Kinetics of temperature response of PEO-b-PNIPAM-b-PAA triblock terpolymer aggregates and of their complexes with lysozyme

Papagiannopoulos, Aristeidis; Meristoudi, Anastasia; Hong, Kunlun; Pispas, Stergios

doi:10.1016/j.polymer.2015.12.023

Title: Kinetics of temperature response of PEO-b-PNIPAM-b-PAA triblock terpolymer aggregates and of their complexes with lysozyme

Journal Article · Fri Dec 18 00:00:00 EST 2015 · Polymer

DOI:https://doi.org/10.1016/j.polymer.2015.12.023· OSTI ID:1237639

Papagiannopoulos, Aristeidis ^[1]; Meristoudi, Anastasia ^[1]; Hong, Kunlun ^[2]; Pispas, Stergios ^[1]

National Hellenic Research Foundation, Athens (Greece)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We present the kinetics of temperature response of a PEO-b-PNIPAM-b-PAA triblock terpolymer and of its complexes with lysozyme in aqueous solution. It is found that during the coil-to-globule transition of PNIPAM new bonds within the polymer aggregates are created, making the transition of the aggregates partially irreversible. This effect is also found for the protein loaded PEO-b-PNIPAM-b-PAA aggregates whereas in this case protein globules appear to enhance the formation of bonds, making the transition totally irreversible. The internal dynamics of both aggregates and complexes are “frozen” once the temperature is increased upon PINIPAM's LCST in water and remain so even when the temperature drops below LCST. As a result, we investigate the complexation kinetics of lysozyme and PEO-b-PNIPAM-b-PAA and observe that it occurs in two stages, one where protein globules adsorb on single pre-formed aggregates and one where protein globules cause inter-aggregate clustering.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1237639

Journal Information:: Polymer, Vol. 83, Issue C; ISSN 0032-3861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 11 works

Citation information provided by
Web of Science

References (36)

Emerging applications of stimuli-responsive polymer materials Stuart, Martien A. Cohen; Huck, Wilhelm T. S.; Genzer, Jan Nature Materials, Vol. 9, Issue 2, p. 101-113 https://doi.org/10.1038/nmat2614	journal	January 2010
Structure and design of polymeric surfactant-based drug delivery systems Torchilin, Vladimir P. Journal of Controlled Release, Vol. 73, Issue 2-3 https://doi.org/10.1016/S0168-3659(01)00299-1	journal	June 2001
Spherical polyelectrolyte brushes Ballauff, M. Progress in Polymer Science, Vol. 32, Issue 10 https://doi.org/10.1016/j.progpolymsci.2007.05.002	journal	October 2007
Self-Cross-Linked Polymer Nanogels: A Versatile Nanoscopic Drug Delivery Platform Ryu, Ja-Hyoung; Chacko, Reuben T.; Jiwpanich, Siriporn Journal of the American Chemical Society, Vol. 132, Issue 48 https://doi.org/10.1021/ja1069932	journal	December 2010
Thermoresponsive hydrogels in biomedical applications Klouda, Leda; Mikos, Antonios G. European Journal of Pharmaceutics and Biopharmaceutics, Vol. 68, Issue 1 https://doi.org/10.1016/j.ejpb.2007.02.025	journal	January 2008
Hydrogels in drug delivery: Progress and challenges Hoare, Todd R.; Kohane, Daniel S. Polymer, Vol. 49, Issue 8 https://doi.org/10.1016/j.polymer.2008.01.027	journal	April 2008
Microgels as Nanoreactors: Applications in Catalysis Welsch, Nicole; Ballauff, Matthias; Lu, Yan Chemical Design of Responsive Microgels https://doi.org/10.1007/12_2010_71	book	January 2010
Reduction and temperature dual-responsive crosslinked polymersomes for targeted intracellular protein delivery Cheng, Ru; Meng, Fenghua; Ma, Shoubao Journal of Materials Chemistry, Vol. 21, Issue 47 https://doi.org/10.1039/c1jm13536h	journal	January 2011
Morphological transitions in aggregates of thermosensitive poly(ethylene oxide)- b -poly( N -isopropylacrylamide) block copolymers prepared via RAFT polymerization: Morphological Transitions in PEO- b -PNIPAM Zhao, Junpeng; Zhang, Guangzhao; Pispas, Stergios Journal of Polymer Science Part A: Polymer Chemistry, Vol. 47, Issue 16 https://doi.org/10.1002/pola.23470	journal	July 2009
Living Radical Polymerization by the RAFT Process - A Second Update Moad, Graeme; Rizzardo, Ezio; Thang, San H. Australian Journal of Chemistry, Vol. 62, Issue 11 https://doi.org/10.1071/CH09311	journal	January 2009
Micellar and fractal aggregates formed by two triblock terpolymers with different arrangements of one charged, one neutral hydrophilic and one hydrophobic block Papagiannopoulos, Aristeidis; Karayianni, Maria; Mountrichas, Grigoris Polymer, Vol. 63 https://doi.org/10.1016/j.polymer.2015.03.004	journal	April 2015
Light Scattering by Fractal Aggregates: A Review Sorensen, C. M. Aerosol Science and Technology, Vol. 35, Issue 2 https://doi.org/10.1080/02786820117868	journal	January 2001
Dynamic light scattering study of internal motions of polymer coils in dilute solution Chu, Benjamin; Wang, Zhulun; Yu, Jiqun Macromolecules, Vol. 24, Issue 26 https://doi.org/10.1021/ma00026a005	journal	December 1991
Asymptotic behavior and long-range interactions in aqueous solutions of poly(ethylene oxide) Devanand, K.; Selser, J. C. Macromolecules, Vol. 24, Issue 22 https://doi.org/10.1021/ma00022a008	journal	October 1991
Characterization of Poly(N-isopropylmethacrylamide) in Water Kubota, Kenji; Hamano, Kenzi; Kuwahara, Nobuhiro Polymer Journal, Vol. 22, Issue 12 https://doi.org/10.1295/polymj.22.1051	journal	December 1990
Structure of Micelles of Poly( n -butyl acrylate)- block -poly(acrylic acid) Diblock Copolymers in Aqueous Solution Colombani, Olivier; Ruppel, Markus; Burkhardt, Markus Macromolecules, Vol. 40, Issue 12 https://doi.org/10.1021/ma0609580	journal	June 2007
Thermoresponsive transition of a PEO-b-PNIPAM copolymer: From hierarchical aggregates to well defined ellipsoidal vesicles Papagiannopoulos, Aristeidis; Zhao, Junpeng; Zhang, Guangzhao Polymer, Vol. 54, Issue 23 https://doi.org/10.1016/j.polymer.2013.09.016	journal	November 2013
Thermoresponsive aggregation of PS–PNIPAM–PS triblock copolymer: A combined study of light scattering and small angle neutron scattering Papagiannopoulos, Aristeidis; Zhao, Junpeng; Zhang, Guangzhao European Polymer Journal, Vol. 56 https://doi.org/10.1016/j.eurpolymj.2014.04.013	journal	July 2014
Interchain Hydrogen-Bonding-Induced Association of Poly(acrylic acid)- graft -poly(ethylene oxide) in Water Hao, Jinkun; Yuan, Guangcui; He, Weidong Macromolecules, Vol. 43, Issue 4 https://doi.org/10.1021/ma9025515	journal	February 2010
Globule-to-Coil Transition of a Single Homopolymer Chain in Solution Wu, Chi; Wang, Xiaohui Physical Review Letters, Vol. 80, Issue 18 https://doi.org/10.1103/PhysRevLett.80.4092	journal	May 1998
Kinetics of aggregation in micellar solutions of thermoresponsive triblock copolymers – influence of concentration, start and target temperatures Adelsberger, Joseph; Grillo, Isabelle; Kulkarni, Amit Soft Matter, Vol. 9, Issue 5 https://doi.org/10.1039/C2SM27152D	journal	January 2013
Kinetics of Collapse Transition and Cluster Formation in a Thermoresponsive Micellar Solution of P(S-b-NIPAM-b-S) Induced by a Temperature Jump Adelsberger, Joseph; Metwalli, Ezzeldin; Diethert, Alexander Macromolecular Rapid Communications, Vol. 33, Issue 3 https://doi.org/10.1002/marc.201100631	journal	January 2012
Mechanism of Microgel Formation via Cross-Linking of Polymers in Their Dilute Solutions: Mathematical Explanation with Computer Simulations Schmitz, Kenneth S.; Wang, Benlian; Kokufuta, Etsuo Macromolecules, Vol. 34, Issue 23 https://doi.org/10.1021/ma010956+	journal	October 2001
On the hydrodynamic radius of fractal aggregates Van Saarloos, Wim Physica A: Statistical Mechanics and its Applications, Vol. 147, Issue 1-2 https://doi.org/10.1016/0378-4371(87)90111-7	journal	November 1987
Light scattering studies on core–shell systems: determination of size parameters of sterically stabilized poly(methylmethacrylate) dispersions Hirzinger, B.; Helmstedt, M.; Stejskal, J. Polymer, Vol. 41, Issue 8 https://doi.org/10.1016/S0032-3861(99)00472-3	journal	April 2000
Structure formation of surfactants in concentrated sulphuric acid: a light scattering study M�ller, A.; Burchard, W. Colloid & Polymer Science, Vol. 273, Issue 9 https://doi.org/10.1007/BF00657636	journal	September 1995
Thermo-sensitive poly(N-vinylcaprolactam-co-acetoacetoxyethyl methacrylate) microgels: 1—synthesis and characterization Boyko, Volodymyr; Pich, Andrij; Lu, Yan Polymer, Vol. 44, Issue 26 https://doi.org/10.1016/j.polymer.2003.09.037	journal	December 2003
Temperature-Controlled Assembly and Release from Polymer Vesicles of Poly(ethylene oxide)-block- poly(N-isopropylacrylamide) Qin, S.; Geng, Y.; Discher, D. E. Advanced Materials, Vol. 18, Issue 21 https://doi.org/10.1002/adma.200601019	journal	November 2006
Reversibly crosslinked temperature-responsive nano-sized polymersomes: synthesis and triggered drug release Xu, Haifei; Meng, Fenghua; Zhong, Zhiyuan Journal of Materials Chemistry, Vol. 19, Issue 24 https://doi.org/10.1039/b901141b	journal	January 2009
Spectral interpretation of thermally irreversible recovery of poly(N-isopropylacrylamide-co-acrylic acid) hydrogel Sun, Shengtong; Hu, Jun; Tang, Hui Physical Chemistry Chemical Physics, Vol. 13, Issue 11 https://doi.org/10.1039/c0cp01939a	journal	January 2011
Homopolymer Self-Assembly into Stable Nanoparticles: Concerted Action of Hydrophobic Association and Hydrogen Bonding in Thermoresponsive Poly(alkylacrylic acid)s Sedlák, Marián The Journal of Physical Chemistry B, Vol. 116, Issue 8 https://doi.org/10.1021/jp208445p	journal	February 2012
Volume phase transition in a nonionic gel Hirokawa, Yoshitsugu; Tanaka, Toyoichi The Journal of Chemical Physics, Vol. 81, Issue 12 https://doi.org/10.1063/1.447548	journal	December 1984
Formation of an Intrapolymer Complex from Human Serum Albumin and Poly(ethylene glycol) Azegami, Shinji; Tsuboi, Atsushi; Izumi, Tsuyoshi Langmuir, Vol. 15, Issue 4 https://doi.org/10.1021/la9809269	journal	February 1999
Protein Separation via Polyelectrolyte Coacervation: Selectivity and Efficiency Wang, Y. -f.; Gao, J. Y.; Dubin, P. L. Biotechnology Progress, Vol. 12, Issue 3 https://doi.org/10.1021/bp960013+	journal	June 1996
Charge Stoichiometry Inside Polyelectrolyte−Protein Complexes: A Direct SANS Measurement for the PSSNa−Lysozyme System Gummel, Jérémie; Boué, François; Demé, Bruno The Journal of Physical Chemistry B, Vol. 110, Issue 49 https://doi.org/10.1021/jp064383k	journal	December 2006
Starch Fractions as Examples for Nonrandomly Branched Macromolecules. 4. Angular Dependence in Dynamic Light Scattering Galinsky, Gabriela; Burchard, Walther Macromolecules, Vol. 30, Issue 22 https://doi.org/10.1021/ma961776g	journal	November 1997

Cited By (1)

Formation of complexes in aqueous solutions of amphiphilic triblock polyelectrolytes of different topologies and an oppositely charged protein Papagiannopoulos, Aristeidis; Karayianni, Maria; Pispas, Stergios Soft Matter, Vol. 14, Issue 15 https://doi.org/10.1039/c8sm00208h	journal	January 2018

Similar Records

Assembling PNIPAM-Capped Gold Nanoparticles in Aqueous Solutions

Journal Article · Wed Nov 22 00:00:00 EST 2023 · ACS Macro Letters · OSTI ID:1237639

Nayak, Binay P.; Kim, Hyeong Jin; Nayak, Srikanth; +4 more

Fluorine-Containing ABC Linear Triblock Terpolymers: Synthesis and Self-assembly in Solution

Journal Article · Sat Jan 01 00:00:00 EST 2011 · Journal of Polymer Science, Part A: Polymer Chemistry · OSTI ID:1237639

He, Lihong; Hinestrosa Salazar, Juan P; Pickel, Joseph M; +4 more

Temperature-dependent conformational change of PNIPAM grafted chains at high surface density in water.

Journal Article · Tue Jul 01 00:00:00 EDT 2003 · Proposed for publication in Macromolecules. · OSTI ID:1237639

Satija, Sushil K; Mendez, Sergio; Balamurugan, Sreelatha S; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
thermoresponsive polymers
protein complexation
kinetics

Title: Kinetics of temperature response of PEO-b-PNIPAM-b-PAA triblock terpolymer aggregates and of their complexes with lysozyme

Citation Formats

References (36)

Cited By (1)

Similar Records

Related Subjects