Functionalization, single macromolecular

Covalent and metallosupramolecular block copolymers have been combined in a single macromolecular structure. In this respect a terpyridine-functionalized PS-P2 VP has been complexed with a terpyridine-functionalized PEO, leading to a PS32-P2VPi3-[Ru]-PE07o ABC triblock copolymer [330]. This copolymer was further used to prepare core-shell-corona micelles consisting of a PS core, a pH-responsive P2VP shell, and a PEO corona. 

Hydrophobic associations in random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and some methacrylamides and methacrylates substituted with bulky hydrophobes are described with a focus on preferential intrapolymer self-association which leads to the formation of single-macromolecular assemblies (i.e., unimolecular micelles). Structural parameters that critically determine the type of the macromolecular association (i.e., intra- vs. interpolymer associations) are discussed, which include the type of hydrophobes, their content in a polymer, sequence distribution of electrolyte and hydrophobic monomer units, and the type of spacer bonding. Functionalization of single-macromolecular assemblies with some photoactive chromophores is also presented. 

This chapter will discuss hydrophobic associations in random copolymers of AMPS and some hydrophobic methacrylamide and methacrylate comonomers with a focus on the intra- versus interpolymer self-association in connection witih the type of hydrophobes, their content in the polymers, and spacer bonding. A particular emphasis will be placed on intrapolymer association of hydrophobes which leads to single-molecular self-assemblies. Functionalization of the single-macromolecular assemblies with some photoactive chromophores will also be presented briefly. 

Polyamines, such as second-generation polypropylene imine dendrimers and polyethyleneimine have been used as cross-linkers increasing the cross-link density above the level obtained with CL alone. Polyethyleneimine-functionalized single-walled carbon nanotubes (SWNTs) have been also used as macromolecular cross-linking agents (Homenick et al., 2010). 

This impossibility of reducing a complex process to single macromolecules explains the co-existence of different levels of explanation in biologists molecular descriptions. This does not mean that the nature of the molecular components is of no importance, nor that the complex functions originate only from the rules of assembly of the different macromolecular components. The organization of living beings is based both on the precise nature of the molecular components and on the way that these molecular components are assembled. 

The set of stochastic equations given by (3.37) is equivalent (in the linear case) to equations (3.11) with the memory functions defined in Section 3.3, but, in contrast to equations (3.11), set (3.37) is written as a set of Markov stochastic equations. This enables us to determine the variables that describe the collective motion of the set of macromolecules. In this particular approximation, the interaction between neighbouring macromolecules ensures that the phase variables of the elementary motion are co-ordinates, velocities, and some other vector variables - the extra forces. This set of phase variables describes the dynamics of the entire set of entangled macromolecules. Note that the Markovian representation of the equation of macromolecular dynamics cannot be made for any arbitrary case, but only for some simple approximations of the memory functions. We are considering the case with a single relaxation time, but generalisation for a case with a few relaxation times is possible. 

Macromolecular conformations describe the positions of the atoms that occur due to rotation about the single bonds in the main chain.2 Polymer chains in solution, melt, or amorphous state exist in what is termed a random coil. The chains may take up a number of different conformations, varying with time. Figure 15.4 shows one possible conformation for a single polymer chain. In order to describe the chain, polymer scientists utilize the root mean square end-to-end distance ((r2)m), which is the average over many conformations. This end-to-end distance is a function of the bond lengths, the number of bonds, and a characteristic ratio, C, for the specific polymer. 

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