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Title: Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent

Abstract

Here, many applications of deep eutectic solvents (DES) rely on exploitation of their unique yet complex liquid structures. Due to the ionic nature of the DES components, their diffuse structures are perturbed in the presence of a charged surface. We hypothesize that it is possible to perturb the bulk DES structure far (> 100 nm) from a curved, charged surface with mesoscopic dimensions. We performed in situ, synchrotron-based ultra-small angle X-ray scattering (USAXS) experiments to study the solvent distribution near the surface of charged mesoporous silica particles (MPS) (≈ 0.5 µm in diameter) suspended in both water and a common type of DES (1:2 choline Cl-:ethylene glycol). A careful USAXS analysis reveals that the perturbation of electron density distribution within the DES extends ≈ 1 μm beyond the particle surface, and that this perturbation can be manipulated by the addition of salt ions (AgCl). The concentration of the pore-filling fluid is greatly reduced in the DES. Notably, we extracted the real-space structures of these fluctuations from the USAXS data using a simulated annealing approach that does not require a priori knowledge about the scattering form factor, and can be generalized to a wide range of complex small-angle scattering problems.

Authors:
 [1];  [2];  [3]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1466360
Alternate Identifier(s):
OSTI ID: 1769113
Report Number(s):
LLNL-JRNL-735609
Journal ID: ISSN 0021-9797; 140715
Grant/Contract Number:  
AC02-06CH11357; AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Colloid and Interface Science
Additional Journal Information:
Journal Volume: 520; Journal Issue: C; Journal ID: ISSN 0021-9797
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Electrostatic stabilization; Deep eutectic solvents; Pore activity; Nanoparticle stabilization; Small angle scattering; Mesoporous silica; Drug delivery; Green technology; Meso-scale solvent fluctuations; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hammons, Joshua A., Zhang, Fan, and Ilavsky, Jan. Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent. United States: N. p., 2018. Web. doi:10.1016/j.jcis.2018.02.078.
Hammons, Joshua A., Zhang, Fan, & Ilavsky, Jan. Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent. United States. https://doi.org/10.1016/j.jcis.2018.02.078
Hammons, Joshua A., Zhang, Fan, and Ilavsky, Jan. Sat . "Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent". United States. https://doi.org/10.1016/j.jcis.2018.02.078. https://www.osti.gov/servlets/purl/1466360.
@article{osti_1466360,
title = {Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent},
author = {Hammons, Joshua A. and Zhang, Fan and Ilavsky, Jan},
abstractNote = {Here, many applications of deep eutectic solvents (DES) rely on exploitation of their unique yet complex liquid structures. Due to the ionic nature of the DES components, their diffuse structures are perturbed in the presence of a charged surface. We hypothesize that it is possible to perturb the bulk DES structure far (> 100 nm) from a curved, charged surface with mesoscopic dimensions. We performed in situ, synchrotron-based ultra-small angle X-ray scattering (USAXS) experiments to study the solvent distribution near the surface of charged mesoporous silica particles (MPS) (≈ 0.5 µm in diameter) suspended in both water and a common type of DES (1:2 choline Cl-:ethylene glycol). A careful USAXS analysis reveals that the perturbation of electron density distribution within the DES extends ≈ 1 μm beyond the particle surface, and that this perturbation can be manipulated by the addition of salt ions (AgCl). The concentration of the pore-filling fluid is greatly reduced in the DES. Notably, we extracted the real-space structures of these fluctuations from the USAXS data using a simulated annealing approach that does not require a priori knowledge about the scattering form factor, and can be generalized to a wide range of complex small-angle scattering problems.},
doi = {10.1016/j.jcis.2018.02.078},
journal = {Journal of Colloid and Interface Science},
number = C,
volume = 520,
place = {United States},
year = {2018},
month = {3}
}

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Figures / Tables:

Table 1 Table 1: Physical parameter of MPS obtained via least-squares fitting of the scattering profiles of MPS in H2O suspensions. The mathematically formulations are described by Eqns. (3) – (9). The uncertainties were acquired from the Jacobian matrix during the least-squares fitting. Modeling of the weakest signal data (νp = 1%)more » required that some parameters be held constant. these parameters are denoted with a “*” symbol.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.