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Polymer and Biopolymer Systems of Complex Architecture and Composition

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Molecular Biophysics".

Deadline for manuscript submissions: closed (10 November 2021) | Viewed by 4683

Special Issue Editor

Special Issue Information

Dear Colleagues,

It is well known that natural polymers of complex composition (proteins, polysaccharides, and DNA) with different primary sequences of monomers form the basis of all living organisms. Branched polymers and their mixtures with linear polymers are also widespread in nature (e.g., glycogen, starch (branched amylopectin mixed with linear amylose), and dextran). In the late 1970s, the first artificial regular hyperbranched polymers, dendrimers, were synthesized. Currently, natural and synthetic polymers and polymer systems of complex architecture and composition are widely used in industry and in biomedical applications.

The purpose of this Special Issue is to obtain a broad picture of the current state of polymer science in this area based on reviews and scientific articles devoted to (but not limited to) the following systems and methods of their study:

Systems with a complex monomeric composition of polymers: Linear polymers of a complex composition, for example, synthetic diblock and triblock copolymers, DNA, peptides, and polysaccharides having different primary sequence of the corresponding monomers.

Systems with complex polymer chemical architectures: Branched synthetic polymers, such as graft copolymers, polymer stars, dendrimers, dendrigrafts, hyperbranched polymers, and branched polysaccharides and peptides. Hybrid polymers such as linear-dendron molecules and dendron-dendron molecules (for example, Janus dendrimers). Various crosslinked polymer systems including polymer networks and gels.

Systems with a complex composition of polymer systems components: For example, mixtures of various polymer molecules, complexes of linear and branched polymers, and complexes for the delivery of small and large bioactive molecules (drugs, peptides, oligo- and polysaccharides, DNA and RNA).

Systems capable of self-ordering: Association (including micelle formation in solution) and ordering of all the above polymeric molecules into complex spatial structures.

Methods: Synthesis of polymer and biopolymer molecules, and their characterization using various experimental methods. Theory, modeling, and applications of these systems in industry and biomedicine.

Prof. Dr. Igor Neelov
Guest Editor

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Keywords

  • polymers and biopolymers
  • dendrimers, dendrigrafts, hyperbranched polymers, hybrid molecules, micelles
  • synthesis, characterization, theory, computer simulation

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Published Papers (2 papers)

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Research

23 pages, 8030 KiB  
Article
Thermoresponsive Molecular Brushes with a Rigid-Chain Aromatic Polyester Backbone and Poly-2-alkyl-2-oxazoline Side Chains
by Elena Tarabukina, Emil Fatullaev, Anna Krasova, Maria Sokolova, Mikhail Kurlykin, Igor Neelov, Andrey Tenkovtsev and Alexander Filippov
Int. J. Mol. Sci. 2021, 22(22), 12265; https://doi.org/10.3390/ijms222212265 - 12 Nov 2021
Cited by 4 | Viewed by 1626
Abstract
A new polycondensation aromatic rigid-chain polyester macroinitiator was synthesized and used to graft linear poly-2-ethyl-2-oxazoline as well as poly-2-isopropyl-2-oxazoline by cationic polymerization. The prepared copolymers and the macroinitiator were characterized by NMR, GPC, AFM, turbidimetry, static, and dynamic light scattering. The molar masses [...] Read more.
A new polycondensation aromatic rigid-chain polyester macroinitiator was synthesized and used to graft linear poly-2-ethyl-2-oxazoline as well as poly-2-isopropyl-2-oxazoline by cationic polymerization. The prepared copolymers and the macroinitiator were characterized by NMR, GPC, AFM, turbidimetry, static, and dynamic light scattering. The molar masses of the polyester main chain and the grafted copolymers with poly-2-ethyl-2-oxazoline and poly-2-isopropyl-2-oxazoline side chains were 26,500, 208,000, and 67,900, respectively. The molar masses of the side chains of poly-2-ethyl-2-oxazoline and poly-2-isopropyl-2-oxazoline and their grafting densities were 7400 and 3400 and 0.53 and 0.27, respectively. In chloroform, the copolymers conformation can be considered as a cylinder wormlike chain, the diameter of which depends on the side chain length. In water at low temperatures, the macromolecules of the poly-2-ethyl-2-oxazoline copolymer assume a wormlike conformation because their backbones are well shielded by side chains, whereas the copolymer with short side chains and low grafting density strongly aggregates, which was visualized by AFM. The phase separation temperatures of the copolymers were lower than those of linear analogs of the side chains and decreased with the concentration for both samples. The LCST were estimated to be around 45 °C for the poly-2-ethyl-2-oxazoline graft copolymer, and below 20 °C for the poly-2-isopropyl-2-oxazoline graft copolymer. Full article
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22 pages, 4585 KiB  
Article
Why the Orientational Mobility in Arginine and Lysine Spacers of Peptide Dendrimers Designed for Gene Delivery Is Different?
by Valeriy V. Bezrodnyi, Oleg V. Shavykin, Sofia E. Mikhtaniuk, Igor M. Neelov, Nadezhda N. Sheveleva and Denis A. Markelov
Int. J. Mol. Sci. 2020, 21(24), 9749; https://doi.org/10.3390/ijms21249749 - 21 Dec 2020
Cited by 8 | Viewed by 2363
Abstract
New peptide dendrimer with Lys-2Arg repeating units was recently studied experimentally by NMR (RSC Advances, 2019, 9, 18018) and tested as gene carrier successfully (Int. J. Mol. Sci., 2020, 21, 3138). The unusual slowing down of the orientational mobility of 2Arg spacers in [...] Read more.
New peptide dendrimer with Lys-2Arg repeating units was recently studied experimentally by NMR (RSC Advances, 2019, 9, 18018) and tested as gene carrier successfully (Int. J. Mol. Sci., 2020, 21, 3138). The unusual slowing down of the orientational mobility of 2Arg spacers in this dendrimer was revealed. It has been suggested that this unexpected behavior is caused by the Arg-Arg pairing effect in water, which leads to entanglements between dendrimer branches. In this paper, we determine the reason for this slowing down using atomistic molecular dynamics simulation of this dendrimer. We present that the structural properties of Lys-2Arg dendrimer are close to those of the Lys-2Lys dendrimer at all temperatures (Polymers, 2020, 12, 1657). However, the orientational mobility of the H-H vector in CH2-N groups of 2Arg spacers in Lys-2Arg dendrimer is significantly slower than the mobility of the same vector in the Lys-2Lys dendrimer. This result is in agreement with the recent NMR experiments for the same systems. We revealed that this difference is not due to the arginine-arginine pairing, but is due to the semiflexibility effect associated with the different contour length from CH2-N group to the end of the side arginine or lysine segment in spacers. Full article
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