skip to main content


Title: Controlling Surfactant Adsorption on Highly Charged Nanoparticles to Stabilize Bijels
Bicontinuous particle-stabilized emulsions (bijels) are networks of interpenetrating oil/water channels with applications in catalysis, tissue engineering, and energy storage. Bijels can be generated by arresting solvent transfer induced phase separation (STrIPS) via interfacial jamming of nanoparticles. However, until now, STrIPS bijels have only been formed with silica nanoparticles of low surface charge densities, limiting their potential applications in catalysis and fluid transport. Here, we show how strongly charged silica nanoparticles can stabilize bijels. To this end, we carry out a systematic study employing dynamic light scattering, zeta potential, acid/base titrations, turbidimetry, surface tension, and confocal microscopy. We find that moderating the adsorption of oppositely charged surfactants on the particles is crucial to facilitate particle dispersibility in the bijel casting mixture and bijel stabilization. Our results potentially introduce a general understanding for bijel fabrication with different inorganic nanoparticle materials of variable charge density.  more » « less
Award ID(s):
1751479
NSF-PAR ID:
10161210
Author(s) / Creator(s):
Date Published:
Journal Name:
Journal of physical chemistry
Volume:
124
Issue:
23
ISSN:
1932-7455
Page Range / eLocation ID:
12417–12423
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Bicontinuous interfacially jammed emulsion gels (bijels) formed via solvent transfer induced phase separation (STrIPS) are new soft materials with potential applications in separations, healthcare, or catalysis. To facilitate their applications, means to fabricate STrIPS bijels with nanoparticles of various surface chemistries are needed. Here, we investigate the formation of STrIPS bijels with nanoparticles of different wettabilities, ranging from partially hydrophobic to extremely hydrophilic. To this end, the surface wettability of silica nanoparticles is tailored by functionalization with ligands bearing either hydrophobic or hydrophilic terminal groups. We show that partially hydrophobic particles with acrylate groups can impart short-term stability to STrIPS bijels on their own. However, to enable long-term stability, the use of cationic surfactants is needed. Partially hydrophobic particles require short chain surfactants for morphological stability while glycerol-functionalized hydrophilic particles require double chain cationic surfactants. Variation of the surfactant concentration results in various STrIPS bijel morphologies with controllable domain sizes. Last, we show that functional groups on the nanoparticles facilitate interfacial cross-linking for the purposes of reinforcing STrIPS bijels. Our research lays the foundation for the use of a wide variety of solid particles, irrespective of their surface wettabilities, to fabricate bijels with potential applications in Pickering interfacial catalysis and as cross-flow microreactors. 
    more » « less
  2. Porous materials possess numerous useful functions because of their high surface area and ability to modulate the transport of heat, mass, fluids, and electromagnetic waves. Unlike highly ordered structures, disordered porous structures offer the advantages of ease of fabrication and high fault tolerance. Bicontinuous interfacially jammed emulsion gels (bijels) are kinetically trapped disordered biphasic materials that can be converted to porous materials with tunable features. Current methods of bijel fabrication result in domains that are micrometers or larger, and non-uniform in size, limiting their surface area, mechanical strength, and interaction with electromagnetic waves. In this work, scalable synthesis of bijels with uniform and sub-micrometer domains is achieved via a two-step solvent removal process. The resulting bijels are characterized quantitatively to verify the uniformity and sub-micrometer scale of the domains. Moreover, these bijels have structures that resemble the microstructure of the scale of the white beetle Cyphochilus. We find that such bijel films with relatively small thicknesses (<150 μm) exhibit strong solar reflectance as well as high brightness and whiteness in the visible range. Considering their scalability in manufacturing, we believe that VIPS-STRIPS bijels have great potential in large-scale applications including passive cooling, solar cells, and light emitting diodes (LEDs). 
    more » « less
  3. Rationale

    A two‐component matrix of 2‐nitrophloroglucinol (2‐NPG) and silica nanoparticles was used for matrix‐assisted laser desorption ionization (MALDI) mass spectrometry imaging of high‐charge‐state biomolecules in tissue. Potential advantages include increased effective mass range and efficiency of fragmentation.

    Methods

    A mixture of 2‐NPG matrix and silica nanoparticles was applied to cyrosectioned 10 μm thick mouse brain tissue. The mixture was pipetted onto the tissue for profiling and sprayed for tissue imaging. MALDI images were obtained under high vacuum in a commercial time‐of‐flight mass spectrometer.

    Results

    The combined 2‐NPG and nanoparticle matrix produced highly charged ions from tissue with high‐vacuum MALDI. Nanoparticles of 20, 70, 400, and 1000 nm in diameter were tested, the 20 nm particles producing the highest charge states. Images of mouse brain tissue obtained from highly charged ions show similar spatial localization.

    Conclusions

    The combined 2‐NPG and nanoparticle matrix produces highly charged ions from tissue through a mechanism that may rely on the high surface area of the particles which can dry the tissue, and their ability to bind analyte molecules thereby assisting in crystal formation and production of multiply charged ions on laser irradiation.

     
    more » « less
  4. Silica nanomaterials have been studied based on their potential applications in a variety of fields, including biomedicine and agriculture. A number of different molecules have been condensed onto silica nanoparticles’ surfaces to present the surface chemistry needed for a given application. Among those molecules, (3-aminopropyl)triethoxysilane (APS) is one of the most commonly applied silanes used for nanoparticle surface functionalization to achieve charge reversal as well as to enable cargo loading. However, the colloidal stability of APS-functionalized silica nanoparticles has not been thoroughly studied, which can be problematic when the high reactivity of amine groups is considered. In this study, four different types of silica nanoparticles with varied location of added APS have been prepared via a reverse micro emulsion process, and their colloidal stability and dissolution behavior have been investigated. Systematic characterization has been accomplished using transmission electron microscopy (TEM), silicomolybdic acid (SMA) spectrophotometric assay, nitrogen adsorption–desorption surface area measurement, and aerosol ion mobility-mass spectrometry to track the nanoparticles’ physical and chemical changes during dissolution. We find that when APS is on the interior of the silica nanoparticle, it facilitates dissolution, but when APS is condensed both on the interior and exterior, only the exterior siloxane bonds experience catalytic hydrolysis, and the interior dissolution is dramatically suppressed. The observation and analyses that silica nanoparticles show different hydrolysis behaviors dependent on the location of the functional group will be important in future design of silica nanoparticles for specific biomedical and agricultural applications. 
    more » « less
  5. Abstract

    Yolk–shell magnetic mesoporous microspheres exhibit potential applications in biomedicine, bioseparation, and catalysis. Most previous reports focus on establishing various interface assembly strategies to construct yolk–shell mesoporous structures, while little work has been done to control their surface topology and study their relevant applications. Herein, a unique kind of broccoli‐like yolk–shell magnetic mesoporous silica (YS‐BMM) microsphere is fabricated through a surfactant‐free kinetic controlled interface assembly strategy. The obtained YS‐BMM microspheres possess a well‐defined structure consisting of a magnetic core, middle void, mesoporous silica shell with tunable surface roughness, large superparamagnetism (36.4 emu g−1), high specific surface area (174 m2g−1), and large mesopores of 10.9 nm. Thanks to these merits and properties, the YS‐BMM microspheres are demonstrated to be an ideal support for immobilization of ultrafine Pt nanoparticles (≈3.7 nm) and serve as superior nanocatalysts for hydrogenation of 4‐nitrophenol with yield of over 90% and good magnetic recyclability. Furthermore, YS‐BMM microspheres show excellent biocompatibility and can be easily phagocytosed by osteoclasts, revealing a potential candidate in sustained drug release in orthopedic disease therapy.

     
    more » « less