging Studies of Polarity Gradients Prepared by Infusion-Withdrawal Dip-Coating
Dipak Giri (2014)
Tuning cell adhesion on gradient poly(2-hydroxyethyl methacrylate)-grafted surfaces.
Ying Mei (2005)
Controlling adhesion force by means of nanoscale surface roughness.
S. N. Ramakrishna (2011)
Chemically Modified Electrodes. IX. X-Ray Photoelectron Spectroscopy of Alkylaminesilanes Bound to Metal Oxide Electrodes.
P. Moses (1978)
Effect of Heterogenic Surfaces on Contact Angle Hysteresis: Dynamic Contact Angle Analysis in Material Sciences
F. Rupp (2002)
Molecular Approaches to Chromatography Using Single Molecule Spectroscopy
Lydia Kisley (2015)
Surface-bound soft matter gradients.
J. Genzer (2008)
Effect of Ormosil and Polymer Doping on the Morphology of Separately and Co-hydrolyzed Silica Films Formed by a Two-Step Aqueous Processing Method
G. Goring (2007)
Sol-gel thin film formation
C. Brinker (1990)
Single molecule observations of desorption-mediated diffusion at the solid-liquid interface.
Robert Walder (2011)
Structure, chemistry, and applications of sol-gel derived materials
M. Collinson (2001)
Fast directed motion of "fakir" droplets.
R. Petrie (2004)
Acid-base properties and the chemical imaging of surface-bound functional groups studied with scanning force microscopy
E. W. V. D. Vegte (1997)
Construction and Reactivity Mapping of a Platinum Catalyst Gradient Using the Scanning Electrochemical Microscope
S. Jayaraman (2001)
Synthesis and evaluation of polymeric continuous bed (monolithic) reversed-phase gradient stationary phases for capillary liquid chromatography and capillary electrochromatography.
A. Maruška (2007)
Recent trends in analytical applications of organically modified silicate materials
M. Collinson (2002)
A new technique to prepare gradient surfaces using density gradient solutions
C. Gölander (1989)
Self-assembly fronts in collision: impinging ordering organosilane layers
K. Efimenko (2013)
Construction of a tethered poly(ethylene glycol) surface gradient for studies of cell adhesion kinetics.
K. Mougin (2005)
Formation mechanisms and properties of semifluorinated molecular gradients on silica surfaces.
J. Genzer (2006)
Contact angle hysteresis: a review of fundamentals and applications
H. B. Eral (2012)
Trajectory of isoelectric focusing from gels to capillaries to immobilized gradients in capillaries
B. Koshel (2012)
Cooperative Effects in Aligned and Opposed Multicomponent Charge Gradients Containing Strongly Acidic, Weakly Acidic, and Basic Functional Groups.
K. Ashraf (2016)
Controlling the assembly of nanoparticles using surface grafted molecular and macromolecular gradients
R. R. Bhat (2003)
Versatile platform for creating gradient combinatorial libraries via modulated light exposure.
Brian C. Berry (2007)
Directed nanoparticle motion on an interfacial free energy gradient.
Robert Walder (2010)
Separation of transition metals using inorganic adsorbents modified with chelating ligands
Y. Shiraishi (2002)
Different types of phase separation in binary monolayers of long chain alkyltrichlorosilanes on silicon oxide
Simon Desbief (2012)
Aminoalkoxysilane reactivity in surface amine gradients prepared by controlled-rate infusion.
B. Kannan (2012)
Investigation of thermally responsive block copolymer thin film morphologies using gradients.
Jennifer Y. Kelly (2010)
Designed Hybrid Organic−Inorganic Nanocomposites from Functional Nanobuilding Blocks
C. Sanchez (2001)
Disorder in Alkylsilane Monolayers Assembled on Surfaces with Nanoscopic Curvature
R. Jones (2009)
The surface density gradient of grafted poly (ethylene glycol): preparation, characterization and protein adsorption.
Y. S. Lin (1994)
Organic Chemistry within Ceramic Matrixes: Doped Sol-Gel Materials
D. Avnir (1995)
Fabrication of Chemical Gradient Using Space Limited Plasma Oxidation and its Application for Droplet Motion
Xiaojun Han (2012)
Homogeneously and gradually anchored self-assembled monolayer by tunable vapor phase-assisted silanization
Grégoire Souharce (2013)
Separation of transition and heavy metals using stationary phase gradients and thin layer chromatography.
Stacy L. Stegall (2016)
Measurement of cell migration on surface-bound fibronectin gradients.
J. T. Smith (2004)
Active Spatiotemporal Control of Arg-Gly-Asp-Containing Tetradecapeptide Organomercaptans on Gold with In−Plane Electrochemical Potential Gradients
Q. W. and (2003)
A combinatorial approach to study solvent-induced self-assembly of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica substrates: effect of relative grafting density.
B. Zhao (2004)
Continuous stationary phase gradients for planar chromatographic media.
B. Kannan (2011)
Single-molecule studies of diffusion by oligomer-bound dyes in organically modified sol-gel-derived silicate films.
Skylar A Martin-Brown (2005)
Formation and Structure of Self-Assembled Monolayers.
A. Ulman (1996)
Enzymes and Other Proteins Entrapped in Sol-Gel Materials
D. Avnir (1994)
Chelation gradients for investigation of metal ion binding at silica surfaces.
B. Kannan (2014)
Fabricating Planar Nanoparticle Assemblies with Number Density Gradients
R. R. Bhat (2002)
Fast drop movements resulting from the phase change on a gradient surface.
S. Daniel (2001)
Single Molecule Catch and Release: Potential-Dependent Plasmid DNA Adsorption along Chemically Graded Electrode Surfaces.
Z. Li (2017)
Protein and nanoparticle adsorption on orthogonal, charge-density-versus-net-charge surface-chemical gradients.
Eva Beurer (2012)
Monolithic polymer layer with gradient of hydrophobicity for separation of peptides using two-dimensional thin layer chromatography and MALDI-TOF-MS detection.
Iva Urbanová (2011)
Profile control in surface amine gradients prepared by controlled-rate infusion.
B. Kannan (2011)
Spatiotemporal Evolution of Fixed and Mobile Dopant Populations in Silica Thin-Film Gradients as Revealed by Single Molecule Tracking
Chenchen Cui (2011)
Tuning the number density of nanoparticles by multivariant tailoring of attachment points on flat substrates
R. Bhat (2007)
Spatial Dispersion in Electrochemically Generated Surface Composition Gradients Visualized with Covalently Bound Fluorescent Nanospheres
S. Plummer (2002)
A systematic comparison of contact angle methods
L. Lander (1993)
Single-Molecule Perspective on Mass Transport in Condensed Water Layers over Gradient Self-Assembled Monolayers
Dipak Giri (2015)
Chemical modification of self-assembled silane based monolayers by surface reactions.
C. Hänsch (2010)
Mechanism of the ninhydrin reaction
C. B. Bottom (1978)
Cellular responses on a wettability gradient surface with continuous variations in surface compositions of carbonate and hydroxyl groups
Tomoko Ueda-Yukoshi (1995)
Monolithic columns with a gradient of functionalities prepared via photoinitiated grafting for separations using capillary electrochromatography.
Vincenzo Pucci (2004)
Surface-Bound Gradients for Studies of Soft Materials Behavior
J. Genzer (2012)
Phase separation of binary mixtures in thin films: Effects of an initial concentration gradient across the film.
P. K. Jaiswal (2012)
Generation of monolayer gradients in surface energy and surface chemistry for block copolymer thin film studies.
J. Albert (2009)
Engineering silicon oxide surfaces using self-assembled monolayers.
S. Onclin (2005)
Nile Red as a solvatochromic dye for measuring solvent strength in normal liquids and mixtures of normal liquids with supercritical and near critical fluids
Jerry F. Deye (1990)
A Simple, Reproducible Approach to the Preparation of Surface-Chemical Gradients
S. Morgenthaler (2003)
Surface-chemical and -morphological gradients.
S. Morgenthaler (2008)
Directed transport by surface chemical potential gradients for enhancing analyte collection in nanoscale sensors.
A. Sitt (2015)
Effect of annealing on self-organized gradient film obtained from poly(3-[tris(trimethylsilyloxy)silyl] propyl methacrylate-co-methyl methacrylate)/poly(methyl methacrylate-co-n-butyl acrylate) blend latexes
L. Hu (2012)
Electrochemical Applications of Silica-Based Organic−Inorganic Hybrid Materials
A. Walcarius (2001)
Base Layer Influence on Protonated Aminosilane Gradient Wettability.
K. Ashraf (2017)
Analytical applications of organically modified silicates
M. Collinson (1998)
The desorption of ribonuclease A from charge density gradient surfaces studied by spatially-resolved total internal reflection fluorescence.
Y. S. Lin (1995)
How to Make Water Run Uphill
M. Chaudhury (1992)
Haptotaxis and the Mechanism of Cell Motility
S. Carter (1967)
Water-collecting capability of radial-wettability gradient surfaces generated by controlled surface reactions.
Daewha Hong (2010)
Beyond sequencing: optical mapping of DNA in the age of nanotechnology and nanoscopy.
Michal Levy-Sakin (2013)
The sol-gel process
L. Hench (1990)
Generation of contact-printing based poly(ethylene glycol) gradient surfaces with micrometer-sized steps.
Y. Cai (2010)
Wetting and plasma-protein adsorption studies using surfaces with a hydrophobicity gradient
C. Gölander (1990)
Amine Gradient Stationary Phases on In-House Built Monolithic Columns for Liquid Chromatography.
V. Dewoolkar (2016)
The movement of a water droplet on a gradient surface prepared by photodegradation.
Y. Ito (2007)
Imaging of phase segregation in gradient copolymers: Island and hole surface topography
Michelle M. Mok (2012)
Hybrid Inorganic-Organic Materials by Sol-Gel Processing of Organofunctional Metal Alkoxides
U. Schubert (1995)
Review of sol-gel thin film formation
C. Brinker (1992)
Organic/Inorganic Hybrid Network Materials by the Sol−Gel Approach
J. Wen (1996)
Combinatorial approach to study enzyme/surface interactions.
K. Loos (2005)
A wettability gradient method for studies of macromolecular interactions at the liquid/solid interface
H. Elwing (1987)
Gradient and Low‐Temperature Thin‐Layer Chromatography
E. Stahl (1964)
Directed single molecule diffusion triggered by surface energy gradients.
P. Burgos (2009)
Effect of Block Length on Solvent Response of Block Copolymer Brushes: Combinatorial Study with Block Copolymer Brush Gradients
Chang Xu (2006)
Micrometer-scaled Gradient Surfaces Generated Using Contact Printing of Octadecyltrichlorosilane
Sung-Hwan Choi (2003)
Dynamic Monolayer Gradients: Active Spatiotemporal Control of Alkanethiol Coatings on Thin Gold Films
Roger H. Terrill (2000)
Fabrication of surface charge gradients in open-tubular capillaries and their characterization by spatially resolved pulsed streaming potential measurements.
B. Kannan (2013)
Amine-phenyl multi-component gradient stationary phases.
V. Dewoolkar (2015)
This paper is referenced by
In situ silanization for continuous stationary phase gradients on particle packed LC columns
Anna V. Forzano (2019)
On the Importance of Silane Infusion Order on the Microscopic and Macroscopic Properties of Multifunctional Charge Gradients
K. Ashraf (2020)
Amine/phenyl gradient derived base layer as a comprehensive extractive phase for headspace cooled in-tube microextraction of volatile organic compounds in saliva.
Marzieh Enteshari Najafabadi (2020)
Fabrication and Characterization of a Reversed-Phase/Strong Cation Exchange Stationary Phase Gradient.
Caitlin N. Cain (2020)
Experimental- and simulation-based investigations of coupling a mobile phase gradient with a continuous stationary phase gradient.
Caitlin N. Cain (2019)
Creating Directionality in Nanoporous Carbon Materials: Adjustable Combinations of Structural and Chemical Gradients
Jochen Bahner (2019)