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This paper reports microcontact printing (µCP) to immobilize an alkoxyamine initiator (regulator) on glass and silicon substrates and subsequent surface-initiated alternating nitroxide-mediated copolymerization (siNMP) of hexafluoroisopropyl acrylate (HFIPA) and 7-octenylvinyl ether (OVE). The resulting patterned polymer brushes are analyzed by using atomic force microscopy (AFM). In addition, site-specific post-functionalization of the alternating polymer brushes by applying two orthogonal surface reactions is achieved with thiols and amines through µCP. The versatility of this post-polymerization modification approach is demonstrated by site-selective immobilization of small organic molecules, fluorophores, and ligands providing a binary bioactive surface. The successful side-by-side orthogonal immobilization is verified by using X-ray photoelectron spectroscopy (XPS) and fluorescence microscopy.
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Nanoclays are nanomaterials with versatile adsorptive properties. This contribution describes the generation of micropatterns of a nanoclay ("laponite") on ammonium-terminated, self-assembled monolayers (SAMs) on glass and silicon. Microstructured immobilization of the laponite was performed using micromolding in capillaries (MIMIC). The immobilization was verified using contact angle goniometry, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and fluorescence microscopy. Furthermore, laponite was modified with Nile red to generate a fluorescence enhancement-based surface sensor for the vitamin choline.
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The potential application of molecular switches as active elements in information storage has been demonstrated through numerous works. Importantly, such switching capabilities have also been reported for self-assembled monolayers (SAMs). SAMs of electroactive molecules have recently been exploited as electrochemical switches. Typically, the state of these switches could be read out through their optical and/or magnetic response. These output reading processes are difficult to integrate into devices, and furthermore, there is a need to use liquid environments for switching the redox-active molecular systems. In this work, both of these challenges were overcome by using an ionic gel as the electrolyte medium, which led to an unprecedented solid-state device based on a single molecular layer. Moreover, electrochemical impedance has been successfully exploited as the output of the system.
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This Communication describes a bioconjugation method for the generation of enzyme microarrays on surfaces using photochemical thiol-ene chemistry in combination with microcontact printing. Glucose oxidase and lactase were readily immobilized (i.e., printing time 2 min) on alkene terminated self-assembled monolayers on glass as demonstrated by X-ray photoelectron spectroscopy and fluorescence microscopy. Furthermore, the activity of both immobilized enzymes was confirmed in single enzyme as well as cascade transformations.
Assuntos
Química Click , Enzimas Imobilizadas/química , Compostos de Sulfidrila/química , Alcenos/química , Enzimas Imobilizadas/metabolismo , Desenho de Equipamento , Glucose Oxidase/química , Glucose Oxidase/metabolismo , Lactase/química , Lactase/metabolismo , Microscopia de Fluorescência , Modelos Moleculares , Espectroscopia Fotoeletrônica , Análise Serial de Proteínas , Propriedades de SuperfícieRESUMO
The use of time-of-flight secondary ion mass spectrometry (SIMS) is of increasing interest for biological and medical applications due to its ability to provide chemical information on a submicrometer scale. However, the detection of larger biomolecules such as phospholipids and peptides is often inhibited by high fragmentation rates and low ionization efficiencies. One way to increase the secondary ion molecular yield is to chemically modify the surface using the matrix-enhanced SIMS approach, where an organic matrix is placed upon the surface. In this study, a Knudsen cell type matrix coater was developed in order to produce well-defined thicknesses of a matrix on a sample in order to study the effect of these matrix layers on the secondary ions. Using this technique, an order of magnitude enhancement of the useful ion yield for lipids was observed and clear enhancement of image contrast for lipids in brain tissue was demonstrated. The study shows that the layer thickness has a great influence on the emission of secondary ions, and therefore, its precise control is important for optimal yield enhancement.
Assuntos
Técnicas de Preparação Histocitológica/métodos , Lipídeos/análise , Espectrometria de Massa de Íon Secundário/métodos , Propriedades de Superfície , Animais , Química Encefálica , Feminino , Camundongos Endogâmicos C57BLRESUMO
The generation of carbohydrate patterns on surfaces enables a wide range of analytical and diagnostic applications and efficient methods for carbohydrate immobilization are crucial for this purpose. We report on surface O-glycosylation by catalytic printing as a novel, effective method for the covalent immobilization of carbohydrates in micropatterns. Beside the verification of surface functionalization, the suitability of the generated surface for ligand protein interactions was demonstrated.