TY - JOUR
T1 - Conjugated Polymer Nanoparticles in Aqueous Media by Assembly with Phospholipids via Dense Alkyl Chain Packing
AU - Choi, Yeol Kyo
AU - Lee, Dabin
AU - Lee, Sang Yup
AU - Shin, Tae Joo
AU - Park, Juhyun
AU - Ahn, Dong June
N1 - Funding Information:
This research was supported by the Korea Research Foundation (Grants NRF-2017R1A2B3006770, 2016M3D1A1952972, and 2016R1D1A1A02937538) and Korea University Grant, Republic of Korea. Experiments at PLS-II 6D and 9A beamlines were supported in part by UCRF, MSIP, and POSTECH. The authors especially thank Dr. Byeongdu Lee at Argonne National Laboratory, who has developed a peak indexing program in the Matlab environment for analyzing GIXD patterns.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/9/12
Y1 - 2017/9/12
N2 - Revealing the nature of chain packing in conjugated polymer nanoparticles (CPNs) is one of the important issues to polymer physics research. Surfactant-stabilized CPNs in water show significantly enhanced luminescence intensity in comparison to small molecular organic dyes and single polymer chains dissolved in solvents. The importance of the conjugated polymer structure in nanomaterials is undoubted. However, details of the relationship between alignment of conjugated polymer backbone in CPNs and its luminescent property have not been established. Furthermore, there are yet no methods that can predict the atom-resolved structure of conjugated polymer in the CPNs. Herein, we employ coarse-grained (CG) molecular dynamic simulations to investigate the structure of phase-separated film and the film shattering process for a mixture of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and 1,2-dioctanoyl-sn-glycero-3-phosphocholine (D8PC). The - stacked structure of PCPDTBT is significantly enhanced when the ratio of D8PC increases in both dried and water exposed film. We also show that the amount of D8PC is at least 2.5 times larger than that of PCPDTBT to wrap the conjugated polymer chain, and the direct retrieval of atomistic details is achieved through back-mapping from the morphology of CG. Finally, we confirmed that conjugated backbones inside the nanoparticles were completely shielded from the aqueous solution by the dense layers of alkyl chains, resulting in remarkably enhanced chain packing. These simulated results are correlated with experimentally observed structure through UV-vis-near-infrared (UV-vis-NIR) spectrometry, scanning electron microscopy (SEM), particle size analyzer (PSA), transmission electron microscopy (TEM), and grazing-incidence X-ray diffraction (GIXD).
AB - Revealing the nature of chain packing in conjugated polymer nanoparticles (CPNs) is one of the important issues to polymer physics research. Surfactant-stabilized CPNs in water show significantly enhanced luminescence intensity in comparison to small molecular organic dyes and single polymer chains dissolved in solvents. The importance of the conjugated polymer structure in nanomaterials is undoubted. However, details of the relationship between alignment of conjugated polymer backbone in CPNs and its luminescent property have not been established. Furthermore, there are yet no methods that can predict the atom-resolved structure of conjugated polymer in the CPNs. Herein, we employ coarse-grained (CG) molecular dynamic simulations to investigate the structure of phase-separated film and the film shattering process for a mixture of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and 1,2-dioctanoyl-sn-glycero-3-phosphocholine (D8PC). The - stacked structure of PCPDTBT is significantly enhanced when the ratio of D8PC increases in both dried and water exposed film. We also show that the amount of D8PC is at least 2.5 times larger than that of PCPDTBT to wrap the conjugated polymer chain, and the direct retrieval of atomistic details is achieved through back-mapping from the morphology of CG. Finally, we confirmed that conjugated backbones inside the nanoparticles were completely shielded from the aqueous solution by the dense layers of alkyl chains, resulting in remarkably enhanced chain packing. These simulated results are correlated with experimentally observed structure through UV-vis-near-infrared (UV-vis-NIR) spectrometry, scanning electron microscopy (SEM), particle size analyzer (PSA), transmission electron microscopy (TEM), and grazing-incidence X-ray diffraction (GIXD).
UR - http://www.scopus.com/inward/record.url?scp=85029364541&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.7b01367
DO - 10.1021/acs.macromol.7b01367
M3 - Article
AN - SCOPUS:85029364541
SN - 0024-9297
VL - 50
SP - 6935
EP - 6944
JO - Macromolecules
JF - Macromolecules
IS - 17
ER -