Online citations, reference lists, and bibliographies.
← Back to Search

Organosilane Chemical Gradients: Progress, Properties, And Promise.

M. Collinson, D. Higgins
Published 2017 · Chemistry, Medicine

Cite This
Download PDF
Analyze on Scholarcy
Share
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
10.1021/la204524w
Chemical imaging of protein adsorption and crystallization on a wettability gradient surface.
S. Glassford (2012)
10.1021/J100727A046
Reactions of chlorosilanes with silica surfaces
M. Hair (1969)
10.1021/LA050482Y
Wetting-dewetting transition line in thin polymer films.
K. M. Ashley (2005)
10.1021/acsami.6b08607
Molecular Combing of λ-DNA using Self-Propelled Water Droplets on Wettability Gradient Surfaces.
Dipak Giri (2016)
10.1021/CM1003752
Fluorescence Spectroscopy Studies of Silica Film Polarity Gradients Prepared by Infusion-Withdrawal Dip-Coating
F. Ye (2010)
10.1063/1.1906165
Analytical instrumentation infrastructure for combinatorial and high-throughput development of formulated discrete and gradient polymeric sensor materials arrays
R. Potyrailo (2005)
10.1021/AC00190A004
Isoelectric focusing in immobilized pH gradients
P. G. Righetti (1989)
10.1039/C3MH00046J
Reactive self-assembled monolayers: from surface functionalization to gradient formation
C. Nicosia (2014)
10.1021/jp4008398
Measuring the spatial distribution of dielectric constants in polymers through quasi-single molecule microscopy.
Chelsea Hess Haupt (2013)
10.1021/LA00058A043
Moisture absorption characteristics of organosiloxane self-assembled monolayers
David L. Angst (1991)
10.1021/LA050473P
Phase separation in class II organically modified silicate films as probed by phase-imaging atomic force microscopy.
J. Striová (2005)
10.1146/ANNUREV.PHYSCHEM.58.032806.104427
Single-molecule probing of adsorption and diffusion on silica surfaces.
M. Wirth (2007)
10.1021/MA0004662
High-Throughput Measurement of Polymer Blend Phase Behavior
J. Meredith (2000)
10.1016/J.APSUSC.2006.04.052
Fabricating Tunable Nanoparticle Density Gradients with the Contact Printing Based Approach
F. Song (2006)
10.1021/MA001298G
Combinatorial Materials Science for Polymer Thin-Film Dewetting
J. Meredith (2000)
10.1039/C2SM25221J
pH-tunable gradients of wettability and surface potential
A. Mierczynska (2012)
10.1021/LA0526840
Submicrometer structure of surface-chemical gradients prepared by a two-step immersion method.
S. Morgenthaler (2006)
10.1021/la304226v
Study of adhesion and friction properties on a nanoparticle gradient surface: transition from JKR to DMT contact mechanics.
S. N. Ramakrishna (2013)
10.1016/S0021-9673(00)96151-X
Role of solvent and base in the silanization reaction of silicas for reversed-phase high-performance liquid chromatography
J. Kinkel (1984)
10.1073/pnas.0601400103
Vesicles surfing on a lipid bilayer: Self-induced haptotactic motion
Jérôme Solon (2006)
10.1021/LA036301E
Chemical force microscopy of mixed self-assembled monolayers of alkanethiols on gold: evidence for phase separation.
N. J. Brewer (2004)
10.1021/la2005908
Versatile wettability gradients prepared by chemical modification of polymer brushes on polymer foils.
S. Neuhaus (2011)
10.1002/ADMA.200602221
Universal Gradient Substrates for “Click” Biofunctionalization
N. Gallant (2007)
10.1021/JP412508C
Single-Molecule Spectroscopic Imaging Studies of Polarity Gradients Prepared by Infusion-Withdrawal Dip-Coating
Dipak Giri (2014)
10.1021/LA050668X
Tuning cell adhesion on gradient poly(2-hydroxyethyl methacrylate)-grafted surfaces.
Ying Mei (2005)
10.1021/la201727t
Controlling adhesion force by means of nanoscale surface roughness.
S. N. Ramakrishna (2011)
10.1021/AC50026A010
Chemically Modified Electrodes. IX. X-Ray Photoelectron Spectroscopy of Alkylaminesilanes Bound to Metal Oxide Electrodes.
P. Moses (1978)
10.1002/1521-4125(20020910)25:9<877::AID-CEAT877>3.0.CO;2-D
Effect of Heterogenic Surfaces on Contact Angle Hysteresis: Dynamic Contact Angle Analysis in Material Sciences
F. Rupp (2002)
10.1021/ac5039225
Molecular Approaches to Chromatography Using Single Molecule Spectroscopy
Lydia Kisley (2015)
10.1021/la7033164
Surface-bound soft matter gradients.
J. Genzer (2008)
10.1021/CM071577J
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)
10.1016/0022-3093(90)90147-E
Sol-gel thin film formation
C. Brinker (1990)
10.1103/PHYSREVLETT.107.156102
Single molecule observations of desorption-mediated diffusion at the solid-liquid interface.
Robert Walder (2011)
10.1016/B978-012513745-4/50047-0
Structure, chemistry, and applications of sol-gel derived materials
M. Collinson (2001)
10.1021/LA048612A
Fast directed motion of "fakir" droplets.
R. Petrie (2004)
10.1021/JP9709060
Acid-base properties and the chemical imaging of surface-bound functional groups studied with scanning force microscopy
E. W. V. D. Vegte (1997)
10.1021/LA010930B
Construction and Reactivity Mapping of a Platinum Catalyst Gradient Using the Scanning Electrochemical Microscope
S. Jayaraman (2001)
10.1016/J.JBBM.2006.10.011
Synthesis and evaluation of polymeric continuous bed (monolithic) reversed-phase gradient stationary phases for capillary liquid chromatography and capillary electrochromatography.
A. Maruška (2007)
10.1016/S0165-9936(01)00125-X
Recent trends in analytical applications of organically modified silicate materials
M. Collinson (2002)
10.1016/0166-6622(89)80084-8
A new technique to prepare gradient surfaces using density gradient solutions
C. Gölander (1989)
10.1039/C2SM27600C
Self-assembly fronts in collision: impinging ordering organosilane layers
K. Efimenko (2013)
10.1021/LA050613V
Construction of a tethered poly(ethylene glycol) surface gradient for studies of cell adhesion kinetics.
K. Mougin (2005)
10.1021/LA061016R
Formation mechanisms and properties of semifluorinated molecular gradients on silica surfaces.
J. Genzer (2006)
10.1007/s00396-012-2796-6
Contact angle hysteresis: a review of fundamentals and applications
H. B. Eral (2012)
10.1002/pmic.201200213
Trajectory of isoelectric focusing from gels to capillaries to immobilized gradients in capillaries
B. Koshel (2012)
10.1021/acs.langmuir.6b00638
Cooperative Effects in Aligned and Opposed Multicomponent Charge Gradients Containing Strongly Acidic, Weakly Acidic, and Basic Functional Groups.
K. Ashraf (2016)
10.1088/0957-4484/14/10/313
Controlling the assembly of nanoparticles using surface grafted molecular and macromolecular gradients
R. R. Bhat (2003)
10.1063/1.2755729
Versatile platform for creating gradient combinatorial libraries via modulated light exposure.
Brian C. Berry (2007)
10.1021/la903753z
Directed nanoparticle motion on an interfacial free energy gradient.
Robert Walder (2010)
10.1021/IE020119B
Separation of transition metals using inorganic adsorbents modified with chelating ligands
Y. Shiraishi (2002)
10.1039/C2RA01327D
Different types of phase separation in binary monolayers of long chain alkyltrichlorosilanes on silicon oxide
Simon Desbief (2012)
10.1021/la303580c
Aminoalkoxysilane reactivity in surface amine gradients prepared by controlled-rate infusion.
B. Kannan (2012)
10.1021/am100695m
Investigation of thermally responsive block copolymer thin film morphologies using gradients.
Jennifer Y. Kelly (2010)
10.1021/CM011061E
Designed Hybrid Organic−Inorganic Nanocomposites from Functional Nanobuilding Blocks
C. Sanchez (2001)
10.1021/JP8081358
Disorder in Alkylsilane Monolayers Assembled on Surfaces with Nanoscopic Curvature
R. Jones (2009)
10.1016/0927-7765(93)01114-7
The surface density gradient of grafted poly (ethylene glycol): preparation, characterization and protein adsorption.
Y. S. Lin (1994)
10.1021/AR00056A002
Organic Chemistry within Ceramic Matrixes: Doped Sol-Gel Materials
D. Avnir (1995)
10.1002/ADFM.201201121
Fabrication of Chemical Gradient Using Space Limited Plasma Oxidation and its Application for Droplet Motion
Xiaojun Han (2012)
10.1039/C3RA41471J
Homogeneously and gradually anchored self-assembled monolayer by tunable vapor phase-assisted silanization
Grégoire Souharce (2013)
10.1016/j.chroma.2016.04.005
Separation of transition and heavy metals using stationary phase gradients and thin layer chromatography.
Stacy L. Stegall (2016)
10.1021/LA0489763
Measurement of cell migration on surface-bound fibronectin gradients.
J. T. Smith (2004)
10.1021/JP030329H
Active Spatiotemporal Control of Arg-Gly-Asp-Containing Tetradecapeptide Organomercaptans on Gold with In−Plane Electrochemical Potential Gradients
Q. W. and (2003)
10.1021/LA047681M
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)
10.1016/j.chroma.2011.10.075
Continuous stationary phase gradients for planar chromatographic media.
B. Kannan (2011)
10.1021/AC0491511
Single-molecule studies of diffusion by oligomer-bound dyes in organically modified sol-gel-derived silicate films.
Skylar A Martin-Brown (2005)
10.1021/CR9502357
Formation and Structure of Self-Assembled Monolayers.
A. Ulman (1996)
10.1021/CM00046A008
Enzymes and Other Proteins Entrapped in Sol-Gel Materials
D. Avnir (1994)
10.1021/la502088k
Chelation gradients for investigation of metal ion binding at silica surfaces.
B. Kannan (2014)
10.1021/LA025524M
Fabricating Planar Nanoparticle Assemblies with Number Density Gradients
R. R. Bhat (2002)
10.1126/SCIENCE.291.5504.633
Fast drop movements resulting from the phase change on a gradient surface.
S. Daniel (2001)
10.1021/acs.langmuir.7b00044
Single Molecule Catch and Release: Potential-Dependent Plasmid DNA Adsorption along Chemically Graded Electrode Surfaces.
Z. Li (2017)
10.1021/la203964a
Protein and nanoparticle adsorption on orthogonal, charge-density-versus-net-charge surface-chemical gradients.
Eva Beurer (2012)
10.1002/jssc.201100202
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)
10.1021/la104448n
Profile control in surface amine gradients prepared by controlled-rate infusion.
B. Kannan (2011)
10.1021/JP109757K
Spatiotemporal Evolution of Fixed and Mobile Dopant Populations in Silica Thin-Film Gradients as Revealed by Single Molecule Tracking
Chenchen Cui (2011)
10.1088/0957-4484/18/2/025301
Tuning the number density of nanoparticles by multivariant tailoring of attachment points on flat substrates
R. Bhat (2007)
10.1021/LA011742O
Spatial Dispersion in Electrochemically Generated Surface Composition Gradients Visualized with Covalently Bound Fluorescent Nanospheres
S. Plummer (2002)
10.1021/LA00032A055
A systematic comparison of contact angle methods
L. Lander (1993)
10.1021/ACS.JPCC.5B01958
Single-Molecule Perspective on Mass Transport in Condensed Water Layers over Gradient Self-Assembled Monolayers
Dipak Giri (2015)
10.1039/b920491a
Chemical modification of self-assembled silane based monolayers by surface reactions.
C. Hänsch (2010)
10.1016/0307-4412(78)90153-X
Mechanism of the ninhydrin reaction
C. B. Bottom (1978)
10.1021/LA00010A080
Cellular responses on a wettability gradient surface with continuous variations in surface compositions of carbonate and hydroxyl groups
Tomoko Ueda-Yukoshi (1995)
10.1002/JSSC.200401828
Monolithic columns with a gradient of functionalities prepared via photoinitiated grafting for separations using capillary electrochromatography.
Vincenzo Pucci (2004)
10.1146/ANNUREV-MATSCI-070511-155050
Surface-Bound Gradients for Studies of Soft Materials Behavior
J. Genzer (2012)
10.1103/PHYSREVE.85.041602
Phase separation of binary mixtures in thin films: Effects of an initial concentration gradient across the film.
P. K. Jaiswal (2012)
10.1021/nn900750w
Generation of monolayer gradients in surface energy and surface chemistry for block copolymer thin film studies.
J. Albert (2009)
10.1002/ANIE.200500633
Engineering silicon oxide surfaces using self-assembled monolayers.
S. Onclin (2005)
10.1021/AC00205A015
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)
10.1021/LA034707L
A Simple, Reproducible Approach to the Preparation of Surface-Chemical Gradients
S. Morgenthaler (2003)
10.1039/B715466F
Surface-chemical and -morphological gradients.
S. Morgenthaler (2008)
10.1021/acs.nanolett.5b00595
Directed transport by surface chemical potential gradients for enhancing analyte collection in nanoscale sensors.
A. Sitt (2015)
10.1007/s00396-011-2582-x
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)
10.1021/CM0110167
Electrochemical Applications of Silica-Based Organic−Inorganic Hybrid Materials
A. Walcarius (2001)
10.1021/acs.langmuir.7b00614
Base Layer Influence on Protonated Aminosilane Gradient Wettability.
K. Ashraf (2017)
10.1007/BF01244737
Analytical applications of organically modified silicates
M. Collinson (1998)
10.1016/0927-7765(94)01150-4
The desorption of ribonuclease A from charge density gradient surfaces studied by spatially-resolved total internal reflection fluorescence.
Y. S. Lin (1995)
10.1126/science.256.5063.1539
How to Make Water Run Uphill
M. Chaudhury (1992)
10.1038/213256A0
Haptotaxis and the Mechanism of Cell Motility
S. Carter (1967)
10.1021/la102379s
Water-collecting capability of radial-wettability gradient surfaces generated by controlled surface reactions.
Daewha Hong (2010)
10.1016/j.copbio.2013.01.009
Beyond sequencing: optical mapping of DNA in the age of nanotechnology and nanoscopy.
Michal Levy-Sakin (2013)
10.1021/CR00099A003
The sol-gel process
L. Hench (1990)
10.1016/j.colsurfb.2009.08.023
Generation of contact-printing based poly(ethylene glycol) gradient surfaces with micrometer-sized steps.
Y. Cai (2010)
10.1016/0166-6622(90)80111-G
Wetting and plasma-protein adsorption studies using surfaces with a hydrophobicity gradient
C. Gölander (1990)
10.1021/acs.analchem.6b00895
Amine Gradient Stationary Phases on In-House Built Monolithic Columns for Liquid Chromatography.
V. Dewoolkar (2016)
10.1021/LA0624992
The movement of a water droplet on a gradient surface prepared by photodegradation.
Y. Ito (2007)
10.1002/POLB.22393
Imaging of phase segregation in gradient copolymers: Island and hole surface topography
Michelle M. Mok (2012)
10.1021/CM00059A007
Hybrid Inorganic-Organic Materials by Sol-Gel Processing of Organofunctional Metal Alkoxides
U. Schubert (1995)
10.1016/S0022-3093(05)80653-2
Review of sol-gel thin film formation
C. Brinker (1992)
10.1021/CM9601143
Organic/Inorganic Hybrid Network Materials by the Sol−Gel Approach
J. Wen (1996)
10.1021/LA0469304
Combinatorial approach to study enzyme/surface interactions.
K. Loos (2005)
10.1016/0021-9797(87)90260-8
A wettability gradient method for studies of macromolecular interactions at the liquid/solid interface
H. Elwing (1987)
10.1002/ANIE.196407841
Gradient and Low‐Temperature Thin‐Layer Chromatography
E. Stahl (1964)
10.1021/nn900991r
Directed single molecule diffusion triggered by surface energy gradients.
P. Burgos (2009)
10.1021/MA051405C
Effect of Block Length on Solvent Response of Block Copolymer Brushes: Combinatorial Study with Block Copolymer Brush Gradients
Chang Xu (2006)
10.1021/LA035027L
Micrometer-scaled Gradient Surfaces Generated Using Contact Printing of Octadecyltrichlorosilane
Sung-Hwan Choi (2003)
10.1021/JA993442N
Dynamic Monolayer Gradients: Active Spatiotemporal Control of Alkanethiol Coatings on Thin Gold Films
Roger H. Terrill (2000)
10.1021/la402934m
Fabrication of surface charge gradients in open-tubular capillaries and their characterization by spatially resolved pulsed streaming potential measurements.
B. Kannan (2013)
10.1016/j.chroma.2015.07.089
Amine-phenyl multi-component gradient stationary phases.
V. Dewoolkar (2015)



This paper is referenced by
Semantic Scholar Logo Some data provided by SemanticScholar