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Supramolecular Structures and Self-Association Processes in Polymer Systems Physiol. Res. 65 (Suppl. 2): S165-S178, 2016 https://doi.org/10.33549/physiolres.933419 REVIEW Supramolecular Structures and Self-Association Processes in Polymer Systems M. HRUBÝ1, S. K. FILIPPOV1, P. ŠTĚPÁNEK1 1Institute of Macromolecular Chemistry of the Czech Academy of Sciences, Prague, Czech Republic Received July 14, 2016 Accepted July 14, 2016 Summary synthesize macromolecules (Hadjichristidis et al. 2002) Self-organization in a polymer system appears when a balance is with more complex and controlled composition, along achieved between long-range repulsive and short-range with a better understanding of the physical-chemical attractive forces between the chemically different building blocks. processes interactions have provided the basis not only Block copolymers forming supramolecular assemblies in aqueous for a rational design and fabrication of sophisticated self- media represent materials which are extremely useful for the assembled nanostructures but, more generally, the basis construction of drug delivery systems especially for cancer for a new and powerful nanotechnology (Forster and applications. Such formulations suppress unwanted physico- Konrad 2003). In particular, the development of self- chemical properties of the encapsulated drugs, modify assembling block copolymers with different blocks being biodistribution of the drugs towards targeted delivery into tissue able to segregate in immiscible phases under appropriate of interest and allow triggered release of the active cargo. In this conditions, have proven their enormous potential to review, we focus on general principles of polymer self- obtain different nanostructures of interest, both in 2 and organization in solution, phase separation in polymer systems 3 dimensions (Hamley 1999). This naturally leads to (driven by external stimuli, especially by changes in temperature, investigation of physical (Strobl 2007) and biophysical pH, solvent change and light) and on effects of copolymer aspects of self-assembled polymer materials since self- architecture on the self-assembly process. organization is the governing principle of many biophysical activities and structures. Key words Both biotechnology and pharmaceutical Copolymers • Nanoparticles • Phase separation • Responsivity industries have produced wide variety of new medical treatments based on the key biomacromolecules: DNA, Corresponding author RNA, peptides and proteins. While these therapeutics P. Štěpánek, Institute of Macromolecular Chemistry of the have tremendous potential, developing effective delivery Czech Academy of Sciences, Heyrovského nám. 2, 162 06 formulations is a great challenge. Among the important Prague 6, Czech Republic. Fax: +420 296 809 410. E-mail: factors in the successful clinical application of such drugs [email protected] is securing of their sufficient stability, administration, absorption, metabolism and bioavailability at the target Introduction site. Polymer or biopolymer nanoparticles, which are formed by association of various macromolecules, are Self-organisation in a polymer system appears frequently used for drug delivery purposes (Kabanov et when a balance is achieved between long-range repulsive al. 1998). The formation of suitable nanoparticles should and short-range attractive forces between the chemically be properly sensitive to the actual bio-environment which different building blocks. The increasing capacity to is usually achieved by adequate changes in the PHYSIOLOGICAL RESEARCH • ISSN 0862-8408 (print) • ISSN 1802-9973 (online) 2016 Institute of Physiology of the Czech Academy of Sciences, Prague, Czech Republic Fax +420 241 062 164, e-mail: [email protected], www.biomed.cas.cz/physiolres S166 Hrubý et al. Vol. 65 conformation, shape, hydrophilicity of building polymers, common arrangements are polymersomes or layered etc. Therefore, stimuli-responsive, “intelligent” or structures. “smart” polymers that respond with large property The common approach applied to describing changes to small physical or chemical stimuli have been such structures is based on controlling the extent of frequently investigated (Hoffman 1997, Park 1997, macrophase separation that occurs in a mixture of two Swarbich 1994, Jeong et al. 2002, Leroux et al. 2001, compounds (solvents or polymers) that became Lazzari et al. 2006). The main impetus for studying these immiscible or incompatible as a result of a change of an polymers has been the need for a better understanding of external variable. This parameter can be temperature, pH the physical mechanism of co-operative interactions in or addition of a co-solvent, in principle it could also be biopolymers which, in turn, stimulated the research of a change in pressure but the latter is not very practical mimicking the co-operative behavior in synthetic since usually large pressure changes are needed to systems. Stimuli-responsive polymers were developed, achieve relatively small changes in phase diagrams due to which respond in a desired way to a change in low compressibility of common liquids. temperature, pH, electric or magnetic field, or in another A phase diagram for a polymer A/polymer B or parameter. “Smart” polymers can be used as an active polymer/solvent system is schematically represented in part of stimuli-responsive nanoparticles formed by self- Figure 1. In the classical case the energy of the system is association of macromolecules. given by enthalpic and entropic contributions and the Self-assembled nanoparticles can be categorized interaction parameter χ is given by the Flory-Huggins in different ways; a useful classification is according to relation: the dominant type of polymer-polymer interaction where χ =aT/ + b five major categories of nanoparticles can be where T is absolute temperature and a and b are distinguished: specific for the polymer/polymer or polymer/solvent pair. (1) stereocomplexes formed via van der Waals For more complex systems, a third term χs has to be forces; included: (2) polyelectrolyte (or polyionic) complexes χχ=aT/ ++ b s (1) which are formed between polymer acids and bases or In this simple representation the third term their salts and are stabilized by ionic bonds; includes all additional interactions in the system, in (3) complexes formed by hydrogen bonding particular the effect of different temperature expansions between polyelectrolytes and non-ionic polymers; of the system components and that of various specific (4) micelles, vesicles and other micelle-like interactions in the system (hydrogen bonds, ionic nanoparticles formed by hydrophobic interactions. interactions, ...) that may be dominant compared to the Some nanoparticles exhibit a combination of enthalpic/entropic terms a, b. these phenomena. Interpolymer nanoparticles often display physical and biological properties very different from those of individual constituent polymers. 20 Very commonly used structure-forming polymeric materials are block copolymers, in particular 15 diblock copolymers where the long-range repulsion N 10 interaction is given by the incompatibility of the blocks χ and the short-range attraction is provided by the covalent bond between the blocks (Forster and Konrad 2003, 5 Hadjichristidis et al. 2002). In the presence of solvent in 0 the system several types of self-assembled structures exist 0 0.2 0.4 0.6 0.8 1.0 the structure of which is governed by the thermodynamic φ interactions between the solvent and the blocks of the copolymer. A classic example is a micellar structure of Fig. 1. A schematic phase diagram for a polymer A/polymer B or a diblock copolymer solution occurring when the solvent polymer/solvent. ϕ is the volume fraction of the first component is selective (thermodynamically good for one block and of the system, N the number of monomeric units in the polymer chain and χ the interaction parameter describing the strength of bad for the second block); other types of possible interaction between polymer A and B or between the polymer and solvent. 2016 Polymer Self-Association S167 Once a macrophase separation has been initiated, nanoparticles formed by association of the the spatial extent of inhomogeneities produced by macromolecules. nucleation or spinodal decomposition can be controlled The most often studied polymers are and/or limited by accumulated charge on the surface of thermosensitive polymers where the phase separation is growing nuclei preventing macrophase separation due to achieved by a change in temperature T in Eq. (1): poly(N- electrostatic repulsion or by addition of amphiphilic isopropyl acrylamide) (PNIPAM) (Aseyev et al. 2006, molecules chosen in such a way that one part of this Kujawa et al. 2006, Tailor and Cerenkowski 1975) amphiphile interacts attractively with the nucleated poly(N-vinylcaprolactam) and poly(methyl vinyl ether) material while the other part interacts attractively with the (Aseyev et al. 2006, Kujawa et al. 2006) and their surrounding solvent. If the amount of added amphiphiles copolymers with either hydrophobic or hydrophilic is sufficient, the surface of the nucleated material then monomers and polymers. PNIPAM is a water-soluble becomes covered with the amphiphilic molecules which polymer with many attractive properties. It undergoes effectively terminates the phase separation and a coil-to-globule transition upon heating at 32 °C (lower stabilizes the system in a dispersed state. The formation critical solution temperature, LCST (Saiyto et al. 1993)), of nanoparticles is always driven by thermodynamics a property that is the result
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