Block amphiphilic

Fig. 5 Linear Rf-Rh diblocks are amphisteric (different cross sections of the F- and //-blocks), amphiphilic (distinct cohesive energy density), and amphidynamic (distinct flexibility, conformations). The dashed arrow indicates the direction of the dipole moment arising at the CH2-CF2 connection. Reproduced with permission [66], copyright 2009, American Chemical Society (ACS)...

Block Copolymers are macromolecules which are composed of blocks usually in linear as it shown in Fig. 3.20, where it is illustrated a classical block copolymer. Main block copolymers are amphiphilic block copolymers having united hydrophilic blocks to hydrophobic blocks. Amphiphilic block copolymer have surfactant properties and form different kinds of associations, such as micelles, nanospheres, nanocapsules and polymersomes This tipe of association can act like excellent vehicles of several active principles. The composition, aggregate formation and the different applications of these materials have been reviewed [112], Figure 3.20 also illustrates the nanoparticulate drug delivery systems formed by amphiphilic block copolymers and their general characteristics. 

Cores of Block Copolymer Micelles. In selective solvents (a good solvent only for one block), amphiphilic block copolymers form micelles, the characteristics of which (size and shape) depend on the chemical structure and molecular weight of each block and on the solvent type [27-29]. If the coreforming block contains functional groups, which are able to react with metal... 

Core-shell PU NPs can also be prepared by appropriate choice of isocyanate [166]. Blocked amphiphilic prepolymers were prepared by Cheong et al., where the hydrophobic block is composed of IPDI-polytetramethylene adipate polyol (PTMA) and the hydrophilic block is MDI-DMPA. The resulting polymer is added drop-wise to water under stirring, resulting in a core-shell structure with the hydrophobic IPDI-PTMA in the core and hydrophilic MDI-DMPA in the shell (80-100 nm diameter) [166]. 

Na 2-Acrylamido-2-methylpropanesulfonate-N,N-dimethylacrylamide-styrene block copolymer [305] PAA-poly(benzyl ether) anionic linear-dendritic block amphiphiles [306]... 

Zhu, L., et al. (2000). Synthesis and solution properties of anionie linear-dendritic block amphiphiles. J. Polym. Sci., Part A Polym. Chem., 38(23) 4282-4288. 

Therefore, star polymers 18 are expected to possess properties that differ from those of the star block amphiphiles, where outer segments may render inner segments restricted in motion, and govern the properties of the star polymer. 

Such amphiphilic graft polymers may have almost uniform number of branches, provided that living polymerization of 23 is available. In addition, unlike the various types of star-shaped polymers previously reported [7,12,13], graft polymer 24 has no hydrophobic microgel core that may possess some dimensions. Therefore, the amphiphilic graft polymers are expected to possess properties and functions differing from those of the corresponding star block amphiphiles. 

This parameter corresponds to cylindrical packing shapes. Surfactants and amphiphiles falling in this range often produce planar bilayers and lamellar mesophases. Such cylindrical building blocks also contribute to many... 

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. 

FIG. 1 Self-assembled structures in amphiphilic systems micellar structures (a) and (b) exist in aqueous solution as well as in ternary oil/water/amphiphile mixtures. In the latter case, they are swollen by the oil on the hydrophobic (tail) side. Monolayers (c) separate water from oil domains in ternary systems. Lipids in water tend to form bilayers (d) rather than micelles, since their hydrophobic block (two chains) is so compact and bulky, compared to the head group, that they cannot easily pack into a sphere [4]. At small concentrations, bilayers often close up to form vesicles (e). Some surfactants also form cyhndrical (wormlike) micelles (not shown). 

In a somewhat wider sense, one can define amphiphiles as molecules in which chemically very different units are linked together. For example, the structures formed by A B block copolymers in demixed A and/or B homopolymer melts and their phase behavior are very similar to those of classical amphiphiles in water and/or oil [13,14]. Copolymers are used not only to disperse immiscible homopolymer phases in one another, but also to create new, mesoscopically structured materials with unusual and interesting properties [15]. 

The term poloxamer is widely used to describe a series of ABA block coploymers of polyethylene oxide and polypropylene oxide, extensively used in industry as antifoams, emulsifiers, wetting agents, rinse aids, and in numerous other applications [1-5]. Poloxamers are amphiphilic in character, being comprised of a central polypropylene oxide (PO) block, which is hydrophobic, sandwiched between two hydrophilic polyethylene oxide (EO) blocks as shown below ... 

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... 

Fig. 3 a-c. Summary of data from different laboratories, obtained by surface force measurement, on the average layer thickness L as a function of tethered chain length for flat, tethered layers constructed by adsorption of amphiphilic polymers on mica. Adapted from Ref. 21. (a) Data of reference 20 on poly-tert-butylstyrene chains anchored by adsorbing blocks of poly-2-vinylpyridine. (b) Data of references 11 and 12 on polystyrene chains anchored by adsorbing blocks of poly-2-vinylpyridine. (c) Data of references 13 and 14 on polystyrene chains anchored by adsorbing zwitterionic groups [13] or by small adsorbing blocks of polyethyleneoxide [14]... 

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... 

This polypeptide is structurally identical to ABA-type triblock copolymer with a central hydrophdic elastomeric end-block capped with two hydrophobic plastic end-blocks and exhibits amphiphilic characteristics. The end-blocks of the polymer were chosen in such a way that their LCST would reside at or near room temperature. Thus the polymer exhibits phase separation, which is analogue to conventional TPEs, and offers TPE gels under physiological relevant conditions [104]. Glutamic acid residue is placed periodically in the elastomeric mid-block to increase its affinity towards the aqueous... 

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... 

Fig. 1 Vesicle construct formed from poly(L-lysine)-i)-poly(L-leucme) polypeptides where the poly(L-leucine) block corresponds to the a-helical hydrophobic segments and the poly (L-lysine) block corresponds to the random coil hydrophilic segments. Note that this is one specific example and not all vesicle constructs have a-helical and random coil blocks. Moreover, the amphiphilic copolymer can be comprised of either a pure block copolypeptide or a macromolecule consisting of a polypeptide and another type of polymer. Adapted from [20] with permission. Copyright 2010 American Chemical Society...

Fig. 5 Polypeptide vesicles demonstrate the ability to utilize the EPR effect, (a) Chemical structure of the amphiphilic block polypeptide PSar-b-PMLG. (b) Fluorescence image using fluorescently labeled PEG. Fluorescence is not observed in the cancer site although accumulation is observed in the bladder, (c) Fluorescence image using ICG-labeled vesicles, showing evidence of vesicle accumulation due to the EPR effect. Adapted from [41] with permission. Copyright 2008 American Chemical Society...

Hamley IW, Ansari A, Castelletto V et al (2005) Solution self-assembly of hybrid block copolymers containing poly(ethylene glycol) and amphiphilic beta-strand peptide sequences. 

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