title: Highly robust crystalsome via directed polymer crystallization at curved liquid/liquid interface.
abstract: Lipids and amphiphilic block copolymers spontaneously self-assemble in water to form a plethora of micelles and vesicles. They are typically fluidic in nature and often mechanically weak for applications such as drug delivery and gene therapeutics. Mechanical properties of polymeric materials could be improved by forming crystalline structures. However, most of the self-assembled micelles and vesicles have curved surfaces and precisely tuning crystallization within a nanoscale curved space is challenging, as the curved geometry is incommensurate with crystals having three-dimensional translational symmetry. Herein, we report using a miniemulsion crystallization method to grow nanosized, polymer single-crystal-like capsules. We coin the name crystalsome to describe this unique structure, because they are formed by polymer lamellar crystals and their structure mimics liposomes and polymersomes. Using poly(L-lactic acid) (PLLA) as the model polymer, we show that curved water/p-xylene interface formed by the miniemulsion process can guide the growth of PLLA single crystals. Crystalsomes with the size ranging from ∼148 nm to over 1 μm have been formed. Atomic force microscopy measurement demonstrate a two to three orders of magnitude increase in bending modulus compared with conventional polymersomes. We envisage that this novel structure could shed light on investigating spherical crystallography and drug delivery.
authors.affiliation: Department of Materials Science and Engineering, Drexel University, 3141 Chestnut Street, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Wenda
authors.initials: W
authors.lastname: Wang
authors.affiliation: Department of Materials Science and Engineering, Drexel University, 3141 Chestnut Street, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Hao
authors.initials: H
authors.lastname: Qi
authors.affiliation: Department of Materials Science and Engineering, Drexel University, 3141 Chestnut Street, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Tian
authors.initials: T
authors.lastname: Zhou
authors.affiliation: Department of Materials Science and Engineering, Drexel University, 3141 Chestnut Street, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Shan
authors.initials: S
authors.lastname: Mei
authors.affiliation: School of Biomedical Engineering, Science and Health Systems, Drexel University, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Lin
authors.identifier: http://orcid.org/0000-0003-4180-1288
authors.initials: L
authors.lastname: Han
authors.affiliation: Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai 980-8577, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Higuchi
authors.affiliation: Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai 980-8577, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Jinnai
authors.affiliation: Department of Materials Science and Engineering, Drexel University, 3141 Chestnut Street, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Christopher Y
authors.initials: CY
authors.lastname: Li
references.citation: J Phys Chem Lett. 2011 Jul 7;2(13):1612-1623
references.pmid: 22110844
references.citation: ACS Macro Lett. 2014 Feb 18;3(2):175-179
references.pmid: 35590500
references.citation: Soft Matter. 2007 Jul 17;3(8):945-955
references.pmid: 32900043
references.citation: Langmuir. 2013 Aug 6;29(31):9814-23
references.pmid: 23886008
references.citation: Angew Chem Int Ed Engl. 2009;48(25):4488-507
references.pmid: 19455531
references.citation: Macromolecules. 2006 Mar 7;39(5):1673-1675
references.pmid: 20975926
references.citation: Chem Commun (Camb). 2013 Dec 21;49(98):11521-3
references.pmid: 24175314
references.citation: Chem Soc Rev. 2006 Nov;35(11):1068-83
references.pmid: 17057836
references.citation: Soft Matter. 2007 Sep 19;3(10):1231-1248
references.pmid: 32900090
references.citation: Proc R Soc Lond B Biol Sci. 1972 Jul 25;182(1066):89-102
references.pmid: 4403086
references.citation: Langmuir. 2012 Aug 28;28(34):12629-36
references.pmid: 22860888
references.citation: Soft Matter. 2015 Feb 7;11(5):898-907
references.pmid: 25491780
references.citation: Biomacromolecules. 2003 Sep-Oct;4(5):1301-7
references.pmid: 12959598
references.citation: Science. 1999 May 14;284(5417):1143-6
references.pmid: 10325219
references.citation: J Mech Behav Biomed Mater. 2013 Feb;18:20-8
references.pmid: 23237877
references.citation: Acc Chem Res. 2011 Oct 18;44(10):1039-49
references.pmid: 21608994
references.citation: Science. 2003 Mar 14;299(5613):1716-8
references.pmid: 12637740
references.citation: Science. 2002 Aug 9;297(5583):967-73
references.pmid: 12169723
references.citation: Ultramicroscopy. 1988;24(1):7-18
references.pmid: 3344552
references.citation: Science. 2002 Nov 1;298(5595):1006-9
references.pmid: 12411700
references.citation: Macromolecules. 2010 Dec 14;43(23):9736-9746
references.pmid: 21499509
references.citation: J Am Chem Soc. 2010 Aug 4;132(30):10256-9
references.pmid: 20662505
references.citation: Microscopy (Oxf). 2013 Apr;62(2):243-58
references.pmid: 23183966