title: Hierarchies of networked phases induced by multiple liquid-liquid critical points.
abstract: Nanoparticles and colloids functionalized by four single strands of DNA can be thought of as designed analogs to tetrahedral network-forming atoms and molecules, with a difference that the attached DNA strands allow for control of the length scale of bonding relative to the core size. We explore the behavior of an experimentally realized model for nanoparticles functionalized by four single strands of DNA (a tetramer), and show that this single-component model exhibits a rich phase diagram with at least three critical points and four thermodynamically distinct amorphous phases. We demonstrate that the additional critical points are part of the Ising universality class, like the ordinary liquid-gas critical point. The dense phases consist of a hierarchy of interpenetrating networks, reminiscent of a woven cloth. Thus, bonding specificity of DNA provides an effective route to generate new nano-networked materials with polyamorphic behavior. The concept of network interpenetration helps to explain the generation of multiple liquid phases in single-component systems, suggested to occur in some atomic and molecular network-forming fluids, including water and silica.
authors.affiliation: Department of Physics, Wesleyan University, Middletown, CT 06459, USA.
authors.forename: Chia Wei
authors.initials: CW
authors.lastname: Hsu
authors.forename: Julio
authors.initials: J
authors.lastname: Largo
authors.forename: Francesco
authors.initials: F
authors.lastname: Sciortino
authors.forename: Francis W
authors.initials: FW
authors.lastname: Starr
mesh_terms: D004247:DNA / Q000737:chemistry; D050091:Dendrimers / Q000737:chemistry; D008958:Models, Molecular; D044367:Phase Transition
chemical_list: D050091:Dendrimers; D004247:DNA
references.citation: Proc Natl Acad Sci U S A. 2005 Nov 15;102(46):16558-62
references.pmid: 16267132
references.citation: Phys Rev E Stat Phys Plasmas Fluids Relat Interdiscip Topics. 2000 Jul;62(1 Pt A):73-6
references.pmid: 11088436
references.citation: Phys Rev E Stat Nonlin Soft Matter Phys. 2004 Dec;70(6 Pt 1):061507
references.pmid: 15697374
references.citation: Phys Rev E Stat Phys Plasmas Fluids Relat Interdiscip Topics. 1999 Jul;60(1):1084-7
references.pmid: 11969860
references.citation: J Am Chem Soc. 2004 Feb 25;126(7):2050-7
references.pmid: 14971939
references.citation: Phys Rev E Stat Nonlin Soft Matter Phys. 2007 Jul;76(1 Pt 1):011402
references.pmid: 17677436
references.citation: Curr Opin Chem Biol. 2000 Dec;4(6):609-18
references.pmid: 11102864
references.citation: Nature. 2008 Jan 31;451(7178):553-6
references.pmid: 18235497
references.citation: Phys Rev Lett. 2005 Jul 22;95(4):046101
references.pmid: 16090823
references.citation: J Phys Condens Matter. 2006 Jul 5;18(26):L347-53
references.pmid: 21690795
references.citation: Nature. 2003 Jan 23;421(6921):427-31
references.pmid: 12540916
references.citation: Nature. 2000 Jan 13;403(6766):170-3
references.pmid: 10646596
references.citation: J Chem Phys. 2005 Jul 22;123(4):044515
references.pmid: 16095377
references.citation: Nature. 2001 Feb 8;409(6821):692-5
references.pmid: 11217853
references.citation: Nat Mater. 2007 Aug;6(8):557-62
references.pmid: 17667968
references.citation: Proc Natl Acad Sci U S A. 2005 Mar 22;102(12):4225-9
references.pmid: 15758072
references.citation: Phys Rev E Stat Nonlin Soft Matter Phys. 2006 Sep;74(3 Pt 1):031108
references.pmid: 17025595
references.citation: Langmuir. 2007 May 22;23(11):5896-905
references.pmid: 17439252
references.citation: Nature. 1996 Aug 15;382(6592):607-9
references.pmid: 8757129
references.citation: Phys Rev Lett. 2005 Feb 11;94(5):058302
references.pmid: 15783705
references.citation: Nat Mater. 2006 Feb;5(2):85-6
references.pmid: 16449989
references.citation: Nat Mater. 2003 Nov;2(11):739-43
references.pmid: 14556000
references.citation: Nature. 1998 Aug 6;394(6693):539-44
references.pmid: 9707114
references.citation: Phys Rev Lett. 2005 Jun 3;94(21):218301
references.pmid: 16090355
references.citation: Nat Rev Genet. 2006 Jul;7(7):565-75
references.pmid: 16770339
references.citation: Nature. 2008 Jan 31;451(7178):549-52
references.pmid: 18235496