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1. Lipophilicity of Cationic Ligands Promotes Irreversible Adsorption of Nanoparticles to Lipid Bilayers

   https://doi.org/10.1021/acsnano.0c09732  

   Lochbaum, Christian A. ; Chew, Alex K. ; Zhang, Xianzhi ; Rotello, Vincent ; Van Lehn, Reid C. ; Pedersen, Joel A. ( January 2021 , ACS Nano)

   A mechanistic understanding of the influence of the surface properties of engineered nanomaterials on their interactions with cells is essential for designing materials for applications such as bioimaging and drug delivery as well as for assessing nanomaterial safety. Ligand-coated gold nanoparticles have been widely investigated because their highly tunable surface properties enable investigations into the effect of ligand functionalization on interactions with biological systems. Lipophilic ligands have been linked to adverse biological outcomes through membrane disruption, but the relationship between ligand lipophilicity and membrane interactions is not well understood. Here, we use a library of cationic ligands coated on 2 nm gold nanoparticles to probe the impact of ligand end group lipophilicity on interactions with supported phosphatidylcholine lipid bilayers as a model for cytoplasmic membranes. Nanoparticle adsorption to and desorption from the model membranes were investigated by quartz crystal microbalance with dissipation monitoring. We find that nanoparticle adsorption to model membranes increases with ligand lipophilicity. The effects of ligand structure on gold nanoparticle attachment were further analyzed using atomistic molecular dynamics simulations, which showed that the increase in ligand lipophilicity promotes ligand intercalation into the lipid bilayer. Together, the experimental and simulation results could be described by a two-state modelmore »that accounts for the initial attachment and subsequent conversion to a quasi-irreversibly bound state. We find that only nanoparticles coated with the most lipophilic ligands in our nanoparticle library undergo conversion to the quasi-irreversible state. We propose that the initial attachment is governed by interaction between the ligands and phospholipid tail groups, whereas conversion into the quasi-irreversibly bound state reflects ligand intercalation between phospholipid tail groups and eventual lipid extraction from the bilayer. The systematic variation of ligand lipophilicity enabled us to demonstrate that the lipophilicity of cationic ligands correlates with nanoparticle-bilayer adsorption and suggested that changing the nonpolar ligand R group promotes a mechanism of ligand intercalation into the bilayer associated with irreversible adsorption.« less
2. The role of nanoparticle size and ligand coverage in size focusing of colloidal metal nanoparticles

   https://doi.org/10.1039/c9na00348g  

   Mozaffari, Saeed ; Li, Wenhui ; Dixit, Mudit ; Seifert, Soenke ; Lee, Byeongdu ; Kovarik, Libor ; Mpourmpakis, Giannis ; Karim, Ayman M. ( October 2019 , Nanoscale Advances)

   Controlling the size distribution of nanoparticles is important for many applications and typically involves the use of ligands during synthesis. In this study, we show that the mechanism of size focusing involves a dependence of the growth rate on the size of the nanoparticles and the ligand coverage on the surface of the nanoparticles. To demonstrate these effects, we used in situ small angle X-ray scattering (SAXS) and population balance kinetic modeling (PBM) to investigate the evolution of size distribution during the synthesis of colloidal Pd metal nanoparticles. Despite temporal overlap of nucleation and growth, our in situ SAXS show size focusing of the distribution under different synthetic conditions (different concentrations of metal and ligand as well as solvent type). To understand the mechanism of size focusing using PBM, we systematically studied how the evolution of the nanoparticle size distribution is affected by nucleation rate, and dependence of the growth rate constant on ligand surface coverage, and size of the nanoparticles. We show that continuous nucleation contributes to size defocusing. However, continuous nucleation results in different reaction times for the nanoparticle population leading to time and size-dependent ligand surface coverage. Using density functional theory (DFT) calculations and Brønsted–Evans–Polanyi relations, wemore »show that as the population grows, larger nanoparticles grow more slowly than smaller ones due to lower intrinsic activity and higher ligand coverage on the surface. Therefore, despite continuous nucleation, the faster growth of smaller nanoparticles in the population leads to size focusing. The size focusing behaviour (due to faster growth of smaller nanoparticles) was found to be model independent and similar results were demonstrated under different nucleation and growth pathways ( e.g. growth via ion reduction on the surface and/or monomer addition). Our results provide a microscopic connection between kinetics and thermodynamics of nanoparticle growth and metal–ligand binding, and their effect on the size distribution of colloidal nanoparticles.« less
3. Do polymer ligands block the catalysis of metal nanoparticles? Unexpected importance of binding motifs in improving catalytic activity

   https://doi.org/10.1039/D0TA03906C  

   Zhang, Lei ; Wei, Zichao ; Meng, Michael ; Ung, Gaël ; He, Jie ( August 2020 , Journal of Materials Chemistry A)

   Metal nanoparticles (NPs) tethered by synthetic polymers are of broad interest for self-assembly, nanomedicine and catalysis. The binding motifs in polymer ligands usually as the end functional groups of polymers are mostly limited to thiolates. Since the binding motif only represents a tiny fraction of many repeating units in polymers, its importance is often ignored. We herein report the uniqueness of polymeric N-heterocyclic carbene (NHC) ligands in providing oxidative stability and promoting the catalytic activity of noble metal NPs. Two “grafting to” methods were developed for polymer NHCs for pre-synthesized metal NPs in various solvents and with different sizes. Remarkably, imidazolium-terminated polystyrene can modify gold NPs (AuNPs) within 2 min while reaching a similar grafting density to polystyrene-thiol (SH) requiring 6 h modification. We demonstrate that polymer NHCs are extremely stable at high temperature in air. Interestingly, the binding motifs of polymer ligands dominate the catalytic activity of metal NPs. Polymer NHC modified metal NPs showed improved activity regardless of the surface crowdedness. In the case of AuNPs, AuNPs modified with polystyrene NHCs are approximately 5.2 times more active than citrate-capped ones and 22 times more active than those modified with polystyrene thiolates. In view of ligand-controlled catalytic properties ofmore »metal NPs, our results illustrate the importance of binding motifs that has been overlooked in the past.« less
4. Effect of (3-aminopropyl)triethoxysilane on dissolution of silica nanoparticles synthesized via reverse micro emulsion

   https://doi.org/10.1039/D2NR01190E  

   Kang, Hyunho ; Lee, Jihyeon ; O'Keefe, Tana ; Tuga, Beza ; Hogan Jr., Christopher J. ; Haynes, Christy L. ( June 2022 , Nanoscale)

   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,more »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.« less
5. Natural organic matter composition determines the molecular nature of silver nanomaterial-NOM corona

   https://doi.org/10.1039/c8en00018b  

   Baalousha, Mohammed ; Afshinnia, Kamelia ; Guo, Laodong ( January 2018 , Environmental Science: Nano)

   Adsorption of natural organic matter (NOM) on nanomaterials (NMs) results in the formation of interfacial area between NMs and the surrounding environment (referred to as NOM-corona), giving rise to NMs' unique surface identity. This unique surface identity is determined by the ligands and their interactions with NM surfaces. Since the chemical structure and functionality is heterogeneous and polydisperse, the molecular composition of NOM-corona is the result of competitive adsorption of NOM molecules on the NM surface. Here, we investigate the molecular composition of NOM-corona formed from two different NOM samples (isolated from the Yukon River and Milwaukee River) on the surface of AgNMs using electrospray ionization-Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). The composition of AgNM-NOM corona varied with the composition of the original NOM. In general, AgNM-NOM corona is rich with N- and S-containing compounds. Furthermore, AgNM-NOM corona is rich with compounds with high molecular weight, high unsaturation, and high number of oxygenated groups. However, CHOS (carbon, hydrogen, oxygen and sulfur) compounds adsorbed on AgNMs from the Yukon River NOM have low molecular weight (LMW) and low saturation index, which might be due to selective adsorption via chemical complexation (Ag–S). On the other hand, NOM compounds with LMW andmore »low unsaturation or compounds containing few oxygenated groups (mainly alcohols and ethers) are preferentially maintained in solution phase. The results here provide evidence of molecular interactions between NOM and NMs, which are critical to understanding NM behavior and toxicity in natural environments.« less