Supercritical CO2-assisted atomization for deposition of cellulose nanocrystals: an experimental and computational study

Nanoparticle spray deposition finds numerous applications in pharmaceutical, electronics, manufacturing, and energy industries and has shown great promises in engineering the functional properties of the coated parts. However, current spray deposition systems either lack the required precision in controlling the morphology of the deposited nanostructures or do not have the capacity for large-scale deposition applications. In this study, we introduce a novel spray system that uses supercritical CO₂ to assist the atomization process and create uniform micron-size water droplets that are used as cellulose nanocrystal (CNC) carriers. CNCs are selected in this study as they are abundant, possess superior mechanical properties, and contain hydroxyl groups that facilitate interaction with neighboring materials. We fundamentally investigate the effect of different process parameters, such as injection pressure, gas-to-liquid ratio, the axial distance between the nozzle and substrate, and CNC concentration on the final patterns left on the substrate upon evaporation of water droplets. To this end, we show how tuning process parameters control the size of carrier droplets, dynamics of evaporation, and self-assembly of CNCs, which in turn dictate the final architecture of the deposited nanostructures. We will particularly investigate the morphology of the nanostructures deposited after evaporation of micron-size droplets that has not been fully disclosed to date. Different characterization techniques such as laser diffraction, polarized microscopy, and high-resolution profilometry are employed to visualize and quantify the effect of each process parameter. Numerical simulations are employed to inform the design of experiments. Finally, it is shown that the fabricated nanostructures can be engineered based on the size of the carrier droplets controlled by adjusting spray parameters and the concentration of nanoparticles in the injected mixture. Process parameters can be selected such that nanoparticles form a ring, disk, or dome-shaped structure. Moderate operational conditions, simplicity, and time efficiency of the process, and use of abundant and biodegradable materials, i.e., water, CNCs, and CO₂ promote the scalability and sustainability of this method.

     

Synthesis and thermal evaluation of novel mono- and bis-adamantylated resorcinol-based phthalonitrile resins with enhanced solubility

Journal of Thermal Analysis and Calorimetry - Phthalonitrile (PN) resins are high-temperature-resistant thermosetting polymers which find applications in military as well as aerospace owing to...     

Inhibition of Thiol-Mediated Uptake with Irreversible Covalent Inhibitors

Thiol-mediated uptake is emerging as method of choice to penetrate cells. This study focuses on irreversible covalent inhibitors of thiol-mediated uptake. High-content high-throughput screening of the so far largest collection of hypervalent iodine reagents affords inhibitors that are more than 250 times more active than Ellman’s reagent and rival the best dynamic covalent inhibitors. Comparison with other irreversible reagents reveals that inhibition within one series follows reactivity, whereas inhibition across series deviates from reactivity. These trends support that molecular recognition, besides dynamic covalent exchange, contributes significantly to thiol-mediated uptake. The most powerful inhibitors besides the best hypervalent iodine reagents were Fukuyama’s nosyl protecting group and super-cinnamaldehydes that have been introduced as irreversible activators of the pain receptor TRPA1. Considering that several viruses use different forms of thiol-mediated uptake to enter cells, the identification of new irreversible inhibitors of thiol-mediated uptake is of general interest for the discovery of new antivirals.     

MS/MS Fragmentation Behavior Study of meso-Phenylporphyrinoids Containing Nonpyrrolic Heterocycles and meso-Thienyl-Substituted Porphyrins

Free base and cobalt(II) complexes of six meso-tetraphenylporphyrinoids containing nonpyrrolic heterocycles and of three meso-thienylporphyrins were investigated using electrospray ionization tandem mass spectrometry (ESI-MS/MS). Their fragmentation was studied in a quadrupole ion trap as a function of the porphyrinoid macrocycle structure and compared with the fragmentation behavior of the benchmark compound meso-tetraphenylporphyrin. In situ oxidation of the neutral cobalt(II) complexes under ESI conditions produced singly charged cobalt(III) porphyrinoid ions; the free bases were ionized by protonation. For the porphyrinoids with an intact porphyrin core, the major fragmentation pathways observed were the losses of the meso-substituent (for meso-phenyl groups) and characteristic fragmentations of one or more meso-substituents (for the meso-thienyl group). Complex fragmentation pathways were observed for porphyrinoids with modifications to the porphyrin core but chemically reasonable structures could be assigned to most fragments, thus delineating general patterns for the behavior of pyrrole-modified porphyrins under CID conditions.

Sensing of Phosphates by Using Luminescent EuIII and TbIII Complexes: Application to the Microalgal Cell Chlorella vulgaris

Phenanthroline‐based chiral ligands L¹ and L² as well as the corresponding Eu^III and Tb^III complexes were synthesized and characterized. The coordination compounds show red and green emission, which was explored for the sensing of a series of anions such as F^?, Cl^?, Br^?, I^?, NO₃^?, NO₂^?, HPO₄^2?, HSO₄^?, CH₃COO^?, and HCO₃^?. Among the anions, HPO₄^2? exhibited a strong response in the emission property of both europium(III) and terbium(III) complexes. The complexes showed interactions with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). Owing to this recognition, these complexes have been applied as staining agents in the microalgal cell Chlorella vulgaris. The stained microalgal cells were monitored through fluorescence microscopy and scanning electron microscopy. Initially, the complexes bind to the outer cell wall and then enter the cell wall through holes in which they probably bind to phospholipids. This leads to a quenching of the luminescence properties.     

Reduction of Oxide Minerals by Hydrogen Plasma: An Overview

Carbothermic reduction of oxide minerals is one of the major routes to obtain the corresponding metals. This process produces a lot of CO₂, which is responsible for greenhouse effect. Alternatively, hydrogen plasma containing hydrogen in atomic, ionic, and excited states can reduce almost every metal oxide even at lower temperatures. Besides this advantage, plasma processing also offers kinetic advantages. Further, hydrogen-water cycle does not pose any environmental problems. However, reduction of metal oxides in hydrogen plasma is not so straightforward—there are issues relating to introduction of material into the plasma zone, residence time, reverse reaction, and scale-up that must be resolved—yet, it holds the key to future environmental challenges particularly with respect to CO₂ emission. This paper provides an overview of reduction of oxide minerals by hydrogen plasma. The influences of various reaction conditions particularly with respect to reduction of oxides are discussed and some aspects of both thermal and non-thermal cold plasma linking oxidative as well as dissociative reduction are presented.     

On-Surface Synthesis of Cumulene-Containing Polymers via Two-Step Dehalogenative Homocoupling of Dibromomethylene-Functionalized Tribenzoazulene

Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on-surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well-controlled ultrahigh-vacuum conditions. Here we report the on-surface synthesis of a polymer linked by cumulene-like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene-like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X-ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on-surface synthesis of cumulene-containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces.