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Hydrogen is an essential gas to multiple industrial processes, and due to its high gravimetric density, it promises a large potential as a clean energy source. The risks of hydrogen at low pressures, however, have deterred substantial progress in improving hydrogen storage technology. Metal-organic frameworks (MOFs) are crystalline porous materials that have emerged as excellent gas adsorbents, and their gas storage properties can be tuned using a variety of synthetic methods. Herein, we leveraged the tunability and porosity of MOFs to introduce defect engineering as a method to improve hydrogen storage technology at low pressure regimes in two zirconium-based MOFs (Zr-MOFs), UiO-66 and NU-403, which feature ideal pore apertures (7 Å) for studying the confinement effect and ease of defect engineering. By reducing the number of defects in these Zr-MOFs, and thereby decreasing the quantity of larger pores, we can induce a structural confinement effect that increases the selectivity of hydrogen adsorption. A combination of thermogravimetric analysis (TGA) and nuclear magnetic resonance (NMR) spectroscopic analysis enabled quantification of the defect levels, confirming that each sample exhibits a distinct level of defectiveness. Gas adsorption measurements revealed that the adsorption of hydrogen is greatly enhanced in samples with fewer defects, while the calculated isosteric heats of enthalpy (Qst) indicate that there are no open metal sites in these MOFs that could be the cause. Overall, we can conclude that defect engineering for pore tailoring is a viable strategy to enhance hydrogen adsorption at low-pressure regimes.

In plants, the timely degeneration of tapetal cells is essential for providing nutrients and other substances to support pollen development. Rapid alkalinization factors (RALFs) are small, cysteine-rich peptides known to be involved in various aspects of plant development and growth, as well as defense against biotic and abiotic stresses. However, the functions of most of them remain unknown, while no RALF has been reported to involve tapetum degeneration. In this study, we demonstrated that a novel cysteine-rich peptide, EaF82, isolated from shy-flowering ‘Golden Pothos’ (Epipremnum aureum) plants, is a RALF-like peptide and displays alkalinizing activity. Its heterologous expression in Arabidopsis delayed tapetum degeneration and reduced pollen production and seed yields. RNAseq, RT-qPCR, and biochemical analyses showed that overexpression of EaF82 downregulated a group of genes involved in pH changes, cell wall modifications, tapetum degeneration, and pollen maturation, as well as seven endogenous Arabidopsis RALF genes, and decreased proteasome activity and ATP levels. Yeast two-hybrid screening identified AKIN10, a subunit of energy-sensing SnRK1 kinase, as its interacting partner. Our study reveals a possible regulatory role for RALF peptide in tapetum degeneration and suggests that EaF82 action may be mediated through AKIN10 leading to the alteration of transcriptome and energy metabolism, thereby causing ATP deficiency and impairing pollen development.

Chloroplasts are organelles responsible for chlorophyll biosynthesis, photosynthesis, and biosynthesis of many metabolites, which are one of key targets for crop improvement. Elucidating and engineering genes involved in chloroplast development are important approaches for studying chloroplast functions as well as developing new crops. In this study, we report a long-lived albino mutant derived from a popular ornamental plant Epipremnum aureum ‘Golden Pothos’ which could be used as a model for analyzing the function of genes involved in chloroplast development and generating colorful plants. Albino mutant plants were isolated from regenerated populations of variegated ‘Golden Pothos’ whose albino phenotype was previously found to be due to impaired expression of EaZIP, encoding Mg-protoporphyrin IX monomethyl ester cyclase. Using petioles of the mutant plants as explants with a traceable sGFP gene, an efficient transformation system was developed. Expressing Arabidopsis CHL27 (a homolog of EaZIP) but not EaZIP in albino plants restored green color and chloroplast development. Interestingly, in addition to the occurrence of plants with solid green color, plants with variegated leaves and pale-yellow leaves were also obtained in the regenerated populations. Nevertheless, our study shows that these long-lived albino plants along with the established efficient transformation system could be used for creating colorful ornamental plants. This system could also potentially be used for investigating physiological processes associated with chlorophyll levels and chloroplast development as well as certain biological activities, which are difficult to achieve using green plants.

Increasing ambient ozone (O3) concentrations and resurgent rust diseases are two concomitant limiting factors to wheat production worldwide. Breeding resilient wheat cultivars bearing rust resistance and O3 tolerance while maintaining high yield is critical for global food security. This study aims at identifying ozone tolerance among key rust-susceptible wheat genotypes [Rust near-universal susceptible genotypes (RnUS)], as a first step towards achieving this goal. Tested RnUS included seven bread wheat genotypes (Chinese Spring, Line E, Little Club, LMPG 6, McNair 701, Morocco and Thatcher), and one durum wheat line (Rusty). Plants were treated with five O3 concentrations (CF, 50, 70, 90, and 110 ppb), in two O3 exposure systems [continuous stirred tank reactors (CSTR) and outdoor-plant environment chambers (OPEC)], at 21–23 Zadoks decimal growth stage. Visible injury and biomass accumulation rate were used to assess O3 responses. Visible injury data showed consistent order of genotype sensitivity (Thatcher, LMPG 6 > McNair 701, Rusty > Line E, Morocco, Little Club > Chinese Spring). Additionally, leaves at different orders showed differential O3 responses. Biomass accumulation under O3 stress showed similar results for the bread wheat genotypes. However, the durum wheat line “Rusty” had the most O3-sensitive biomass production, providing a contrasting O3 response to the tolerance reported in durum wheat. Chinese Spring was the most tolerant genotype based on both parameters and could be used as a source for O3 tolerance, while sensitive genotypes could be used as sensitive parents in mapping O3 tolerance in bread wheat. The suitability of visible symptoms and biomass responses in high-throughput screening of wheat for O3 tolerance was discussed. The results presented in this research could assist in developing future approaches to accelerate breeding wheat for O3 tolerance using existing breeding materials.

Breeding wheat for higher grain yield can contribute to global food security and sustainable production on less land. Tropospheric ozone can injure wheat plants and subsequently reduce grain yield. Identification of ozone tolerance in the wheat genome can assist plant breeders in developing new sources of tolerant germplasm. Our objective was to use the ‘Chinese Spring’ monosomic lines to screen for ozone response and identify the chromosomic locations contributing to ozone tolerance based on foliar injury. Two methodologies, Continuous Stirred Tank Reactors and Outdoor Plant Environment Chambers, were used to expose wheat monosomic lines to varying concentrations and durations of ozone. Each wheat monosomic line in ‘Chinese Spring’ has a missing chromosome in each of the wheat subgenomes (A, B, and D). In both methodologies, we found significant and repeatable data to identify chromosome 7A as a major contributor to tolerance to ozone injury in ‘Chinese Spring’. In every experiment, the absence of chromosome 7A resulted in significant injury to wheat due to ozone. This was not the case when any other chromosome was missing.

A cornerstone of modern synthetic chemistry rests on the ability to manipulate the reactivity of a carbon center by rendering it either electrophilic or nucleophilic. However, accessing a similar reactivity spectrum with boron-based reagents has been significantly more challenging. While classical nucleophilic carbon-based reagents normally do not require steric protection, readily accessible, unprotected boron-based nucleophiles have not yet been realized. Herein, we demonstrate that the bench stable closo-hexaborate cluster anion can engage in a nucleophilic substitution reaction with a wide array of organic and main group electrophiles. The resulting molecules containing B‒C bonds can be further converted to tricoordinate boron species widely used in organic synthesis.

The synthesis of [1,1'-bis(o-carboranyl)]boranes was achieved through the deprotonation of 1,1'-bis(o-carborane) reagents followed by salt metathesis with (iPr)2NBCl2. X-ray crystallography confirms planar central BC4 rings and Gutmann-Beckett studies reveal an increase in Lewis acidity at the boron center in comparison to their biphenyl congener, 9-borafluorene.

Global reliance on fossil fuel combustion for energy production has contributed to the rising concentration of atmospheric CO2, creating significant global climate challenges. In this regard, direct air capture (DAC) of CO2 from the atmosphere has emerged as one of the most promising strategies to counteract the harmful effects on the environment, and the further development and commercialization of this technology will play a pivotal role in achieving the goal of net‐zero emissions by 2050. Among various DAC adsorbents, metal–organic frameworks (MOFs) show great potential due to their high porosity and ability to reversibly adsorb CO2 at low concentrations. However, the adsorption efficiency and cost‐effectiveness of these materials must be improved to be widely deployed as DAC sorbents. To that end, this perspective provides a critical discussion on several types of benchmark MOFs that have demonstrated high CO2 capture capacities, including an assessment of their stability, CO2 capture mechanism, capture‐release cycling behavior, and scale‐up synthesis. It then concludes by highlighting limitations that must be addressed for these MOFs to go from the research laboratory to implementation in DAC devices on a global scale so they can effectively mitigate climate change. [ABSTRACT FROM AUTHOR]

We report a discovery that perfunctionalized icosahedral dodecaborate clusters of the type B12(OCH2Ar)12 (Ar = Ph or C6F5) can undergo photo-excitation with visible light, leading to a new class of metal-free photooxidants. Excitation in these species occurs as a result of the charge transfer between low-lying orbitals located on the benzyl substituents and an unoccupied orbital delocalized throughout the boron cluster core. Here we show how these species, photo-excited with a benchtop blue LED source, can exhibit excited-state reduction potentials as high as 3 V and can participate in electron-transfer processes with a broad range of styrene monomers, initiating their polymerization. Initiation is observed in cases of both electron-rich and electron-deficient styrene monomers at cluster loadings as low as 0.005 mol%. Furthermore, photo-excitation of B12(OCH2C6F5)12 in the presence of a less activated olefin such as isobutylene results in the production of highly branched poly(isobutylene). This work introduces a new class of air-stable, metal-free photo-redox reagents capable of mediating chemical transformations.