Thiol Coordination Softens Liquid Metal Particles To Improve On-Demand Conductivity.

Achieving tunable rupturing of eutectic gallium indium (EGaIn) particles holds great significance in flexible electronic applications, particularly pressure sensors. We tune the mechanosensitivity of EGaIn particles by preparing them in toluene with thiol surfactants and demonstrate an improvement over typical preparations in ethanol. We observe, across multiple length scales, that thiol surfactants and the nonpolar solvent synergistically reduce the applied stress requirements for electromechanical actuation. At the nanoscale, dodecanethiol and propanethiol in toluene suppress gallium oxide growth, as characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. Quantitative AFM imaging produces force-indentation curves and height images, while conductive AFM measures current while probing individual EGaIn particles. As the applied force increases, thiolated particles demonstrate intensified softening, rupturing, and stress-induced electrical activation at forces 40% lower than those for bare particles in ethanol. To confirm that thiolation facilitates rupturing at the macroscale, a laser is used to ablate samples of EGaIn particles. Scanning electron microscopy and resistance measurements across macroscopic samples confirm that thiolated EGaIn particles coalesce to exhibit electrical activation at 0.1 W. Particles prepared in ethanol, however, require 3 times higher laser power to demonstrate a similar behavior. This unique collection of advanced techniques demonstrates that our particle synthesis conditions can facilitate on-demand functionality to benefit electronic applications.

Low-Cost, High-Pressure-Synthesized Oxygen-Entrapping Materials to Improve Treatment of Solid Tumors.

Tumor hypoxia drives resistance to many cancer therapies, including radiotherapy and chemotherapy. Methods that increase tumor oxygen pressures, such as hyperbaric oxygen therapy and microbubble infusion, are utilized to improve the responses to current standard-of-care therapies. However, key obstacles remain, in particular delivery of oxygen at the appropriate dose and with optimal pharmacokinetics. Toward overcoming these hurdles, gas-entrapping materials (GeMs) that are capable of tunable oxygen release are formulated. It is shown that injection or implantation of these materials into tumors can mitigate tumor hypoxia by delivering oxygen locally and that these GeMs enhance responsiveness to radiation and chemotherapy in multiple tumor types. This paper also demonstrates, by comparing an oxygen (O2 )-GeM to a sham GeM, that the former generates an antitumorigenic and immunogenic tumor microenvironment in malignant peripheral nerve sheath tumors. Collectively the results indicate that the use of O2 -GeMs is promising as an adjunctive strategy for the treatment of solid tumors.

Takes Two to Tango: Choreography of the Coadsorption of CTAB and Hexanol at the Oil-Water Interface.

Mixed surfactant systems at the oil-water interface play a vital role in applications ranging widely from drug delivery to oil-spill remediation. Synergistic mixtures are superior emulsifiers and more effective at modifying surface tension than either component alone. Mixtures of surfactants with dissimilar polar head groups are of particular interest because of the additional degree of control they offer. The interplay of hydrophobic and electrostatic effects in these systems is not well understood, in part because of the difficulty in examining their behavior at the buried oil-water interface where they reside. Here, surface-specific vibrational sum frequency spectroscopy is utilized in combination with surface tensiometry and computational methods to probe the cooperative molecular interactions between a cationic surfactant cetyltrimethylammonium bromide (CTAB) and a nonionic alcohol (1-hexanol) that induce the two initially reluctant surfactants to coadsorb synergistically at the interface. A careful deuteration study of CTAB reveals that hexanol cooperates with CTAB such that both molecules preferentially orient at the interface for sufficiently large enough concentrations of hexanol. This work's methodology is unique and serves as a guide for future explorations of macroscopic properties in these complex systems. Results from this work also provide valuable insights into how interfacial ordering impacts surface tensiometry measurements for nonionic surfactants.