Sum frequency generation spectroscopy of fluorinated organic material-based interfaces: a tutorial review.

Molecular interactions at interfaces have a significant effect on the wetting properties of surfaces on a macroscale. Sum frequency generation (SFG) spectroscopy, one of a few techniques capable of probing such interactions, generates a surface vibrational spectrum sensitive to molecular structures and has been used to determine the orientation of molecules at interfaces. The purpose of this review is to assess SFG spectroscopy's ability to determine the molecular orientations of interfaces composed of fluorinated organic molecules. We will explore three different types of fluorinated organic material-based interfaces, naming liquid-air, solid-air, and solid-liquid interfaces, to see how SFG spectroscopy can be used to gain valuable and unique information regarding the molecular orientation of each interface. We hope this review will help to broaden the understanding of how to employ SFG spectroscopy to obtain more complex structural information for various fluorinated organic material-based interfaces in the future.

Functionalized N-Heterocyclic Carbene Monolayers on Gold for Surface-Initiated Polymerizations.

Although N-heterocyclic carbenes (NHCs) are superior to thiol adsorbates in that they form remarkably stable bonds with gold, the generation of NHC-based self-assembled monolayers (SAMs) typically requires a strong base and an inert atmosphere, which limits the utility of such films in many applications. Herein, we report the development and use of bench-stable NHC adsorbates, benzimidazolium methanesulfonates, for the direct formation of NHC films on gold surfaces under an ambient atmosphere at room temperature without the need for extraordinary precautions. The generated NHC SAMs were fully characterized using ellipsometry, X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS), and contact angle measurements, and they were compared to analogous SAMs generated from an NHC bicarbonate adsorbate. Based on these findings, a unique radical initiator α,ω-bidentate azo-terminated NHC adsorbate, NHC15AZO[OMs], was designed and synthesized for the preparation of SAMs on gold surfaces with both NHC headgroups bound to the surface. The adsorbate molecules in NHC15AZO SAMs can exist in a hairpin or a linear conformation depending on the concentration of the adsorbate solution used to prepare the SAM. These conformations were studied by a combination of ellipsometry, XPS, PM-IRRAS, and scanning electron microscopy using gold nanoparticles (AuNPs) as a tag material. Moreover, the potential utility of these unique radical-initiating NHC films as surface-initiated polymerization platforms was demonstrated by controlling the thickness of polystyrene brush films grown from azo-terminated NHC monolayer surfaces simply by adjusting the reaction time of the photoinitiated radical polymer growth process.

Machine learning investigation of viscosity and ionic conductivity of protic ionic liquids in water mixtures.

Ionic liquids (ILs) are well classified as designer solvents based on the ease of tailoring their properties through modifying the chemical structure of the cation and anion. However, while many structure-property relationships have been developed, these generally only identify the most dominant trends. Here, we have used machine learning on existing experimental data to construct robust models to produce meaningful predictions across a broad range of cation and anion chemical structures. Specifically, we used previously collated experimental data for the viscosity and conductivity of protic ILs [T. L. Greaves and C. J. Drummond, Chem. Rev. 115, 11379-11448 (2015)] as the inputs for multiple linear regression and neural network models. These were then used to predict the properties of all 1827 possible cation-anion combinations (excluding the input combinations). These models included the effect of water content of up to 5 wt. %. A selection of ten new protic ILs was then prepared, which validated the usefulness of the models. Overall, this work shows that relatively sparse data can be used productively to predict physicochemical properties of vast arrays of ILs.

Multifunctional Iron Oxide Magnetic Nanoparticles for Biomedical Applications: A Review.

Due to their good magnetic properties, excellent biocompatibility, and low price, magnetic iron oxide nanoparticles (IONPs) are the most commonly used magnetic nanomaterials and have been extensively explored in biomedical applications. Although magnetic IONPs can be used for a variety of applications in biomedicine, most practical applications require IONP-based platforms that can perform several tasks in parallel. Thus, appropriate engineering and integration of magnetic IONPs with different classes of organic and inorganic materials can produce multifunctional nanoplatforms that can perform several functions simultaneously, allowing their application in a broad spectrum of biomedical fields. This review article summarizes the fabrication of current composite nanoplatforms based on integration of magnetic IONPs with organic dyes, biomolecules (e.g., lipids, DNAs, aptamers, and antibodies), quantum dots, noble metal NPs, and stimuli-responsive polymers. We also highlight the recent technological advances achieved from such integrated multifunctional platforms and their potential use in biomedical applications, including dual-mode imaging for biomolecule detection, targeted drug delivery, photodynamic therapy, chemotherapy, and magnetic hyperthermia therapy.

Fe3O4 Nanoparticles: Structures, Synthesis, Magnetic Properties, Surface Functionalization, and Emerging Applications.

Magnetite (Fe3O4) nanoparticles (NPs) are attractive nanomaterials in the field of material science, chemistry, and physics because of their valuable properties, such as soft ferromagnetism, half-metallicity, and biocompatibility. Various structures of Fe3O4 NPs with different sizes, geometries, and nanoarchitectures have been synthesized, and the related properties have been studied with targets in multiple fields of applications, including biomedical devices, electronic devices, environmental solutions, and energy applications. Tailoring the sizes, geometries, magnetic properties, and functionalities is an important task that determines the performance of Fe3O4 NPs in many applications. Therefore, this review focuses on the crucial aspects of Fe3O4 NPs, including structures, synthesis, magnetic properties, and strategies for functionalization, which jointly determine the application performance of various Fe3O4 NP-based systems. We first summarize the recent advances in the synthesis of magnetite NPs with different sizes, morphologies, and magnetic properties. We also highlight the importance of synthetic factors in controlling the structures and properties of NPs, such as the uniformity of sizes, morphology, surfaces, and magnetic properties. Moreover, emerging applications using Fe3O4 NPs and their functionalized nanostructures are also highlighted with a focus on applications in biomedical technologies, biosensing, environmental remedies for water treatment, and energy storage and conversion devices.

Antifouling Coatings Generated from Unsymmetrical Partially Fluorinated Spiroalkanedithiols.

Biofouling negatively impacts modern society on a daily basis, especially with regard to the important industries of medicine, oil, and shipping. This manuscript describes the preparation and study of model antifouling coatings generated from the adsorption of unsymmetrical partially fluorinated spiroalkanedithiols on gold. The antifouling properties of the self-assembled monolayers (SAMs) derived from the spiroalkanedithiols were compared to SAMs derived from analogous monodentate partially fluorinated and nonfluorinated alkanethiols. The antifouling properties were evaluated using in situ surface plasmon resonance spectroscopy (SPR), ex situ electrochemical quartz crystal microbalance (QCM) measurements, and ex situ ellipsometric thickness measurements. The resistance to nonspecific protein adsorption of the SAMs was evaluated with proteins having a wide range of properties and applications including protamine, lysozyme, bovine serum albumin, and fibrinogen. The results from the SPR and the QCM measurements demonstrated that in most cases, the SAM coatings derived from the partially fluorinated spiroalkanedithiols having mixed hydrocarbon and fluorocarbon tail groups exhibited better antifouling performance when compared to the SAMs derived from their single-component monodentate counterparts. The studies also revealed that while the SPR and the QCM measurements in most cases were able to distinguish the adsorption trends for the SAMs and proteins examined, the ellipsometric thickness measurements were markedly less discriminating. On the whole, these studies validate the use of unsymmetrical partially fluorinated spiroalkanedithiols for generating effective antifouling coatings on metal substrates.

Semihollow Core-Shell Nanoparticles with Porous SiO2 Shells Encapsulating Elemental Sulfur for Lithium-Sulfur Batteries.

Lithium-sulfur batteries have shown great promise as next-generation high energy density power sources, but their commercial applications are hindered by short battery cycle life arising from the dissolution and shuttling of polysulfides. To address this shortcoming, we prepared two types of semihollow core-shell nanoparticles in which (1) elemental sulfur is encapsulated within a porous silica shell (S@SiO2) and (2) elemental sulfur is encapsulated within a porous silica shell where the inner surface of the shell is decorated with small Au nanoparticles (S@Au@SiO2). These core-shell nanoparticles, both ∼300 nm in diameter, were generated from analogous zinc sulfide-based core-shell nanoparticles (ZnS@SiO2 and ZnS@Au@SiO2, respectively) by converting the ZnS cores to elemental sulfur upon treatment with Fe(NO3)3. With a high surface area and strong host-polysulfide interaction, the SiO2 shells effectively trap the polysulfides; moreover, the internal void space of these nanostructures accommodates the volume expansion of the sulfur core upon lithiation. By decorating ∼5-7 nm Au nanoparticles evenly on the inner surface of the porous SiO2 shells (i.e., S@Au@SiO2), electron transport is enhanced, with consequently enhanced sulfur conversion kinetics at high current rates. Studies of battery performance showed that the S@SiO2 cathode can deliver an initial capacity of 1153 mA h g-1 under 0.2 C and retain 816 mA h g-1 after 100 cycles. More importantly, the Au-decorated S@Au@SiO2 cathode can deliver a high capacity of 500 mA h g-1 under 5 C.

Nanoparticle-Based Strategies to Combat COVID-19.

Coronavirus disease 2019 (COVID-19) is the worst pandemic disease of the current millennium. This disease is caused by the highly contagious severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), which first exhibited human-to-human transmission in December 2019 and has infected millions of people within months across 213 different countries. Its ability to be transmitted by asymptomatic carriers has put a massive strain on the currently available testing resources. Currently, there are no clinically proven therapeutic methods that clearly inhibit the effects of this virus, and COVID-19 vaccines are still in the development phase. Strategies need to be explored to expand testing capacities, to develop effective therapeutics, and to develop safe vaccines that provide lasting immunity. Nanoparticles (NPs) have been widely used in many medical applications, such as biosensing, drug delivery, imaging, and antimicrobial treatment. SARS-CoV-2 is an enveloped virus with particle-like characteristics and a diameter of 60-140 nm. Synthetic NPs can closely mimic the virus and interact strongly with its proteins due to their morphological similarities. Hence, NP-based strategies for tackling this virus have immense potential. NPs have been previously found to be effective tools against many viruses, especially against those from the Coronaviridae family. This Review outlines the role of NPs in diagnostics, therapeutics, and vaccination for the other two epidemic coronaviruses, the 2003 severe acute respiratory syndrome (SARS) virus and the 2012 Middle East respiratory syndrome (MERS) virus. We also highlight nanomaterial-based approaches to address other coronaviruses, such as human coronaviruses (HCoVs); feline coronavirus (FCoV); avian coronavirus infectious bronchitis virus (IBV); coronavirus models, such as porcine epidemic diarrhea virus (PEDV), porcine reproductive and respiratory syndrome virus (PRRSV), and transmissible gastroenteritis virus (TGEV); and other viruses that share similarities with SARS-CoV-2. This Review combines the salient principles from previous antiviral studies with recent research conducted on SARS-CoV-2 to outline NP-based strategies that can be used to combat COVID-19 and similar pandemics in the future.

Dissecting Porosity in Molecular Crystals: Influence of Geometry, Hydrogen Bonding, and [π···π] Stacking on the Solid-State Packing of Fluorinated Aromatics.

Porous molecular crystals are an emerging class of porous materials that is unique in being built from discrete molecules rather than being polymeric in nature. In this study, we examined the effects of molecular structure of the precursors on the formation of porous solid-state structures with a series of 16 rigid aromatics. The majority of these precursors possess pyrazole groups capable of hydrogen bonding, as well as electron-rich aromatics and electron-poor tetrafluorobenzene rings. These precursors were prepared using a combination of Pd- and Cu-catalyzed cross-couplings, careful manipulations of protecting groups on the nitrogen atoms, and solvothermal syntheses. Our study varied the geometry and dimensions of precursors, as well as the presence of groups capable of hydrogen bonding and [π···π] stacking. Thirteen derivatives were crystallographically characterized, and four of them were found to be porous with surface areas between 283 and 1821 m2 g-1. Common to these four porous structures were (a) rigid trigonal geometry, (b) [π···π] stacking of electron-poor tetrafluorobenzenes with electron-rich pyrazoles or tetrazoles, and