Hybrid block copolymers self-assembly

Kakizawa Y, Kataoka K. Block copolymer self-assembly into monodispersive nanoparticles with hybrid core of antisense DNA and calcium phosphate. Langmuir 2002 18 4539-4543. 

Design and Applications of Multiscale Organic-Inorganic Hybrid Materials Derived from Block Copolymer Self-Assembly... 

Sanwaria S, Singh S, Horech3 y A, Formanek P, Stamm M, Srivastava R, Nandan B (2015) Multifunctional core-shell polymer-inorganic hybrid nanofibers prepared via block copolymer self-assembly. RSC Adv 5 89861-89868... 

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. 

Liu B, Lewis AK, Shen W (2009) Physical hydrogels photo-cross-linked from self- assembled macromers for potential use in tissue engineering. Biomacromolecules 10 3182-3187 Vandermeulen GWM, Tziatzios C, Duncan R et al (2005) Peg-based hybrid block copolymers containing alpha-helical coiled coil peptide sequences control of self- assembly and preliminary biological evaluation. Macromolecules 38 761-769... 

The synthesis of polypeptide hybrid block copolymers is an area that has been under study for three decades. Initially, this field suffered from limitations in the synthesis of the polypeptide components that required excessive sample purification and fractionation to obtain well-defined copolymers. In recent years, vast improvements in NCA polymerizations now allow the synthesis of hybrid block copolymers of controlled dimensions (molecular weight, sequence, composition, and molecular weight distribution). Such well-defined materials will greatly assist in the identification of new self-assembled structures possible using ordered polypeptide segments, as well as yield new materials with a wide range of tunable properties. 

The transition from hybrid block copolymers with a homopeptide block toward those with sequence-defined peptide segments enriches the self-assembly behavior strongly. Ayers et smdied water-soluble block copolymers composed of a PEO block and a peptide block with comb architecture, which was obtained by the controlled polymerization of oligopeptide... 

A particularly interesting feature of these hybrid block copolymers is that the aggregation number and pH sensitivity of the nanoobjects can be controlled via direrted single and double mutations of the peptide primary structure. This may be relevant in light of possible biomedical applications because preliminary experiments have shown that the biological properties of the PEGylated coiled coils correlate to their self-assembly behavior. Another example that is worth mentioning is the work by Velonia et who studied the... 

Figure 6.3 Routes for surface modification of polymersomes with biofunctionalities by (A) end-group functionalization of block copolymers before self-assembly, (B) biomolecule conjugated hybrid block copolymers used for self-assembly, and (C) surface conjugation of biomolecules to preformed vesicles.

Polymer-polypeptide hybrid block copolymers are able to self-assemble either in bulk (microphase separation) or in selective solvents (micellization), like conventional block copolymers, and in addition are organized within the microphases into a-helix or j5-sheet... 

Babin, J., Rodriguez-Hemandez, J., Lecommandoux, S. etal. (2005) Self-assembled nanostnictures from peptide-synthetic hybrid block copolymers Complex, stimuU-responsive rod-coil architectures. Faraday Discussions, 128,179-192. 

Integrating block copolymer-directed nanostmcture control of hybrid materials with other stmcture formation processes is one future direction that this research will most likely take. A more fundamental direction is the transition from AB or ABA diblock copolymers to ABC terblock copolymers or even higher-order multiblock copolymers as stmcture-directing agents for inorganic materials. The introduction of a third block in ABC terblock copolymer self-assembly leads to a... 

Kros A, Jesse W, Metselaar GA, Comelissen JJLM (2005) Synthesis and self-assembly of rod-rod hybrid poly(gamma-benzyl L-glutamate)-block-polyisocyanide copolymers. Angew Chem hit Ed 44 4349 352... 

Time-resolved in situ Small Angle Neutron Scattering (SANS) investigations have provided direct experimental evidence for the initial steps in the formation of the SBA-15 mesoporous material, prepared using the non-ionic tri-block copolymer Pluronic 123 and TEOS as silica precursor. Upon time, three steps take place during the cooperative self-assembly of the Pluronic micelles and the silica species. First, the hydrolysis of TEOS is completed, without modifications of the Pluronic spherical micelles. Then, when silica species begin to interact with the micelles, a transformation from spherical to cylindrical micelles takes place before the precipitation of the ordered SBA-15 material. Lastly, the precipitation occurs and hybrid cylindrical micelles assemble into the two-dimensional hexagonal structure of SBA-15. 

Covalently connecting two incompatible polymers at their ends leads to a fascinating class of self-assembling materials [1]. Block copolymers constitute a well-studied and well-documented set of nanostructured hybrid materials [2], Many synthetic techniques are available for generating AB diblock, ABA triblock, ABC triblock and even more complicated block architectures [3,4], Furthermore, the thermodynamics governing the self-assembly... 

Figure 5.10 Diverse applications using hydrogen bonding interactions employed by Rotello and coworkers (Arumugam et al. 2007) (a) self-assembled dendronized polymer and (b) inorganic-organic hybrid material using barbiturate functionalized nanoparticles and Hamilton wedge functionalized block copolymers.

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