Phytotoxic effect of sub-3-nm crystalline ceria nanoparticles on the hydroponic growth of Daikon radish microgreens.

Cerium oxide nanoparticles (ceria NPs) have been widely used in many industrial applications. They have been proposed as a potential remedy for reducing oxidative stress in biological systems. General concerns over the toxicity of engineered ceria NPs have led to studies of their phytotoxicity in plants. Most of these plant growth studies were conducted in soil using grain crops and commercial ceria NPs of sizes from 6 nm to 100's nm. In this paper, we report our evaluation of the phytotoxicity and uptake of sub-3-nm crystalline ceria NPs by exposing Daikon radish (Raphanus sativus var. longipinnatus) microgreens to these NPs with environmentally relevant concentrations under hydroponic growth conditions. Aqueous suspensions of different concentrations of these ceria NPs (0.1 ppm, 1 ppm, and 10 ppm) were applied to these microgreens for the last 7 days of the 12-day growth period. Our results revealed the uptake of cerium by plant roots and the translocation of cerium to the stems and the cotyledons (seed leaves). The accumulation of cerium was found to be maximum at the roots, followed by the cotyledons and the stems of the plants. Even at the lowest concentration (0.1 ppm) of the sub-3-nm ceria NPs, the accumulation of cerium at the roots significantly stunted the root growth. However, these NP treatments did not show significant changes to the distributions of macro-minerals (Mg, K, and Ca) and micro-minerals (Zn and Cu) in the microgreens at the end of the 12-day growth period. The phytotoxic effect of sub-3-nm crystalline ceria nanoparticles on the hydroponic growth of Daikon radish microgreens was studied. The cerium uptake by the plant and its effect on the bioavailability of major macro-minerals and micro-minerals within the plant were examined.

Formation of dimethyl carbonate via direct esterification of CO2 with methanol on reduced or stoichiometric CeO2(111) and (110) surfaces.

CeO2-Catalyzed esterification of CO2, a well-known greenhouse gas, with methanol has been widely recognized as a promising alternative method to produce dimethyl carbonate (DMC). Herein, we performed a comprehensive study of catalytic mechanisms underlying the formation of DMC from CO2 and methanol on both stoichiometric and reduced CeO2(111) and (110) surfaces. To this end, the saddle-point searching algorithm is employed. Specifically, using the monomethyl carbonate (MMC) as the key intermediate, a three-step Langmuir-Hinshelwood (LH) mechanism, including the formation and esterification of monomethyl carbonate and removal of water molecule, is identified for the catalytic DMC formation on either the reduced or the stoichiometric CeO2(111) and (110) surfaces. For both CeO2(111) and (110) surfaces, our study indicates that the presence of oxygen vacancies can markedly lower the activation energy barrier. Different rate-limiting steps are identified, however, for the reduced CeO2(111) and (110) surfaces. Successful identification of the rate-limiting step and the associated active CO2 species will provide atomic-level guidance on selection of metal-oxide-based catalysts toward direct synthesis of DMC from the green-house gas CO2 and methanol.

Gas hydrates in confined space of nanoporous materials: new frontier in gas storage technology.

Gas hydrates (clathrate hydrates, clathrates, or hydrates) are crystalline inclusion compounds composed of water and gas molecules. Methane hydrates, the most well-known gas hydrates, are considered a menace in flow assurance. However, they have also been hailed as an alternative energy resource because of their high methane storage capacity. Since the formation of gas hydrates generally requires extreme conditions, developing porous material hosts to synthesize gas hydrates with less-demanding constraints is a topic of great interest to the materials and energy science communities. Though reports of modeling and experimental analysis of bulk gas hydrates are plentiful in the literature, reliable phase data for gas hydrates within confined spaces of nanoporous media have been sporadic. This review examines recent studies of both experiments and theoretical modeling of gas hydrates within four categories of nanoporous material hosts that include porous carbons, metal-organic frameworks, graphene nanoslits, and carbon nanotubes. We identify challenges associated with these porous systems and discuss the prospects of gas hydrates in confined space for potential applications.

Growth of carbon dioxide whiskers.

We report the growth of carbon dioxide (CO2) whiskers at low temperatures (-70 °C to -65 °C) and moderate pressure (4.4 to 1.0 bar). Their axial growth was assessed by optical video analysis. The identities of these whiskers were confirmed as CO2 solids by Raman spectroscopy. A vapor-solid growth mechanism was proposed based on the influence of the relative humidity on the growth.

Probing the Aggregation and Signaling Behavior of Some Twisted 9,9'-Bianthryl Derivatives: Observation of Aggregation-Induced Blue-Shifted Emission.

With an aim to understand the photophysical behavior of twisted organic fluorescent molecules in their aggregated state, two twisted biaryl molecules, namely, 9,9'-bianthryl and 10,10'-dicyano-9,9'-bianthryl, have been synthesized and characterized by conventional spectroscopic methods. To understand the role of C-C bond twisting on the photophysical response of biaryl aggregates, monoaryl counterparts (anthracene and 9-anthracenecarbonitrile) of the biaryl systems are also investigated. Photophysical behaviors of these systems along with their monoaryl counterpart are investigated in both solution and aggregated state. Investigations reveal that fluorescence spectra of the biaryl compounds show blue-shifted emission upon aggregation. Interestingly, no blue shift of the emission has been observed for monoaryl aggregates. Photophysical data of biaryl systems compared to monoaryl unit reveal that change in geometry, during self-assembly process, disfavors the formation of charge-transfer state, which eventually causes blue shift in the emission upon aggregation. In addition to this, potential of these systems toward signaling of nitroaromatic explosive has also been explored. Among all of the nitroaromatics, the highest fluorescence quenching is observed for nitrophenols (say picric acid (PA)). The investigation also reveals that compared to monoaryl systems, biaryl systems are more responsive to fluorescence quenching by nitroaromatics. Perrin's model of quenching sphere action has been attributed to nitrophenol (PA) selective signaling behavior of biaryl systems.