skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Polyethylene nano crystalsomes formed at a curved liquid/liquid interface
Crystallization is incommensurate with nanoscale curved space due to the lack of three dimensional translational symmetry of the latter. Herein, we report the formation of single-crystal-like, nanosized polyethylene (PE) capsules using a miniemulsion solution crystallization method. The miniemulsion was formed at elevated temperatures using PE organic solution as the oil phase and sodium dodecyl sulfate as the surfactant. Subsequently, cooling the system stepwisely for controlled crystallization led to the formation of hollow, nanosized PE crystalline capsules, which are named as crystalsomes since they mimic the classical self-assembled structures such as liposome, polymersome and colloidosome. We show that the formation of the nanosized PE crystalsomes is driven by controlled crystallization at the curved liquid/liquid interface of the miniemulson droplet. The morphology, structure and mechanical properties of the PE crystalsomes were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and atomic force spectroscopy. Electron diffraction showed the single-crystal-like nature of the crystalsomes. The incommensurateness between the nanocurved interface and the crystalline packing led to reduced crystallinity and crystallite size of the PE crystalsome, as observed from the X-ray diffraction measurements. Moreover, directly quenching the emulsion below the spinodal line led to the formation of hierarchical porous PE crystalsomes due to the coupling of the PE crystallization and liquid/liquid phase separation. We anticipate that this unique crystalsome represents a new type of nanostructure that might be used as nanodrug carriers and ultrasound contrast agents.  more » « less
Award ID(s):
1709136
PAR ID:
10058386
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Nanoscale
Volume:
10
Issue:
1
ISSN:
2040-3364
Page Range / eLocation ID:
268 to 276
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; (, Macromolecular Rapid Communications)
    Abstract Polymer crystalsomes are a class of hollow crystalline polymer nanoparticles with shells formed by single crystals with broken translational symmetry. They have shown intriguing mechanical, thermal, and biomedical properties associated with spherical packing. Previously reported crystalsomes are formed by quasi‐2D lamellae which can readily tile on a spherical surface. In this work, the formation of polymer crystalsomes formed by 1D polymer crystals is reported. Poly (3‐hexylthiophene) (P3HT) is chosen as the model polymer because of its 1D growth habit. P3HT crystalsomes are successfully fabricated using a miniemulsion solution crystallization method, as confirmed by scanning electron microscopy and transmission electron microscopy. X‐ray diffraction (XRD) and selected area electron diffraction experiments confirm that P3HT crystallized into a Form I crystal structure. XRD, differential scanning calorimetry and UV–Vis results reveal curvature‐dependent structural, thermal and electro‐optical properties. 
    more » « less
  2. ; (, Journal of the American Chemical Society)
    Electrosynthesis of single-crystalline metallic and intermetallic particles with a preferred orientation onto liquid metal electrodes has been performed. Liquid gallium electrodes immersed in aqueous alkaline electrolytes without any molecular additive or external solid seeding substrates were used to electroreduce separately Pb2+, Bi3+, Pd2+, and Mn2+. The crystallinity, composition, and orientation of the electrodeposition products were characterized by using scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, grazing incidence X-ray diffraction, and energy-dispersive X-ray spectroscopy. Electrodeposition of Pb and Bi results in the incipient formation of two-dimensional (2D) nuclei that subsequently direct the growth of Pb and Bi single crystals along the most close-packed [111] and [0001] directions, respectively. The absence of any intervening surface oxides and a low electroreduction flux are necessary to avoid polycrystalline dendrite formation. Under comparable conditions, the electrodeposition of Pd and Mn results in single-crystalline intermetallic particles at the interface. Each crystal exhibits a preferred orientation consistent with the unique atomic packing of the near-surface region of the liquid Ga. The presented study suggests a new concept in electrodeposition processes where the liquid metal structure imparts quasi-epitaxial growth in a system in which the electrode material specifically has no crystallinity or long-range order. This study is thus the first demonstration of highly oriented electrodeposition at a liquid/liquid interface under ambient conditions, highlighting the unique solvation environment of liquid metal interfaces for forming thin metallic and intermetallic films. 
    more » « less
  3. ; ; (, ChemElectroChem)
    Abstract Synthesis of intermetallic crystals by electrodeposition of Ag from alkaline aqueous electrolytes containing AgCN onto liquid metal electrodes via an electrochemical liquid‐liquid‐solid (ec‐LLS) process has been performed. X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy were performed to identify crystalline products. Ec‐LLS experiments performed with pure liquid Hg and Ga electrodes resulted in the formation of polycrystalline Ag2Ga and Ag2Hg3. Experiments performed with In‐containing liquid metals preferentially yielded Ag9In4and AgIn2products with liquid Hg0.35In0.65and Ga0.86In0.14, respectively. The product distribution with liquid Hg0.35In0.65depended on the level of Ag supersaturation during the electrodeposition. A mechanism that accounts for the aforementioned observations is presented and discussed. This work described the formation of Ag−In intermetallic phases by the isothermal electroreduction of Ag into different liquid metal solvents via ec‐LLS. Electrodeposition of Ag into a pure Ga or pure Hg liquid metal pool yielded precisely the compounds predicted from isothermal cross‐sections of the respective binary phase diagrams. These compounds were not found when using liquid Hg or Ga containing appreciable In. The smaller enthalpy of formation for AgIn2was consistent with its synthesis in Ga0.86In0.14. However, the observed product of Ag9In4in Hg‐containing liquid metals could not be rationalized solely from thermodynamic factors. Instead, this observation was consistent with a kinetic pathway based on the lability of Hg‐metal bonds and nearly identical crystal structures of Ag9In4and Ag2Hg3. Site exchange of Hg for In is consistent with our prior observations[23]of In exchange into Hg−Pd structures during Pd electrodeposition. This mechanism is not based on any direct role of electrochemistry other than aspects that dictate the operative supersaturation of the metal solute. 
    more » « less
  4. ; (, Journal of The Electrochemical Society)
    Electrodeposition of Pd from alkaline baths containing Pd(CN) 2 and KCN with liquid metal electrodes has been performed. Data are presented that Pd dissolved into and reacted with the liquid metal electrodes via an electrochemical liquid-liquid-solid (ec-LLS) process. HgPd crystals were obtained with liquid Hg electrodes. On solid In electrodes, In 7 Pd 3 was exclusively formed. In contrast, InPd was the primary product with Hg 1-x In x alloy electrodes. X-ray diffraction, scanning electron microscopy, and electron backscattering diffraction show that the materials were not a pure phase, as minor components of HgPd and In 7 Pd 3 were observed for various liquid Hg-In compositions. A mechanism is proposed where the InPd intermetallic forms through an intermediate phase of HgPd by the substitution of In atoms for the Hg sites of the unit cell. This study thus motivates further exploration of Hg 1-x In x as a versatile medium for intermetallic synthesis by ec-LLS. 
    more » « less
  5. ; (, Macromolecular Chemistry and Physics)
    Abstract Spherical crystals are ubiquitous in nature and the necessary breaks in translational symmetry not seen in flat crystals render them structurally unique. Polymer crystals have been shown to exhibit nonflat morphologies, but control over their formation is difficult to achieve. One strategy is directing the crystallization by spatially and/or temporally tuning chain segmental mobility. This has been studied early on using polymer blends or polymer/solvent systems where coupling liquid–liquid phase separation with crystallization could provide morphological control. In this Trend article, a recent trend in using miniemulsion systems to act as nanoscale confinement on chain segmental mobility is reviewed. The confinement at this length scale causes unique features to arise in ordering processes such as liquid–liquid phase separation and crystallization that are not observed at the macroscale. The generality of this approach makes it a good candidate to direct the formation of new and unique hierarchical polymer nanostructures that could be utilized in numerous applications. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email