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2012 | Book

General Introduction Read chapter Read first chapter

Orthogonal Supramolecular Interaction Motifs for Functional Monolayer Architectures

Author: Mahmut Deniz Yilmaz

Publisher: Springer Berlin Heidelberg

Book Series : Springer Theses

Part of: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik"

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About this book

Deniz Yilmaz' thesis describes a combination of orthogonal supramolecular interactions for the design of functional monolayer architectures on surfaces, that can be used as chemical and biosensors in a wide range of applications. The term “orthogonal supramolecular interactions” refers to non-covalent interactions that do not influence each other's assembly properties. Orthogonal self-assembly thus allows extended control over the self-assembly process and promotes new materials properties. The first part of the thesis employs orthogonal host-guest and lanthanide-ligand coordination interaction motifs to create supramolecular luminescent monolayers. The second part of the thesis describes the fabrication of functional monolayers on silicon and gold substrates for applications in electronics.

The results illustrate the power of weak supramolecular interactions to direct the immobilization of functional systems on surfaces. The combination of host-guest and lanthanide-ligand coordination interaction motifs on surfaces demonstrates that hybrid, multifunctional supramolecular monolayers can be fabricated by integrating different non-covalent interactions in the same system. This combination opens up new avenues for the fabrication of complex hybrid organic-inorganic materials and stimuli-responsive surfaces. Their utility is demonstrated through applications of the functional interfaces to biosensing and nanotechnology.

Table of Contents

Frontmatter
Chapter 1. General Introduction
Abstract
Supramolecular chemistry and self-assembly processes have evolved to be one of the most important fields in modern chemistry of the last two decades. Molecular recognition and self-assembly represent the basic concept of supramolecular chemistry and involved noncovalent interactions. Noncovalent interactions (e.g. hydrogen bonding, metal–ligand coordination, electrostatic, and host–guest interactions) are usually weaker than covalent bonds and they are reversible. The use of supramolecular interactions to direct the spontaneous assembly of molecules is of utmost importance due to their high specificity, controlled affinity, and reversibility. These specific and highly controllable interactions can be manipulated independently and simultaneously, providing orthogonal self-assembly which describes the assembly of components with multiple (i.e. more than one) interaction motifs that do not influence each other’s assembly properties, applied in the same system.
Mahmut Deniz Yilmaz
Chapter 2. Orthogonal Supramolecular Interaction Motifs for Functional Monolayer Architectures
Abstract
This chapter gives an overview on the recent developments of orthogonal supramolecular interactions on surfaces. The first part deals with the use of noncovalent interactions, including hydrogen bonding, metal coordination, electrostatics, and host–guest interactions, to modify surfaces. The second part describes the combination of different, orthogonal supramolecular interaction motifs for the generation of hybrid assemblies and materials. The integration of different supramolecular systems is essential for the self-assembly of complex architectures on surfaces.
Mahmut Deniz Yilmaz
Chapter 3. Expression of Sensitized Eu3+ Luminescence at a Multivalent Interface
Abstract
The assembly of a mixture of guest-functionalized antenna and Eu3+-complexed ligand molecules in a patterned fashion onto a receptor surface was shown to provide local and efficient sensitized Eu3+ emission. Coordination of a carboxylate group of the antenna to the Eu3+ center and noncovalent anchoring of both components to the receptor surface appeared to be prerequisites for efficient energy transfer. A Job plot at the surface confirmed that coordination of the antenna to the Eu3+ center occured in a 1:1 fashion. The efficiency of this intramolecular binding process is promoted by the high effective concentration of both complementary moieties at the surface. The system constitutes, therefore an example of supramolecular expression of a complex consisting of several different building blocks which signals its own correct formation.
Mahmut Deniz Yilmaz
Chapter 4. Ratiometric Fluorescent Detection of an Anthrax Biomarker at Molecular Printboards
Abstract
Anthrax is an acute disease, concurrently a potential biological warfare agent caused by Bacillus Anthracis. The accurate, rapid, sensitive, and selective detection of Bacillus spores plays a vital role in order to prevent a biological attack or outbreak of disease. Bacterial spores contain a main core cell which is enclosed by protective layers. As a major component of these protective layers, bacterial spores contain up to 1 M dipicolinic acid (DPA), accounting for 5−15 % of the dry mass of the bacterial spore. Hence, DPA is a convenient biomarker for these spores. In recent years a number of biological and chemical detection methods for Bacillus Anthracis spores have been investigated. Biological methods are based on polymerase chain reactions and immunoassays. Important chemical methods employ vibrational spectroscopy (FT-IR, Raman and SERS) and photoluminescence. Among them, lanthanide (Ln3+)-based luminescent detection of DPA has been most promising owing to the unique photophysical properties of Ln3+-DPA chelates, including their bright luminescence upon sensitization by DPA, the long luminescence lifetimes compared to free Ln3+, and the concomitantly high luminescence enhancement ratio upon coordination of DPA to the Ln3+ center. Besides the use of DPA itself as a sensitizer, ratiometric fluorescent detection of anthrax spores can be achieved through the displacement of a different sensitizer by DPA.
Mahmut Deniz Yilmaz
Chapter 5. A Supramolecular Sensing Platform in a Microfluidic Chip
Abstract
A supramolecular platform based on self-assembled monolayers (SAMs) has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids which are important for anthrax detection. An Eu(III)-EDTA complex was bound to β-cyclodextrin monolayers via orthogonal supramolecular host–guest interactions. The self-assembly of the Eu(III)-EDTA conjugate and naphthalene β-diketone as an antenna resulted in the formation of a highly luminescent lanthanide complex on the microchannel surface. Detection of different phosphate anions and aromatic carboxylic acids was demonstrated by monitoring the decrease in red emission following displacement of the antenna by the analyte. Parallel fabrication of five sensing SAMs in a single multichannel chip was performed, as a first demonstration of phosphate and carboxylic acid screening in a high-throughput format that allows a general detection platform for both analyte systems in a single test run.
Mahmut Deniz Yilmaz
Chapter 6. Local Doping of Silicon Using Nanoimprint Lithography and Molecular Monolayers
Abstract
Two fabrication schemes for the direct patterning of organic monolayers on oxide-free silicon are reported combining top-down nanoimprint lithography (NIL) and bottom-up monolayer formation. The first approach was designed to form monolayer patterns on the imprinted areas, while the second approach was designed for monolayer formation outside of the imprinted features. By both approaches, covalently bonded Si–C monolayer patterns with feature sizes ranging from 100 nm to 100 μm were created via a hydrosilylation procedure using diluted reagents. This novel patterning strategy was successfully applied for introducing dopant atoms using a phosphorus-containing molecular precursor on oxide-free silicon. The patterned sample was protected by a SiO2 capping layer applied by e-beam evaporation and subjected to rapid thermal annealing (RTA) to diffuse the phosphorus dopant atoms into the bulk silicon locally. The doped sample was investigated by 3D time-of-flight secondary ion mass spectrometry (TOF–SIMS) and electrically characterized by Hall and Van der Pauw measurements.
Mahmut Deniz Yilmaz
Chapter 7. Fabrication of Two-Dimensional Organic Spin Systems on Gold
Abstract
In this chapter, fabrication of monolayers of organic molecules with unpaired spins on a thin gold film is described. XPS and cyclic voltammetry (CV) measurements showed the existence of unpaired spins on gold surface. In a number of systems with diluted monolayers, electrical transport measurements showed an increase of the gold film sheet resistance for temperatures below ~20 K for some examples, possibly implying Kondo physics.
Mahmut Deniz Yilmaz
Backmatter
Metadata
Title
Orthogonal Supramolecular Interaction Motifs for Functional Monolayer Architectures
Author
Mahmut Deniz Yilmaz
Copyright Year
2012
Publisher
Springer Berlin Heidelberg
Electronic ISBN
978-3-642-30257-2
Print ISBN
978-3-642-30256-5
DOI
https://doi.org/10.1007/978-3-642-30257-2

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