Reactions and Reactivity in Self-Assembled Monolayers

Chechik, Victor; Crooks, Richard M.; Stirling, Charles J. M.

doi:10.1002/1521-4095(200008)12:16<1161::aid-adma1161>3.0.co;2-c

Cited by 255 publications

(241 citation statements)

References 95 publications

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“…sensors and biochips, 2,3 photovoltaics, 4,5 fuel cell, 6 biomaterials, 7 and molecular electronics, 4,8,9 as well as to provide fundamental understanding of electron transfer, 10 controlling reactions at surfaces, 11 and tailoring surface properties. 12 Among the many exciting developments, a number of rather sophisticated molecular assemblies have been developed that not only involve organic and organometallic molecules, but also nanomaterials and/or biomolecules.…”

Section: Simone Ciampimentioning

confidence: 99%

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

2011

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The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references). 2011 The Royal Society of Chemistry. The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references).

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Section: Simone Ciampimentioning

confidence: 99%

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

2011

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“…Surface pK 1/2 values can be shifted by 3-4 pK units from solution pK a values. 76 The solution pK a of R f -COOH is estimated to be <1.0 due to the strong electron withdrawal of the fluorinated alkane group, so R f -COOH should be deprotonated at the pH of solutions (from 7 to 10) used in these experiments. R f -CH 2 CH 2 OH Fluorous Solution-FC-3283 and 1H,1H,2H,2H-perfluoro-1-octanol were mixed in a 10:1 (v/v) ratio; the mixture was used within 24 h. R f -OEG Fluorous Solution-Details on R f -OEG extraction from Zonyl FSO-100 can be found in the Supporting Information.…”

Section: Preparation Of Fluorous-soluble Surfactant Solutionsmentioning

confidence: 99%

Controlling Nonspecific Protein Adsorption in a Plug-Based Microfluidic System by Controlling Interfacial Chemistry Using Fluorous-Phase Surfactants

2004

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Control of surface chemistry and protein adsorption is important for using microfluidic devices for biochemical analysis and high-throughput screening assays. This paper describes the control of protein adsorption at the liquid-liquid interface in a plug-based microfluidic system. The microfluidic system uses multiphase flows of immiscible fluorous and aqueous fluids to form plugs, which are aqueous droplets that are completely surrounded by fluorocarbon oil and do not come into direct contact with the hydrophobic surface of the microchannel. Protein adsorption at the aqueous-fluorous interface was controlled by using surfactants that were soluble in fluorocarbon oil but insoluble in aqueous solutions. Three perfluorinated alkane surfactants capped with different functional groups were used: a carboxylic acid, an alcohol, and a triethylene glycol group that was synthesized from commercially available materials. Using complementary methods of analysis, adsorption was characterized for several proteins (bovine serum albumin (BSA) and fibrinogen), including enzymes (ribonuclease A (RNase A) and alkaline phosphatase). These complementary methods involved characterizing adsorption in microliter-sized droplets by drop tensiometry and in nanoliter plugs by fluorescence microscopy and kinetic measurements of enzyme catalysis. The oligoethylene glycolcapped surfactant prevented protein adsorption in all cases. Adsorption of proteins to the carboxylic acid-capped surfactant in nanoliter plugs could be described by using the Langmuir model and tensiometry results for microliter drops. The microfluidic system was fabricated using rapid prototyping in poly(dimethylsiloxane) (PDMS). Black PDMS micro-fluidic devices, fabricated by curing a suspension of charcoal in PDMS, were used to measure the changes in fluorescence intensity more sensitively. This system will be useful for microfluidic bioassays, enzymatic kinetics, and protein crystallization, because it does not require surface modification during fabrication to control surface chemistry and protein adsorption. This paper describes the biocompatibility of a plug-based microfluidic system obtained through control of surface chemistry the aqueous-fluorous interface. This microfluidic system uses multiphase flows of immiscible fluorous and aqueous liquids to form droplets (plugs) and to transport them with rapid mixing and no Taylor-like dispersion. 1 We have previously used the system to measure enzyme kinetics 2 and perform protein crystallization 3-6 using submicroliter volumes of sample.

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“…1,2,8 SAMs are ordered molecular assemblies formed by the adsorption of active surfactants onto a solid surface. The 2-dimensional order of structures in SAMs is produced by a spontaneous chemical synthesis at the interface, as the system approaches equilibrium.…”

Section: Self-assembled Monolayers (Sams)mentioning

confidence: 99%

“…In addition to the molecular control of interfaces by introducing organic functional groups onto surfaces, another aim of surface organic chemistry is to investigate the similarities and differences between chemical reactions in solution (three-dimensional reactions) and interfacial chemical reactions (two-dimensional reactions) 1 because the rules that govern chemical reactions in solution would be different from the rules that govern chemical reactions at interfaces. 2 Several factors, including solvent effect, steric effect and electronic effect, could affect the chemical reactivity of functional groups at surfaces: the characteristics in the local solvation of functional groups at interfaces could be different from those in the bulk solvation, and the local concentration of reagents near the interface also could be different. Sterically demanding reactions may be hindered at surfaces, and it is true especially for well-packed monolayers.…”

Section: Introductionmentioning

confidence: 99%

“…Sterically demanding reactions may be hindered at surfaces, and it is true especially for well-packed monolayers. The pK a values of certain molecules at interfaces were found to be different from those in solution, 2,3 and chemical and biological reactivities are also altered at interfaces. For example, Mrksich and Houseman studied the role of surface density (χ) of a ligand (N-acetylglucosamine, GlcNAc) in the enzymatic activity of bovine β-1,4-galactosyltransferase and reported that the maximum glycosylation occurred with the GlcNAc density of χ = 0.7 (not 1.0).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Biosurface Organic Chemistry: Interfacial Chemical Reactions for Applications to Nanobiotechnology and Biomedical Sciences

Shik¹,

Lee²,

Lee³

et al. 2005

ChemInform

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In this review, the field of biosurface organic chemistry is defined and some examples are presented. The aim of biosurface organic chemistry, composed of surface organic chemistry, bioconjugation, and micro-and nanofabrication, is to control the interfaces between biological and non-biological systems at the molecular level. Biosurface organic chemistry has evolved into the stage, where the lateral and vertical control of chemical compositions is achievable with recent developments of nanoscience and nanotechnology. Some new findings in the field are discussed in consideration of their applicability to nanobiotechnology and biomedical sciences.

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Reactions and Reactivity in Self-Assembled Monolayers

Cited by 255 publications

References 95 publications

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

Controlling Nonspecific Protein Adsorption in a Plug-Based Microfluidic System by Controlling Interfacial Chemistry Using Fluorous-Phase Surfactants

Biosurface Organic Chemistry: Interfacial Chemical Reactions for Applications to Nanobiotechnology and Biomedical Sciences

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