Biopolym. Cell. 2018; 34(3):207-217.
http://dx.doi.org/10.7124/bc.00097B
Bioorganic Chemistry
Fluorine-containing polyamphiphiles of block structure constructed of synthetic and biopolymer blocks
1Paiuk O. L., 1Mitina N. Ye., 2Myagkota O. S., 3Volianiuk K. A., 4Musat N., 4Stryganyuk G. Z., 2Reshetnyak O. V., 1Kinash N. I., 1Hevus O. I., 4Shermolovich Yu. G., 1Zaichenko A. S.
  1. Lviv Polytechnic National University
    12, S. Bandery Str., Lviv, Ukraine, 79013
  2. Ivan Franko National University of Lviv
    1, Universytetska Str., Lviv, Ukraine, 79000
  3. Helmholtz Centre for Environmental Research - UFZ,
    15, Permoserstraße Str., Leipzig, Germany, 04318
  4. Institute of organic chemistry NAS of Ukraine
    5, Murmanska Str., Kyiv, Ukraine, 02660

Abstract

Aim. Purposeful preparation of polymeric surfactants combining hydrophobic fluorine-containing and hydrophilic synthetic and natural blocks via radical and non-radical reactions using peroxide, epoxide and/or amino- terminal groups of the polymeric elementary blocks. Methods. Radical and non-radical condensation reactions, polymerization, spectral (NMR- and luminescence spectroscopy), gel-permeation chromatography and other analytical techniques`. Results. Primary oligomers poly(F-MA)-MP were synthesized via radical polymerization of fluorine-alkyl methacrylate (F-MA) in the presence of peroxide-containing telogen (MP). That provides controlling the oligomer chain length and architectures as well as entering a terminal peroxide group in the macromolecules. Radical polymerization of vinyl pyrrolidone (NVP) initiated by poly(F-MA)-MP as macroinitiator in the presence of epoxide-containing derivative of cumene (CGE) was used for obtaining water soluble poly(F-MA)-block-poly(NVP)-CGE. Finally oligonucleotide (ONC) was attached via condensation reaction of ONC primary amino group with terminal epoxide group of poly(F-MA)-block-poly(NVP)-CGE. Conclusions. A series of novel block/comb-like copolymers with synthetic and natural parts was synthesized. Obtained tri-block copolymers can be used as markers for labeling bacteria and pathological items including cancer cells.
Keywords: fluorinated polyamphiphiles, oligonucleotide, radical and coupling reactions, hybrid block-copolymer, bacteria labeling.
Full text: (PDF, in English)

References

[1] Ahmad Z, Shah A, Siddiq M, Kraatz H. Polymeric micelles as drug delivery vehicles. RCS Adv. 2014; 33(4): 17028–38.
[2] Negishi T, Koizumi F, Uchino H, Kuroda J, Kawaguchi T, Naito S, Matsumura Y. NK105, a paclitaxel-incorporating micellar nanoparticle, is a more potent radiosensitising agent compared to free paclitaxel. Br J Cancer. 2006;95(5):601-6.
[3] Riabtseva A, Mitina N, Boiko N, Garasevich S, Yanchuk I, Stoika R., Slobodyanyuk O, Zaichenko A. Structural and colloidal-chemical characteristics of nanosized drug delivery systems based on pegylated comb-like carriers. Chem Chem Technol. 2012; 6(3):291-5.
[4] Bailey CM, Nagarajan R, Camesano TA. Designing polymer micelles of controlled size, stability, and functionality for siRNA delivery. In: M. A. Ilies Ed. Control of amphiphilie self-assembling at the molecular level: supra-molecular assemblies with tuned physicochemical properties for delivery applications. ACS Symposium Series. 2017; 1271: 35-70.
[5] Kataoka K, Harada A, Nagasaki Y. Block copolymer micelles for drug delivery: design, characterization and biological significance. Adv Drug Deliv Rev. 2001;47(1):113-31.
[6] Ravey JC, Gherbi A, Stebe MJ. Comparative study of fluorinated and hydrogenated nonionic surfactants. I. Surface activity properties and critical concentrations. In: Eds Degiorgio V. Trends in Colloid and Interface Science II. Progress in Colloid & Polymer Science. 1988;76: 234-41.
[7] Wang M, Liu H, Li L, Cheng Y. A fluorinated dendrimer achieves excellent gene transfection efficacy at extremely low nitrogen to phosphorus ratios. Nat Commun. 2014;5:3053.
[8] Knight JC, Edwards PG, Paisey SJ. Fluorinated contrast agents for magnetic resonance imaging; a review of recent developments. RSC Adv. 2011; 1(8): 1415-25.
[9] Porsch C, Zhang Y, Östlund A, Damberg P, Ducani C, Malmström E, Nyström AM. In vitro evaluation of non-protein adsorbing breast cancer theranostics based on 19 f-polymer containing nanoparticles. Part Part Syst Charact. 2013; 30(4):381-90.
[10] Vatsulic P. Chemistry of monomers. Moscov: Izdatielstvo inostrannoi literatury, 1960. 735 p.
[11] Dikii M. A. Synthesis and some rections of peroxide monomers – derivatives of isopropenyl benzene. Russ J Organ Chem. 1981; 17(2): 353.
[12] Kinash NI, Paiuk OL, Dolynska LV, Nadashkevych ZYa, Hevus OI. The synthesis of novel functional derivatives of cumene alcohol. Visnyk NU "Lvivska polytekhnika" Khimiya, tekhnologiya rechovyn ta yih zastosuvannia. 2017; 863: 40-5.
[13] Amann RI, Binder BJ, Olson RJ, Chisholm SW, Devereux R, Stahl DA. Combination of 16S rRNA-targeted oligonucleotide probes with flow cytometry for analyzing mixed microbial populations. Appl Environ Microbiol. 1990;56(6):1919-25.
[14] Oliveira M, Andrade G, Guerra M, Bernardo F. Development of a fluorescent in situ hybridization protocol for the rapid detection and enumeration of Listeria monocytogenes in milk. Rev Port Ciênc Vet. 2003; 98(547): 119-24.
[15] Carte RE. Organic Solvents: Properties, Toxicity, and Industrial Effects. New York: Nova Science Publisher's, 2011; 173 p.
[16] Braun D, Cherdron H, Ritter H. Polymer synthesis: theory and practice. Fundamentals, methods, experiments. Berlin: Springer Science & Business Media, 2013. 404 p.
[17] Matyjaszewski K, Davis TP. Fundamentals of Atom Transfer Radical Polymerization In: Handbook of Radical Polymerization. New York: John Wiley & Sons, 2002; 523-628.
[18] Odian G. Principles of Polymerization, Fourth Edition. Hoboken: John Wiley & Sons, Inc, 2004; 839 p.
[19] Vasiliev VP. The homolytic decomposition of the alkenalkyl peroxide monomer and its polymers, Ph.D. thesis, Lviv: Lviv Polytechnic National University, 1990. 156 p.
[20] Tanaka T. Experimental methods in polymer science: modern methods in polymer research and technology. New York.: Academic Press, 2000; 604 p.
[21] Smith BC. Fundamentals of Fourier Transform Infrared Spectroscopy, Second Edition. Boca Raton: CRC Press, 2011; 207 p.
[22] Fainermanand V, Mille R. Maximum Bubble Pressure Tensiometry. In: Miller R, Liggieri L. (Eds.). Bubble and drop interfaces in progress in colloid and interface science, V.2. Brill, Leiden 2009; 665 p
[23] Zaichenko A, Mitina N, Shevchuk O, Rayevska K, Lobaz V, Skorokhoda T, Stoika R. Development of novel linear, block, and branched oligoelectrolytes and functionally targeting nanoparticles. Pure Appl Chem. 2008; 80 (11): 2309–26.