THEORETICAL & PHYSICAL CHEMISTRY INSTITUTE
 
  Materials Synthesis and Physical Chemistry
  Carbon nanostructures and two-dimensional nanomaterials
  Block copolymer synthesis and self-assembled nanostructures
  Nanostructured biomaterials
  Énvestigations using vibrational spectroscopy/microscopy (Raman and infrared)
AFM/Raman correlative microscopy

  Clay minerals and clay-based hybrid materials
  Low dimensional Hybrid Materials
  Synthesis and physicochemical properties of advanced organic-inorganic materials
  Design and development of Metal Organic Frameworks and/or Covalent Organic Frameworks
  Design and construction of artificial photosynthetic systems for the conversion of solar energy to fuels

Material Synthesis and Physical Chemistry

Block copolymer synthesis and self-assembly
Dr. Asterios (Stergios) Pispas, Research Director
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We utilize controlled polymerization methodologies (RAFT, anionic, cationic, ATRP and NMP based polymerization schemes) as well as post-polymerization chemical functionalization routes in order to synthesize designed copolymers of diverse molecular architectures (linear diblock copolymers, triblock terpolymers, stars and mikto-arms stars, graft and hyperbranched copolymers).

The synthesized copolymers are showing environmentally responsive behavior, e.g. toward stimuli including pH, temperature, ionic strength, due to the rational design of their chemical structure We explore the effects of chemical structure on block copolymer self-assembly in aqueous media, on surfaces and in the bulk and their nanoscale and macroscale properties, in conjunction with chemical, physical and thermodynamic parameters of our systems, trying to elucidate structure-properties relations and provide new functional polymeric nanomaterials. These basic studies allow for the rational use of such functional macromolecules in a gamut of nanotechnological applications, focusing on biomedical, sensing and environmental applications.

We employ a plethora of physicochemical characterization techniques, available at TPCI or in collaborating labs, in order to molecularly characterize the copolymers and their nanoscale self-organized structures.

 

Key publications

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Polym. Chem.  2017, 8, 4538

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J. Polym. Sci. Part A: Polym. Chem. 2019, 57, 1771

   

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Polymers 2020, 12, 1382

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Macromolecules 2020, 53, 4068

   

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J. Polym. Sci. 2021, 59, 1874

 

 

 

 

Recent publications (since 2013)

Block copolymer synthesis and self-assembly
  • M. Karayianni, S. Pispas, "Block copolymer solution self-assembly: Recent advances, emerging trends, and applications", J. Polym. Sci. 2021, 59, 1874. (invited review article)
    DOI: 10.1002/pol.20210430
  • Vagias, A. Papagiannopoulos, L. P. Kreuzer, D. Giaouzi, S. Busch, S. Pispas, P. Muller-Buschbaum, "Effects of Polymer Block Length Asymmetry and Temperature on the Nanoscale Morphology of Thermoresponsive Double Hydrophilic Block Copolymers in Aqueous Solutions", Macromolecules 2021, 54, 7298.
    DOI: 10.1021/acs.macromol.1c01005
  • D. Selianitis, S. Pispas, "P(MMA-co-HPMA)-b-POEGMA copolymers: synthesis, micelle formation in aqueous media and drug encapsulation", Polym. Int. 2021, 70, 1508.
    DOI: 10.1002/pi.6229
  • K. Jiang, G. Wen, A. Skandalis, S. Pispas, Y. Ding, H. Chen, "Influences of subphase pH and temperature on the interfacial aggregation behavior of poly(lauryl methacrylate)-block-poly(methacrylic acid)", Colloids Surf. A: Phys. Eng. Asp. 2021, 620, 126528.
    DOI: 10.1016/j.colsurfa.2021.126528
  • A. Skandalis, T. Sentoukas, D. Giaouzi, M. Kafetzi, S. Pispas, "Latest advances on the synthesis of linear ABC-type triblock terpolymers and star-shaped polymers by RAFT polymerization", Polymers 2021, 13, 1698. (invited review article)
    DOI: 10.3390/polym13111698
  • E. Vlassi, A. Papagiannopoulos, S. Pispas, "Amphiphilic AxBy mikto-arm star copolymers with PLMA and POEGMA arms: Self-assembly and drug encapsulation", J. Polym. Sci. 2021, 59, 775.
    DOI: 10.1002/pol.20210082
  • E. Pavlopoulou, K. Chrissopoulou, S. Pispas, N. Hadjichristidis, S. H. Anastasiadis, "The micellization of well-defined single graft copolymers in block copolymer/homopolymer blends", Polymers 2021, 13, 833.
    DOI: 10.3390/polym13050833
  • M. Kafetzi, S. Pispas, "Multifaceted pH and Temperature Induced Self-Assembly of P(DMAEMA-co-LMA)-b-POEGMA Terpolymers and Their Cationic Analogues in Aqueous Media", Macromol. Chem. Phys. 2021, 222, 2000358.
    DOI: 10.1002/macp.202000358
  • H. Chen, G. Wen, V. Chrysostomou, S. Pispas, H. Li, Z. Sun, "Effects of Ionic Strength and Ion Specificity on the Interface Behavior of Poly(dimethylaminoethyl methacrylate)-Poly(lauryl methacrylate)", Langmuir 2021, 37, 2419.
    DOI: 10.1021/acs.langmuir.0c03424
  • O. Vassiliadou, V. Chrysostomou, S. Pispas, P. A. Klonos, A. Kyritsis, "Molecular dynamics and crystallization in polymers based on ethylene glycol methacrylates (EGMAs) with melt memory characteristics: From linear oligomers to comb-like polymers", Soft Matter 2021, 17, 1284.
    DOI: 10.1039/d0sm01666g
  • M. Kafetzi, S. Pispas, "Effects of hydrophobic modifications on the solution self-assembly of P(DMAEMA-co-QDMAEMA)-b-POEGMA random diblock copolymers",  Polymers 2021, 13, 1.
    DOI: 10.3390/polym13030338
  • J-J. Kang, F. A. Jung, C-H. Ko, K. Shehu, L. C. Barnsley, F. Kohler, H. Dietz, J. Zhao, S. Pispas, C. M. Papadakis, "Thermoresponsive molecular brushes with propylene oxide/ethylene oxide copolymer side chains in aqueous solution", Macromolecules 2020, 53, 4068.
    DOI: 10.1021/acs.macromol.0c00263
  • H. Chen, G. Wen, V. Chrysostomou, S. Pispas, W. Pan, J. Zuo, M. Li, H. Li, and Z. Sun, "Effects of copolymer composition and subphase pH/temperature on the interfacial aggregation behavior of poly(2-(dimethylamino)ethyl methacrylate)-block-poly(lauryl methacrylate)", J. Phys. Chem. C 2020, 124, 4563.
    DOI: 10.1021/acs.jpcc.9b10673
  • M. Kanidi, A. Papagiannopoulos, A. Matei, M. Dinescu, S. Pispas, M. Kandyla, "Functional surfaces of laser-microstructured silicon coated with thermoresponsive PS/PNIPAM polymer blends: Switching reversibly between hydrophilicity and hydrophobicity", Appl. Surf. Sci. 2020, 527, 146841.
    DOI: 10.1016/j.apsusc.2020.146841
  • D. Selianitis, S. Pispas, "PDEGMA‐b‐PDIPAEMA copolymers via RAFT polymerization and their pH and thermoresponsive schizophrenic self‐assembly in aqueous media", J. Polym. Sci. 2020, 58, 1867.
    DOI: 10.1002/pol.20200266
  • W. Pan, H. Chen, G. Wen, D. Giaouzi, S. Pispas, J. Zuo, "Surface micelle structures and monolayer compression moduli of double hydrophilic block copolymer", J. Phys. Chem. C 2020, 124, 17150.
    DOI: 10.1021/acs.jpcc.0c05272
  • D. Giaouzi, S. Pispas, "Effects of chemical modifications on the thermoresponsive behavior of a PDMAEA-b-PNIPAM-b-POEGA triblock terpolymer", Polymers 2020, 12, 1382.
    DOI: 10.3390/polym12061382
  • S. Yang, G. Wen, S. Pispas, K. You, "Effects of spreading and subphase conditions on the interfacial behavior of an amphiphilic copolymer poly(n-butylacrylate)-b-poly(acrylic acid)", Polymer 2019, 172, 66.
    DOI: 10.1016/j.polymer.2019.03.060
  • K. You, G. Wen, A. Skandalis, S. Pispas, S. Yang, H. Li, Z. Sun, "Effects of subphase pH and temperature on the aggregation behavior of poly(lauryl acrylate)-block-poly(N-isopropylacrylamide) at the air/water interface", J. Phys. Chem. C 2019, 123, 10435.
    DOI: 10.1021/acs.jpcc.9b01320
  • M. Kanidi, A. Papagiannopoulos, A. Skandalis, M. Kandyla, S. Pispas, "Thin films of PS/PS-b-PNIPAM and PS/PNIPAM polymer blends with tunable wettability", J. Polym. Sci. Part B: Polym. Phys. 2019, 57, 67.
    DOI: 10.1002/polb.24822
  • D. Giaouzi, S. Pispas, "Synthesis and self-assembly of thermoresponsive poly(N-isopropylacrylamide)-b-poly(oligo ethylene glycol methyl ether methacrylate) double hydrophilic block copolymers", J. Polym. Sci. Part A: Polym. Chem. 2019, 57, 1467.
    DOI: 10.1002/pola.29411
  • Skandalis, S. Pispas, "Synthesis of (AB)n, AnBn, and AxBy-type amphiphilic and double-hydrophilic star copolymers by RAFT polymerization", J. Polym. Sci. Part A: Polym. Chem. 2019, 57, 1771.
    DOI: 10.1002/pola.29447
  • K. You, G. Wen, A. Skandalis, S. Pispas, S. Yang, "Anion specificity effects on the interfacial aggregation behavior of poly(lauryl acrylate)-block-pol(N-isopropylacrylamide)", Langmuir 2019, 35, 9904.
    DOI: 10.1021/acs.langmuir.9b01561
  • Karatza, P. Klonos, S. Pispas, A. Kyritsis, "Glass transition and molecular dynamics in PHPMA-b-POEGMA block copolymers", Polymer 2019, 181, 121794.
    DOI: 10.1016/j.polymer.2019.121794
  • Chroni, S. Pispas, A. Forys, B. Trzebicka, "pH-driven morphological diversity in poly[n-butyl acrylate-block-(2-(dimethylamino)ethyl acrylate)] amphiphilic copolymer solutions", Macromol. Rapid Commun. 2019, 40, 1900477.
    DOI: 10.1002/marc.201900477
  • Y. Wang, G. Wen, S. Pispas, S. Yang, K. You, "Effects of subphase pH, temperature and ionic strength on the aggregation behavior of PnBA-b-PAA at the air/water interface", J. Colloid Interf. Sci. 2018, 512, 862.
    DOI: 10.1016/j.jcis.2017.11.002
  • Papagiannopoulos, A. Meristoudi, S. Pispas, U. Keiderling, "Thermal response and self-organization in an amphiphilic triblock polyelectrolyte and the influence of the globular protein lysozyme", Eur. Polym. J. 2018, 99, 49.
    DOI: 10.1016/j.eurpolymj.2017.12.005
  • V. Chrysostomou, S. Pispas, "Stimuli-responsive amphiphilic PDMAEMA-b-PLMA copolymers and their cationic and zwitterionic analogs", J. Polym. Sci. Part A: Polym. Chem. 2018,56, 598.
    DOI: 10.1002/pola.28931
  • Papagiannopoulos, J. Zhao, G. Zhang, S. Pispas, C. J. Jafta, "Viscosity transitions driven by thermoresponsive self-assembly in PHOS-g-P(PO-r-EO) brush copolymer", Macromolecules 2018, 51, 1644.
    DOI: 10.1021/acs.macromol.7b02711
  • Papagiannopoulos, M. Karayianni, S. Pispas, A. Radulescu, "Formation of complexes in aqueous solutions of amphiphilic triblock polyelectrolytes of different topologies and an oppositely charged protein", Soft Matter 2018, 14, 2826.
    DOI: 10.1039/c8sm00208h
  • N. Pippa, T. Sentoukas, S. Pispas, C. Demetzos, A. Papalois, N. Bouropoulos, "pH-responsive polymeric nanoassemblies encapsulated into alginate beads: morphological characterization and swelling studies", J. Polym. Res. 2018, 25, 117.
    DOI: 10.1007/s10965-018-1519-1
  • Karatza, S. Pispas, "Poly(hydroxyl propyl methacrylate)-b-poly(oligo ethylene glycol methacrylate) thermoresponsive block copolymers by RAFT polymerization", Macromol. Chem. Phys. 2018, 219, 1800060.
    DOI: 10.1002/macp.201800060
  • E. Vlassi, A. Papagiannopoulos, S. Pispas, "Hydrolyzed poly(2-phenyl-2-oxazoline)s in aqueous media and biological fluids", Macromol. Chem. Phys. 2018, 219, 1800047.
    DOI: 10.1002/macp.201800047
  • T. Sentoukas, S. Pispas, "Poly(dimethylaminoethyl methacrylate)-b-poly(hydroxylpropyl methacrylate) copolymers: Synthesis and pH/thermo-responsive behavior in aqueous solutions", J. Polym. Sci. Part A: Polym. Chem. 2018, 56, 1962.
    DOI: 10.1002/pola.29082
  • Skandalis, S. Pispas, "pH- and thermo-responsive solution behavior of amphiphilic, linear triblock terpolymers", Polymer 2018, 157, 9.
    DOI: 10.1016/j.polymer.2018.10.023
  • A. Skandalis, S. Pispas, "PLMA-b-POEGMA amphiphilic block copolymers: Synthesis and self-assembly in aqueous media", J. Polym. Sci. Part A: Polym. Chem. 2017, 55, 155.
    DOI: 10.1002/pola.28379
  • J. Skvarla, R. K. Raya, M. Uchman, J. Zednik, K. Prochazka, V. M. Garamus, A. Meristoudi, S. Pispas, M. Stepanek, "Thermoresponsive behavior of poly(N-isopropylacrylamide)s with dodecyl and carboxyl terminal groups in aqueous solutions: pH-dependent cloud point temperature", Colloid Polym. Sci. 2017, 295, 1343.  (invited article)
    DOI: 10.1007/s00396-017-4067-z
  • Skandalis, S. Pispas, "PDMAEMA-b-PLMA-b-POEGMA triblock terpolymers via RAFT polymerization and their self-assembly in aqueous solutions", Polym. Chem. 2017, 31, 4538.
    DOI: 10.1039/c7py00905d
  • M. Anyfantakis, A. Pamvouxoglou, C. Mantzaridis, S. Pispas, H-J. Butt, G. Fytas, B. Loppinet, "Kinetics of light-induced concentration patterns in transparent polymer solutions", J. Phys. Chem. B 2017, 121, 7180.
    DOI: 10.1021/acs.jpcb.7b02239
  • A. Thanassoulas, A. Papadopoulos, S. Pispas, J. Zhao, G. Zhang, G. Nounesis, "Thermodynamic characterization of poly(4-hydroxystyrene)-g-[poly(propyleneoxide-b-ethylene oxide)] thermoresponsive brush copolymers", Thermochimica Acta 2016, 638, 89.
    DOI: 10.1016/j.tca.2016.06.018
  • S. Kripotou, C. Psylla, K. Kyriakos, K. N. Raftopoulos, J. Zhao, G. Zhang, S. Pispas, C. M. Papadakis, A. Kyritsis, "Structure and crystallization behavior of poly(ethylene oxide) (PEO) chains in core-shell brush copolymers with poly(propylene oxide)-block-poly(ethylene oxide) side chains", Macromolecules 2016, 49, 5963.
    DOI: 10.1021/acs.macromol.6b00879
  • M. Karayianni, S. Pispas, "Self-assembly of amphiphilic block copolymers in selective solvents", in Fluorescence Studies of Polymer Containing Systems, Ed. K. Prochazka, Springer Series on Fluorescence 16, Springer International Publishing, Switzerland, 2016. (invited).
    DOI: 10.1007/978-3-319-26788-3_2
  • A. Papagiannopoulos, M. Karayianni, G. Mountrichas, and S. Pispas, "Micellar and fractal aggregates formed by two triblock terpolymers with different arrangements of one charged, one nutral hydrophilic and one hydrophobic block", Polymer 2015, 63, 134.
    DOI: 10.1016/j.polymer.2015.03.004
  • J. Xu, J. Yang, X. Ye, C. F. Ma, G. Zhang, S. Pispas, "Synthesis and properties of amphiphilic and biodegradable poly(ε-caprolactone-co-glycidol) copolymers", J. Polym. Sci. Part A: Polym. Chem. 2015, 53, 846.
    DOI: 10.1002/pola.27515
  • J. Song, J. Xu, S. Pispas, G. Zhang, "One-pot synthesis of poly(L-lactide)-b-poly(methyl methacrylate) block copolymers", RSC Advances  2015, 5, 38243.
    DOI: 10.1039/c4ra17202g
  • J. Xu, J. Song, S. Pispas, G. Zhang, "Controlled/living ring-opening polymerization of ε-caprolactone with salicylic acid as the organocatalyst", J. Polym. Sci. Part A: Polym. Chem. 2014, 52, 1185.
    DOI: 10.1002/pola.27104
  • O. S. Taskin, I. Erel-Goktepe, M. A. A. Khan, S. Pispas, Y. Yagci, "Polystyrene-b-poly(2-vinyl phenacyl pyridinium) salts as photoinitiators for free radical and cationic polymerizations and their photoinduced molecular associations", J. Photochem. Photobio. A: Chem. 2014, 285, 30.
    DOI: 10.1016/j.jphotochem.2014.03.018
  • A. Papagiannopoulos, J. Zhao, G. Zhang, S. Pispas, A. Radulescu, "Thermoresponsive aggregation of PS-PNIPAM-PS triblock copolymer: A combined study of light scattering and small angle neutron scattering", Eur. Polym. J. 2014, 56, 59.
    DOI: 10.1016/j.eurpolymj.2014.04.013
  • J. Xu, J. Song, S. Pispas, G. Zhang, "Metal-free controlled ring-opening polymerization of ε-caprolactone in bulk using tris(pentafluorophenyl)borane as a catalyst", Polym. Chem. 2014, 5, 4726.
    DOI: 10.1039/c4py00432j
  • J. Xu, W. Lian, S. Pispas, G. Zhang, "One pot synthesis of functional poly(methacrylate) by ATRP and 1,8-diazacyclo-[5,4,0]undec-7-ene catalyzed transesterification", J. Polym. Sci. Part A: Polym. Chem. 2014, 52, 2998.
    DOI: 10.1002/pola.27346
  • J. Skvarla, J. Zednik, M. Slouf, S. Pispas, M. Stepanek, "Poly(N-isopropyl acrylamide)-block-poly(n-butyl acrylate) thermoresponsive amphiphilic copolymers: Synthesis, characterization and self-assembly behaviour in aqueous solutions", Eur. Polym. J. 2014, 61, 124.
    DOI: 10.1016/j.eurpolymj.2014.10.002
  • M. Kalloudis, E. Glynos, S. Pispas, J. Walker, V. Koutsos, "Thin films of poly(isoprene-b-ethylene oxide) diblock copolymers on mica: an atomic force microscopy study", Langmuir 2013, 29, 2339.
    DOI: 10.1021/la400041x
  • H. Yang, J. Xu, S. Pispas, G. Zhang, "One step synthesis of hyperbranched biodegradable polymer", RSC Advances 2013, 3, 6853.
    DOI: 10.1039/c3ra23422c
  • A. Papagiannopoulos, J. Zhao, G. Zhang, S. Pispas, A. Radulescu, "Thermoresponsive transition of a PEO-b-PNIPAM copolymer: From hierarchical aggregates to well defined ellipsoidal vesicles", Polymer 2013, 54, 6373.
    DOI: 10.1016/j.polymer.2013.09.016

 

 

 

 

 

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