Studying Nanoparticle/cell and Nanoparticle/biosurface Interaction with Mass Spectrometry

Nanoparticles (NPs) have been used widely in various fields ranging from biomedical applications to life science due to their highly tunable properties. It is essential to understanding how NPs interact with biological systems of interest, therefore, analytical platforms to efficiently track NPs from cell to animal level are essential. In this thesis, laser desorption ionization mass spectrometry (LDI-MS) and inductively-coupled plasma mass spectrometry (ICP-MS) has been developed and applied to quantify NP/cell and NP/biological surface interactions. These two methods provide fast, label-free and quantitative analysis. New capability of LDI-MS to differentiate cell surface-bound and internalized NPs were established and ICP-MS coupled with a library of surface- functionalized AuNPs were used to probe the affinity between NPs and human hair surface. NPs interacting with biological surfaces and plasma membrane were quantified and the interactions were controlled by the chemical properties of the interface between NP and biological systems

Solvent-Free Electrolyte for High-Temperature Rechargeable Lithium Metal Batteries

The formation of lithiophobic inorganic solid electrolyte interphase (SEI) on Li anode and cathode electrolyte interphase (CEI) on the cathode is beneficial for high-voltage Li metal batteries. However, in most liquid electrolytes, the decomposition of organic solvents inevitably forms organic components in the SEI and CEI. In addition, organic solvents often pose substantial safety risks due to their high volatility and flammability. Herein, an organic-solvent-free eutectic electrolyte based on low-melting alkali perfluorinated-sulfonimide salts is reported. The exclusive anion reduction on Li anode surface results in an inorganic, LiF-rich SEI with high capability to suppress Li dendrite, as evidenced by the high Li plating/stripping CE of 99.4% at 0.5 mA cm−2 and 1.0 mAh cm−2, and 200-cycle lifespan of full LiNi0.8Co0.15Al0.05O2 (2.0 mAh cm−2) || Li (20 µm) cells at 80 °C. The proposed eutectic electrolyte is promising for ultrasafe and high-energy Li metal batteries

ELECTROLYTE DESIGN FOR HIGH-ENERGY METAL BATTERIES

The demand for advanced batteries surged in the past decade because they are at the heart of several tactically important technologies, such as renewable electrification grids and electric vehicles (EVs). These technologies will progressively transform our energy consumption structure toward sustainability and alleviate the global climate crisis. Unlike consumer electronics, EVs require batteries with larger energy storage to avoid "range anxiety". According to the US Advanced Battery Consortium (USABC), breakthroughs are needed to double the battery energy density and reduce the price by 50% for EVs to be competitive in the automobile market. These stringent requirements are unlikely to be met by the Li-ion batteries (LIBs) because the charge storage limits have been reached. Metal batteries using metals as anodes require no host materials and have up to ten times higher charge storage capacities. When metals with low redox potentials (Mg, Ca, and Li) are used, new battery systems that benefit from larger capacities and high cell voltages result in over 100 % leap in energy density to satisfy the USABC's goals for EV applications. On the other hand, the scarcity of materials related to LIBs raises uncertainties and doubts in the transition to electric transportation. Metals such as Mg and Ca are highly abundant in the earth crust, which potentially ensures the reliability of the energy supply in the future.Despite the exciting prospects of metal batteries, there are knowledge gaps in understanding how the electrolyte changes the behaviors of metal plating/stripping. Although electrolytes are considered inert materials in batteries, they are indispensable in maintaining ionic transport, modulating interfacial reaction kinetics, and maintaining reversible electrode reactions through the formation of solid-electrolyte interphase (SEI). In this dissertation, I detailed our efforts to establish the microscopic understanding of the electrolyte structures, SEI components, nucleation, and growth of the electroplated metal with spectroscopic techniques and physical models. These understandings guided the design of electrolytes for reversible metal anodes in practical high-energy battery applications

Electrochemical nanoparticle-enzyme sensors for screening bacterial contamination in drinking water.

Traditional plating and culturing methods used to quantify bacteria commonly require hours to days from sampling to results. We present here a simple, sensitive and rapid electrochemical method for bacterial detection in drinking water based on gold nanoparticle-enzyme complexes. The gold nanoparticles were functionalized with positively charged quaternary amine headgroups that could bind to enzymes through electrostatic interactions, resulting in inhibition of enzymatic activity. In the presence of bacteria, the nanoparticles were released from the enzymes and preferentially bound to the bacteria, resulting in an increase in enzyme activity, releasing a redox-active phenol from the substrate. We employed this strategy for the electrochemical sensing of Escherichia coli and Staphylococcus aureus, resulting in a rapid detection (<1 h) with high sensitivity (10(2) CFU mL(-1))

Immunomodulatory Effects of Coated Gold Nanoparticles in LPS-Stimulated In Vitro and In Vivo Murine Model Systems

The ability of nanoparticle surface functionalities to regulate immune responses during an immunological challenge (i. e. inflammation) would open new doors for their use in non-prophylactic therapeutics. We report here the use of functionalized 2 nm core gold nanoparticles to control the immunological responses of in vitro and in vivo systems presented with an inflammatory challenge. The results showed that NPs bearing a hydrophobic zwitterionic functionality boost inflammatory outcomes while hydrophilic zwitterionic NPs generate minimal immunological responses. Surprisingly, tetra(ethylene glycol) headgroups generate a significant anti-inflammatory response both in vitro and in vivo. These results demonstrate the ability of simple surface ligands to provide immunomodulatory properties, making them promising leads for the therapeutic usage of nanomaterials in diseases involving inflammation

Zwitterionic Ligands Bound to Cdse/Zns Quantum Dots Prevent Adhesion to Mammalian Cells

<div><p></p><p>Zwitterionic materials are useful tools in material science and biology as they provide high water solubility while preventing nonspecific interactions. Quantum dots (QDs) functionalized with zwitterionic and quaternary ammonium ligands were synthesized to investigate their interactions with the outer membrane of HeLa cells. Quaternary ammonium functionalized quantum dots adhered strongly to the cell surface while zwitterionic QDs had no cell adhesion. These results demonstrate that future noninteracting nanoparticles based on this design are possible.</p></div

Solvent-Free Electrolyte for High-Temperature Rechargeable Lithium Metal Batteries

The formation of lithiophobic inorganic solid electrolyte interphase (SEI) on Li anode and cathode electrolyte interphase (CEI) on the cathode is beneficial for high-voltage Li metal batteries. However, in most liquid electrolytes, the decomposition of organic solvents inevitably forms organic components in the SEI and CEI. In addition, organic solvents often pose substantial safety risks due to their high volatility and flammability. Herein, an organic-solvent-free eutectic electrolyte based on low-melting alkali perfluorinated-sulfonimide salts is reported. The exclusive anion reduction on Li anode surface results in an inorganic, LiF-rich SEI with high capability to suppress Li dendrite, as evidenced by the high Li plating/stripping CE of 99.4% at 0.5 mA cm−2 and 1.0 mAh cm−2, and 200-cycle lifespan of full LiNi0.8Co0.15Al0.05O2 (2.0 mAh cm−2) || Li (20 µm) cells at 80 °C. The proposed eutectic electrolyte is promising for ultrasafe and high-energy Li metal batteries.https://doi.org/10.1002/adfm.20230117

High-energy and low-cost membrane-free chlorine flow battery

Partial funding for Open Access provided by the UMD Libraries' Open Access Publishing Fund.Grid-scale energy storage is essential for reliable electricity transmission and renewable energy integration. Redox flow batteries (RFB) provide affordable and scalable solutions for stationary energy storage. However, most of the current RFB chemistries are based on expensive transition metal ions or synthetic organics. Here, we report a reversible chlorine redox flow battery starting from the electrolysis of aqueous NaCl electrolyte and the as-produced Cl2 is extracted and stored in the carbon tetrachloride (CCl4) or mineral spirit flow. The immiscibility between the CCl4 or mineral spirit and NaCl electrolyte enables a membrane-free design with an energy efficiency of >91% at 10 mA/cm2 and an energy density of 125.7 Wh/L. The chlorine flow battery can meet the stringent price and reliability target for stationary energy storage with the inherently low-cost active materials (~$5/kWh) and the highly reversible Cl2/Cl− redox reaction.https://doi.org/10.1038/s41467-022-28880-

Salt-in-Salt Reinforced Carbonate Electrolyte for Li Metal Batteries

The instability of carbonate electrolyte with metallic Li greatly limits its application in high-voltage Li metal batteries. Here, a “salt-in-salt” strategy is applied to boost the LiNO3 solubility in the carbonate electrolyte with Mg(TFSI)2 carrier, which enables the inorganic-rich solid electrolyte interphase (SEI) for excellent Li metal anode performance and also maintains the cathode stability. In the designed electrolyte, both NO3− and PF6− anions participate in the Li+-solvent complexes, thus promoting the formation of inorganic-rich SEI. Our designed electrolyte has achieved a superior Li CE of 99.7 %, enabling the high-loading NCM811||Li (4.5 mAh cm−2) full cell with N/P ratio of 1.92 to achieve 84.6 % capacity retention after 200 cycles. The enhancement of LiNO3 solubility by divalent salts is universal, which will also inspire the electrolyte design for other metal batteries.https://doi.org/10.1002/anie.20221052

High-Performance All-Solid-State Na–S Battery Enabled by Casting–Annealing Technology

Room-temperature all-solid-state Na–S batteries (ASNSBs) using sulfide solid electrolytes are a promising next-generation battery technology due to the high energy, enhanced safety, and earth abundant resources of both sodium and sulfur. Currently, the sulfide electrolyte ASNSBs are fabricated by a simple cold-pressing process leaving with high residential stress. Even worse, the large volume change of S/Na₂S during charge/discharge cycles induces additional stress, seriously weakening the less-contacted interfaces among the solid electrolyte, active materials, and the electron conductive agent that are formed in the cold-pressing process. The high and continuous increase of the interface resistance hindered its practical application. Herein, we significantly reduce the interface resistance and eliminate the residential stress in Na₂S cathodes by fabricating Na₂S-Na₃PS₄-CMK-3 nanocomposites using melting-casting followed by stress-release annealing-precipitation process. The casting–annealing process guarantees the close contact between the Na₃PS₄ solid electrolyte and the CMK-3 mesoporous carbon in mixed ionic/electronic conductive matrix, while the <i>in situ</i> precipitated Na₂S active species from the solid electrolyte during the annealing process guarantees the interfacial contact among these three subcomponents without residential stress, which greatly reduces the interfacial resistance and enhances the electrochemical performance. The <i>in situ</i> synthesized Na₂S-Na₃PS₄-CMK-3 composite cathode delivers a stable and highly reversible capacity of 810 mAh/g at 50 mA/g for 50 cycles at 60 °C. The present casting–annealing strategy should provide opportunities for the advancement of mechanically robust and high-performance next-generation ASNSBs