Surface covalent attachment

Alkanethiols and other sulfur-bearing hydrocarbons covalently attach to metal surfaces alkanethiol onto gold is the most widely studied of these systems [27-29,31,32,45]. These SAMs are ordered provided the alkane chain contains nine or more carbons [32]. Binary solutions of two alkanethiols also appear... 

Protems can be physisorbed or covalently attached to mica. Another method is to innnobilise and orient them by specific binding to receptor-fiinctionalized planar lipid bilayers supported on the mica sheets [15]. These surfaces are then brought into contact in an aqueous electrolyte solution, while the pH and the ionic strength are varied. Corresponding variations in the force-versus-distance curve allow conclusions about protein confomiation and interaction to be drawn [99]. The local electrostatic potential of protein-covered surfaces can hence be detemiined with an accuracy of 5 mV. 

Functionalized conducting monomers can be deposited on electrode surfaces aiming for covalent attachment or entrapment of sensor components. Electrically conductive polymers (qv), eg, polypyrrole, polyaniline [25233-30-17, and polythiophene/23 2JJ-J4-j5y, can be formed at the anode by electrochemical polymerization. For integration of bioselective compounds or redox polymers into conductive polymers, functionalization of conductive polymer films, whether before or after polymerization, is essential. In Figure 7, a schematic representation of an amperomethc biosensor where the enzyme is covalendy bound to a functionalized conductive polymer, eg, P-amino (polypyrrole) or poly[A/-(4-aminophenyl)-2,2 -dithienyl]pyrrole, is shown. Entrapment of ferrocene-modified GOD within polypyrrole is shown in Figure 7. 

Synthetic chiral adsorbents are usually prepared by tethering a chiral molecule to a silica surface. The attachment to the silica is through alkylsiloxy bonds. A study which demonstrates the technique reports the resolution of a number of aromatic compoimds on a 1- to 8-g scale. The adsorbent is a silica that has been derivatized with a chiral reagent. Specifically, hydroxyl groups on the silica surface are covalently boimd to a derivative of f -phenylglycine. A medium-pressure chromatography apparatus is used. The racemic mixture is passed through the column, and, when resolution is successful, the separated enantiomers are isolated as completely resolved fiactions. Scheme 2.5 shows some other examples of chiral stationary phases. 

By covalently attaching reactive groups to a polyelectrolyte main chain the uncertainty as to the location of the associated reactive groups can be eliminated. The location at which the reactive groups experience the macromolecular environment critically controls the reaction rate. If a reactive group is covalently bonded to a macromolecular surface, its reactivity would be markedly influenced by interfacial effects at the boundary between the polymer skeleton and the water phase. Those effects may vary with such factors as local electrostatic potential, local polarity, local hydrophobicity, and local viscosity. The values of these local parameters should be different from those in the bulk phase. 

Morishima et al. [30, 50-54, 73-76] have made extensive investigations on photoinduced ET, using polycyclic aromatic chromophores covalently attached to polyelectrolytes. They were the first to show that the polyeletrolyte molecular surface provides an unusual microenvironment which greatly changes the rate of photoinduced ET and the fate of the charged photoproducts. 

The preparation of polymer brushes by controlled radical polymerization from appropriately functionalized polymer chains, surfaces or particles by a grafting from approach has recently attracted a lot of attention.742 743 The advantages of growing a polymer brush directly on a surface include well-defined grafts, when the polymerization kinetics exhibit living character, and stability due to covalent attachment of the polymer chains to the surface. Most work has used ATRP or NMP, though papers on the use of RAFT polymerization in this context also have begun to appear. 

The synthesis of end functional polymers by NMP, ATRP and RAFT has already been discussed in Section 9.7. The "grafting to approach involves the covalent attachment of an end-funetionalized polymer with reactive surface groups on the substrate. The approach is inherently limited by the crowding of chains at the surface and the limit this places on the final graft density. 

The described procedure allows one to deposit protein, in particular, enzyme, LB films onto the surface of small spheres. Deposited multilayer film was washed in order to leave at the surface only a layer covalently attached to the activated surface. The enzyme... 

Si-C formation technique with hydrogen-terminated silicon substrates can also be used as the covalent attachment of nanomaterials onto silicon surface. The possibility of assembling nanomaterials in order is strongly desired in order to enable efficient utilization of their unique nano-sized properties. Ordered arranging and position controlling of nanomaterials on solid substrates especially on silicon surface have been intensively studied [10]. In this manuscript, the nanoparticle immobilization by thermal Si-C formation will be discussed [11]. 

Covalent attachment of enzymes to surfaces is often intuitively perceived as being more reliable than direct adsorption, but multisite physical interactions can in fact yield a comparably strong and stable union, as demonstrated by several biological examples. The biotin/streptavidin interaction requires a force of about 0.3 nN to be severed [Lee et al., 2007], and protein/protein interactions typically require 0.1 nN to break, but values over 1 nN have also been reported [Weisel et al., 2003]. These forces are comparable to those required to mpture weaker chemical bonds such as the gold-thiolate bond (1 nN for an alkanethiol, and even only 0.3 nN for a 1,3-aUcanedithiol [Langry et al., 2005]) and the poly(His)-Ni(NTA) bond (0.24 nN, [Levy and Maaloum, 2005]). 

Fig. 2.2 (A) Structure of full-length NS3 including the N-terminal protease domain (bottom) and C-terminal helicase domain (top). The NS4A peptide (purple) is covalently attached to the N-terminus of NS3 (see text). Within the protease domain the N- and C-terminal -barrels are at the right and left, respectively. The zinc atom is visible at the bottom left. [98]. (B) Surface view of the NS3 protease domain showing compound (1) bound at the relatively shallow active site (See also Fig. 2.6) [42].

Smith and co-workers (194) have used this chemistry to prepare carboxyl-modified Si(lll) surfaces at which polylysine-tethered DNA is electrostatically adsorbed (Fig. 60). An alternative approach involved covalent attachment of a pre-synthesized oligonucleotide bearing a terminal carboxyl group to an amine-modified Si(001) surface (195). 

A very promising method, immobilized artificial membrane (IAM) chromatography, was developed by Pidgeon and co-workers [299-304,307], where silica resin was modified by covalent attachment of phospholipid-like groups to the surface. The retention parameters mimic the partitioning of drugs into phospholipid bilayers. The topic has been widely reviewed [47,298,307,309-311]. 

Binding of these ligands does not occur in a concave groove located on the surface of the receptor protein as otherwise often imagined. As described in Section 2.2.1, the x-ray structure of rhodopsin showed that retinal is bound deep in the seven-helical structure with major interaction points in TM-III and TM-VI, as well as the covalent attachment point in TM-VII. In fact, rhodopsin interacts with basically all transmembrane segments. Importantly, side-chains from the transmembrane helices cover the retinal molecule on all sides, and its binding site is found deep in the middle of... 

Non Covalent Attachment of Antibodies to a Surface by the Inactive Fc Portion... 

In addition to the covalent binding, some methods derived from bioaffinity chromatography can be used for non covalent attachment of antibodies to a surface by the inactive Fc portion. The advantage is that antigen binding sites stay undamaged and accessible for the analytes due to the orientation of antibody with the active Fab portions towards the tested medium. 

Besides the preparation of glyconanotube conjugates by supramolecular interactions, another synthetic pathway commonly used involved covalent attachment of the saccharidic units on the CNT scaffolds. The progress recently recorded concerning the derivatization of unfunctionalized CNTs, allowing introduction of suitable anchoring functions at their surface, are the basis of this synthetic alternative.255... 

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