Amphiphiles block copolymer

Absorption is widely used as a raw material and/or product recovery technique in separation and purification of gaseous streams containing high concentrations of VOC, especially water-soluble compounds such as methanol, ethanol, isopropanol, butanol, acetone, and formaldehyde. Hydrophobic VOC can be absorbed using an amphiphilic block copolymer dissolved in water. However, as an emission control... 

For gas absorption, the water or other solvent must be treated to remove the captured pollutant from the solution. The effluent from the column may be recycled into the system and used again. This is usually the case if the solvent is costly (e.g., hydrocarbon oils, caustic solutions, amphiphilic block copolymer). Initially, the recycle stream may go to a treatment system to remove the pollutants or the reaction product. Make-up solvent may then be added before the liquid stream reenters the column. 

The multifunctional initiators may be di- and tri-, azo- or peroxy-compounds of defined structure (c.g. 20256) or they may be polymeric azo- or peroxy-compounds where the radical generating functions may be present as side chains 57 or as part of the polymer backbone."58"261 Thus, amphiphilic block copolymers were synthesized using the polymeric initiator 21 formed from the reaction between an a,to-diol and AIBN (Scheme 7.22).26 Some further examples of multifunctional initiators were mentioned in Section 3.3.3.2. It is also possible to produce less well-defined multifunctional initiators containing peroxide functionality from a polymer substrate by autoxidalion or by ozonolysis.-0... 

Perrier RJ (2001) Direct Conversion of 5,6-Unsaturated Hexopyranosyl Compounds to Functionalized Glycohexanones. 215 277-291 Frey H, Schlenk C (2000) Silicon-Based Dendrimers. 210 69-129 Forster S (2003) Amphiphilic Block Copolymers for Templating Applications. 226 1-28 Frullano L, Rohovec J, Peters JA, Geraldes CFGC (2002) Structures of MRI Contrast Agents in Solution. 221 25-60... 

Recently, unique vesicle-forming (spherical bUayers that offer a hydrophilic reservoir, suitable for incorporation of water-soluble molecules, as well as hydrophobic wall that protects the loaded molecules from the external solution) setf-assembUng peptide-based amphiphilic block copolymers that mimic biological membranes have attracted great interest as polymersomes or functional polymersomes due to their new and promising applications in dmg delivery and artificial cells [ 122]. However, in all the cases the block copolymers formed are chemically dispersed and are often contaminated with homopolymer. 

Tailoring block copolymers with three or more distinct type of blocks creates more exciting possibilities of exquisite self-assembly. The possible combination of block sequence, composition, and block molecular weight provides an enormous space for the creation of new morphologies. In multiblock copolymer with selective solvents, the dramatic expansion of parameter space poses both experimental and theoretical challenges. However, there has been very limited systematic research on the phase behavior of triblock copolymers and triblock copolymer-containing selective solvents. In the future an important aspect in the fabrication of nanomaterials by bottom-up approach would be to understand, control, and manipulate the self-assembly of phase-segregated system and to know how the selective solvent present affects the phase behavior and structure offered by amphiphilic block copolymers. 

Bates F.S. and Fredrickson G.H., Block copolymers-designer soft materials, Phys. Today, 52, 32, 1999. Alexandridis P. and Lindman B. (eds.). Amphiphilic Block Copolymers Self-Assembly and Applications, Elsevier, Amsterdam, 2000. 

FOrster S (2003) Amphiphilic Block Copolymers for Templating Applications. 226 1-28... 

The formation of polymeric capsules can also be achieved by the cross-linking of self-assembled amphiphilic block copolymers [85]. The hydrophobic section of the polymer in an aqueous solution will tend to aggregate on the interior of the micelle, whereas the hydrophilic ends will form the outer shell of the micelle. If the hydrophilic end is appropriately functionalized, it can be cross-linked, giving a polymeric shell. The overarching concept is shown in Figure 5.10. 

The vesicles made from lipid bilayers are analogous to polymersomes, which are vesicles formed from high molecular weight amphiphilic block copolymers [94—96], Unlike the micelles discussed earlier from the similar copolymer components, the presence of bilayer walls formed from the aggregation of hydrophobic domains provides new properties. They can be designed to respond, for example, by opening or by disassembly, to external stimuli such as pH, heat, light, and redox processes [97]. This makes them usable as scaffolds for cascade reactions, even those with combinations of enzymes [98, 99]. 

Ferrier RJ (2001) Direct Conversion of 5,6-Unsaturated Hexopyranosyl Compounds to Functionalized Glycohexanones. 215 277-291 FOrster S (2003) Amphiphilic Block Copolymers for Templating Applications. 226 1-28... 

Trialkylsilyl-protected oligo(ethylene glycol)methacrylates, 2- 2- (tert-butyldimethylsilyl)oxy]ethoxy ethyl methacrylate (1), and 2- 2-[2-[(ferf-butyldimethylsilyl)oxy] ethoxy] ethoxy ethyl methacrylate (2) (Scheme 7) were used for the synthesis of amphiphilic block copolymers by anionic poly-... 

Kim, J.M., Sakamoto, Y., Hwang, Y.K., Kwon, Y.U., Terasaki, O., Park, S.E. and Stucky, G.D. (2002) Structural design of mesoporous silica by micelle-packing control using blends of amphiphilic block copolymers. Journal of Physical Chemistry B, 106, 2552— 2558. 

Recently, many studies have focused on self-assembled biodegradable nanoparticles for biomedical and pharmaceutical applications. Nanoparticles fabricated by the self-assembly of amphiphilic block copolymers or hydrophobically modified polymers have been explored as drug carrier systems. In general, these amphiphilic copolymers consisting of hydrophilic and hydrophobic segments are capable of forming polymeric structures in aqueous solutions via hydrophobic interactions. These self-assembled nanoparticles are composed of an inner core of hydrophobic moieties and an outer shell of hydrophilic groups [35, 36]. 

Letchford K, Burt H (2007) A review of the formation and classification of amphiphilic block copolymer nanoparticulate structures micelles, nanospheres, nanocapsules and polymersomes. Eur J Pharm Biopharm 65 259-269... 

Some other degradable (i.e., nonvinyl-type) polymers have been reported as components for amphiphilic block copolymers. For example, Hsiue reported the synthesis of a block copolymer of poly(2-ethyl oxazoline) and PLA by ROP. They reported the use of ABA-type triblock copolymers as pH-responsive polymer... 

Many kinds of nonbiodegradable vinyl-type hydrophilic polymers were also used in combination with aliphatic polyesters to prepare amphiphilic block copolymers. Two typical examples of the vinyl-polymers used are poly(/V-isopropylacrylamide) (PNIPAAm) [149-152] and poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) [153]. PNIPAAm is well known as a temperature-responsive polymer and has been used in biomedicine to provide smart materials. Temperature-responsive nanoparticles or polymer micelles could be prepared using PNIPAAm-6-PLA block copolymers [149-152]. PMPC is also a well-known biocompatible polymer that suppresses protein adsorption and platelet adhesion, and has been used as the hydrophilic outer shell of polymer micelles consisting of a block copolymer of PMPC -co-PLA [153]. Many other vinyl-type polymers used for PLA-based amphiphilic block copolymers were also introduced in a recent review [16]. 

In 1997, Kim and coworkers first developed biodegradable IP systems using a triblock copolymer of PEG and PLLA, PEG-b-PLLA-b-PEG, and demonstrated sustained release of drugs from the hydrogel [127]. After this achievement, many kinds of biodegradable amphiphilic block copolymers (including multiblock copolymers) exhibiting temperature-responsive sol-gel transition have been reported [137, 308-318]. In this review, only several recent results are introduced. 

Fig. 30 Types of nanocarriers for drug delivery, (a) Polymeric nanoparticles polymeric nanoparticles in which drugs are conjugated to or encapsulated in polymers, (b) Polymeric micelles amphiphilic block copolymers that form nanosized core-shell structures in aqueous solution. The hydrophobic core region serves as a reservoir for hydrophobic drugs, whereas hydrophilic shell region stabilizes the hydrophobic core and renders the polymer water-soluble.

Self Organized Nanostructures of Amphiphilic Block Copolymers II... 

Goltner, C. G. Berton, B. Kramer, E. Antonietti, M. 1999. Nanoporous silicas by casting the aggregates of amphiphilic block copolymers The transition from cylinders to lamellae and vesicles. Adv. Mater. 11 395-398. 

A special class ofblock copolymers with blocks of very different polarity is known as amphiphilic (Figure 10.1). In general, the word amphiphile is used to describe molecules that stabilize the oil-water interface (e.g., surfactants). To a certain extent, amphiphilic block copolymers allow the generalization of amphi-philicity. This means that molecules can be designed that stabilize not only the oil-water interface but any interface between different materials with different cohesion energies or surface tensions (e.g., water-gas, oil-gas, polymer-metal, or polymer-polymerinterfaces). This approach is straightforward, since the wide variability of the chemical structure of polymers allows fine and specific adjustment of both polymer parts to any particular stabilization problem. 

Figure 10.1. Schematic drawing of an amphiphilic block copolymer stabilizing the oil-water interface.

Nonionic Amphiphilic Block Copolymers in Aqueous Solution. 89... 

Whenever amphiphilic block copolymer chains are dissolved at a fixed temperature and in a selective solvent for one of the blocks, they self-associate through a closed association process to form micelles similarly to low-MW surfactants. 

Reverse micelles from amphiphilic block copolymers have been widely investigated. In such micelles, the core is typically formed from PEO, PMAA,... 

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