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We report the effect of neutral macromolecular crowders poly(ethylene glycol) (PEG) (8 kDa) and Ficoll (70 kDa) on liquid–liquid phase separation in a polyuridylic acid (polyU)/spermine complex coacervate system. The addition of PEG decreased both the amount of spermine required for phase separation and the coacervation temperature ( T C ). We interpret these effects on phase behavior as arising due to excluded volume and preferential interactions on both the secondary structure/condensation of spermine-associated polyU molecules and on the association of soluble polyU/spermine polyelectrolyte complexes to form coacervate droplets. Examination of coacervates formed in the presence of fluorescently-labeled PEG or Ficoll crowders indicated that Ficoll is accumulated while PEG is excluded from the coacervate phase, which provides further insight into the differences in phase behavior. Crowding agents impact distribution of a biomolecular solute: partitioning of a fluorescently-labeled U15 RNA oligomer into the polyU/spermine coacervates was increased approximately two-fold by 20 wt% Ficoll 70 kDa and by more than two orders of magnitude by 20 wt% PEG 8 kDa. The volume of the coacervate phase decreased in the presence of crowder relative to a dilute buffer solution. These findings indicate that potential impacts of macromolecular crowding on phase behavior and solute partitioning should be considered in model systems for intracellular membraneless organelles.
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Controlled Molecular Assembly of Tetrazine Derivatives on Surfaces
While self-assembly is relatively well-known and widely used to form hierarchical structures and thin film coatings, controlled assembly is less known and utilized. Our prior work has demonstrated the concept of controlled assembly of macromolecules such as star polymers (MW ~383 kDa, hydrodynamic radius R ~ 13.8 nm) in droplets. The present work extends this concept to smaller molecules, in this case, poly(ethylene glycol) bis-tetrazine (PEG-bisTz, Mn 8.1 kDa, R ~1.5 nm). The key to control molecular assembly is to first deliver ultrasmall volumes (sub-fL) of solution containing PEG-bisTz to a substrate. The solvent evaporates rapidly due to the minute volume, thus forcing the assembly of solute, whose overall size and dimension are dictated by the initial liquid geometry and size. Using pre-patterned surfaces, this work revealed that the initial liquid shape can be further tuned, and as such we could control the final assembly of solute such as PEG-bisTz molecules. The degree of control is demonstrated by varying the micropatterns and delivery conditions. This work demonstrates the validity of controlled assembly for PEG-bisTz, and as such enables 3D nanoprinting of functional materials. The technology has promising applications in nanophotonics, nanoelectronics, nanocomposite materials, and tissue engineering.
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- Award ID(s):
- 1808829
- PAR ID:
- 10285372
- Editor(s):
- Zhang, Xi
- Date Published:
- Journal Name:
- CCS Chemistry
- Volume:
- 3
- ISSN:
- 2096-5745
- Page Range / eLocation ID:
- 1789 to 1799
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.31635/ccschem.021.202101088
