Oriented 1D Metal-Organic Frameworks for Selective Chemisorption by a Substitution-Insertion Mechanism.

Chemisorption on organometallic-based adsorbents is crucial for the controlled separation and purification of targeted systems. Herein, oriented 1D NH2-CuBDC·H2O metal-organic frameworks (MOFs) featuring accessible CuII sites are successfully fabricated by bottom-up interfacial polymerization. The prepared MOFs, as deliberately self-assembled secondary particles, exhibit a visually detectable coordination-responsive characteristic induced by the nucleophilic substitution and competitive coordination of guest molecules. As a versatile phase-change chemosorbent, the MOFs exhibit unprecedented NH3 capture (18.83 mmol g-1 at 298 K) and bioethanol dehydration performance (enriching ethanol from 99% to 99.99% within 10 min by direct adsorption separation of liquid mixtures of ethanol and water). Furthermore, the raw materials for preparing the 1D MOFs are inexpensive and readily available, and the facile regeneration with water washing at room temperature effectively minimizes the energy consumption and cost of recycling, enabling it to be the most valuable adsorbent for the removal and separation of target substances.

Crystalline Porous Organic Cage Membranes Constructed Using Fortified Intermolecular Interactions for Molecular Sieving.

Among the various types of materials with intrinsic porosity, porous organic cages (POCs) are distinctive as discrete molecules that possess intrinsic cavities and extrinsic channels capable of facilitating molecular sieving. However, the fabrication of POC membranes remains highly challenging due to the weak noncovalent intermolecular interactions and most reported POCs are powders. In this study, we constructed crystalline free-standing porous organic cage membranes by fortifying intermolecular interactions through the induction of intramolecular hydrogen bonds, which was confirmed by single-crystal X-ray analysis. To elucidate the driving forces behind, a series of terephthaldehyde building blocks containing different substitutions were reacted with flexible triamine under different conditions via interfacial polymerization (IP). Furthermore, density functional theory (DFT) calculations suggest that intramolecular hydrogen bonding can significantly boost the intermolecular interactions. The resulting membranes exhibited fast solvent permeance and high rejection of dyes not only in water, but also in organic solvents. In addition, the membrane demonstrated excellent performance in precise molecular sieving in organic solvents. This work opens an avenue to designing and fabricating free-standing membranes composed of porous organic materials for efficient molecular sieving.

Target of rapamycin (TOR) plays a role in regulating ROS-induced chloroplast damage during cucumber (Cucumis sativus) leaf senescence.

In cucumber production, delaying leaf senescence is crucial for improving cucumber yield and quality. Target of rapamycin (TOR) is a highly conserved serine/threonine protein kinase in eukaryotes, which can integrate exogenous and endogenous signals (such as cell energy state levels) to stimulate cell growth, proliferation, and differentiation. However, no studies have yet examined the regulatory role of TOR signalling in cucumber leaf senescence. In this study, the effects of TOR signalling on dark-induced cucumber leaf senescence were investigated using the TOR activator MHY1485 and inhibitor AZD8055 combined with transient transformation techniques. The results indicate that TOR responds to dark-induced leaf senescence, and alterations in TOR activity/expression influence cucumber leaf resistance to dark-induced senescence. Specifically, in plants with elevated TOR activity/expression, we observed reduced expression of senescence-related genes, less membrane lipid damage, decreased cell apoptosis, lower levels of reactive oxygen species production, and less damage to the photosynthetic system compared to the control. In contrast, in plants with reduced TOR activity/expression, we observed higher expression of senescence-related genes, increased membrane lipid damage, enhanced cell apoptosis, elevated levels of reactive oxygen species production, and more damage to the photosynthetic system. These comprehensive results underscore the critical role of TOR in regulating dark-induced cucumber leaf senescence. These findings provide a foundation for controlling premature leaf senescence in cucumber production and offer insights for further exploration of leaf senescence mechanisms and the development of more effective control methods.

Characterization of caffeoyl shikimate esterase gene family identifies CsCSE5 as a positive regulator of Podosphaera xanthii and Corynespora cassiicola pathogen resistance in cucumber.

KEY MESSAGE: CsCSE genes might be involved in the tolerance of cucumber to pathogens. Silencing of the CsCSE5 gene resulted in attenuated resistance of cucumber to Podosphaera xanthii and Corynespora cassiicola. Caffeoyl shikimate esterase (CSE), a key enzyme in the lignin biosynthetic pathway, has recently been characterized to play a key role in defense against pathogenic infection in plants. However, a systematic analysis of the CSE gene family in cucumber (Cucumis sativus) has not yet been conducted. Here, we identified eight CsCSE genes from the cucumber genome via bioinformatic analyses, and these genes were unevenly distributed on chromosomes 1, 3, 4, and 5. Results from multiple sequence alignment indicated that the CsCSE proteins had domains required for CSE activity. Phylogenetic analysis of gene structure and protein motifs revealed the conservation and diversity of the CsCSE gene family. Collinearity analysis showed that CsCSE genes had high homology with CSE genes in wax gourd (Benincasa hispida). Cis-acting element analysis of the promoters suggested that CsCSE genes might play important roles in growth, development, and stress tolerance. Expression pattern analysis indicated that CsCSE5 might be involved in regulating the resistance of cucumber to pathogens. Functional verification data confirmed that CsCSE5 positively regulates the resistance of cucumber to powdery mildew pathogen Podosphaera xanthii and target leaf spot pathogen Corynespora cassiicola. The results of our study provide information that will aid the genetic improvement of resistant cucumber varieties.

Covalent Organic Network Membranes with Tunable Nanoarchitectonics from Macrocycle Building Blocks for Graded Molecular Sieving.

Traditional piperazine-based polyamide membranes usually suffer from the intrinsic trade-off relationship between selectivity and permeance. The development of macrocycle membranes with customized nanoscale pores is expected to address this challenge. Herein, we introduce 1,4-diazacyclohexane (2N), 1,4,7-triazacyclononane (3N), and 1,4,8,11-tetraazacyclotetradecane (4N) as molecular building blocks to construct the nanoarchitectonics of polyamide membranes prepared from interfacial polymerization (IP). The permeance of covalent organic network membranes follows the trend of 4N-TMC > 3N-TMC > 2N-TMC, while the molecular weight cutoff (MWCO) also follows the same trend of 4N-TMC > 3N-TMC > 2N-TMC, according to their nanopore size of the membranes. The microporosity, orientation, and surface chemistry of covalent organic network membranes can be rationally designed by macrocycle building units. The ordered nanoarchitectonics allows the membranes to attain an excellent performance in graded molecular sieving. Importantly, the novel covalent organic network membranes with tunable nanoarchitectonics prepared from macrocycle building units exhibited high water permeance (32.5 LMH/bar) and retained long-term stability after 100 h of test and bovine serum albumin fouling. These results reveal the enormous potential of 3N-TMC and 4N-TMC membranes in saline textile wastewater treatments and precise molecular sieving.

Cucumis sativus CsbZIP90 suppresses Podosphaera xanthii resistance by modulating reactive oxygen species.

Resistance to disease in plants requires the coordinated action of multiple functionally related genes, as it is difficult to improve disease resistance with a single functional gene. Therefore, the use of transcription factors to regulate the expression of multiple resistance genes to improve disease resistance has become a recent focus in the field of gene research. The basic leucine zipper (bZIP) transcription factor family plays vital regulatory roles in processes, such as plant growth and development and the stress response. In our previous study, CsbZIP90 (Cucsa.134370) was involved in the defense response of cucumber to Podosphaera xanthii, but the relationship between cucumber and resistance to powdery mildew remained unclear. Herein, we detected the function of CsbZIP90 in response to P. xanthii. CsbZIP90 was localized to the cytoplasm and nucleus, and its expression was significantly induced during P. xanthii attack. Transient overexpression of CsbZIP90 in cucumber cotyledons resulted in decreased resistance to P. xanthii, while silencing CsbZIP90 increased resistance to P. xanthii. CsbZIP90 negatively regulated the expression of reactive oxygen species (ROS)-related genes and activities of ROS-related kinases. Taken together, our results show that CsbZIP90 suppresses P. xanthi resistance by modulating ROS. This study will provide target genes for breeding cucumbers resistant to P. xanthii.

Covalent Organic Framework Membranes with Regulated Orientation for Monovalent Cation Sieving.

Continuous covalent organic framework (COF) thin membranes have garnered broad concern over the past few years due to their merits of low energy requirements, operational simplicity, ecofriendliness, and high separation efficiency in the application process. This study marks the first instance of fabricating two distinct, self-supporting COF membranes from identical building blocks through solvent modulation. Notably, the precision of the COF membrane's separation capabilities is substantially enhanced by altering the pore alignment from a random to a vertical orientation. Within these confined channels, the membrane with vertically aligned pores and micron-scale stacking thickness demonstrates rapid and selective transportation of Li+ ions over Na+ and K+ ions, achieving Li+/K+ and Li+/Na+ selectivity ratios of 38.7 and 7.2, respectively. This research not only reveals regulated orientation and layer stacking in COF membranes via strategic solvent selection but also offers a potent approach for developing membranes specialized in Li+ ion separation.

Microporous polyarylate membranes based on 3D phenolphthalein for molecular sieving.

Thin-film composite (TFC) membranes have gradually replaced some traditional technologies in the extraction, separation, and concentration of high value-added pharmaceutical ingredients due to their controllable microstructure. Nevertheless, devising solvent-stable, scalable TFC membranes with high permeance and efficient molecule selectivity is urgently needed to improve the separation efficiency in the separation process. Here, we propose phenolphthalein, a commercial acid-base indicator, as an economical monomer for optimizing the micropore structure of selective layers with thickness down to 30 nanometers formed by in situ interfacial reactions. Molecular dynamics simulations indicate that the polyarylate membranes prepared using three-dimensional phenolphthalein monomers exhibit tunable microporosity and higher pore interconnectivity. Moreover, the TFC membranes show a high methanol permeance (9.9 ± 0.1 liters per square meter per hour per bar) and small molecular weight cutoff (≈289 daltons) for organic micropollutants in organic solvent systems. The polyarylate membranes exhibit higher mechanical strength (2.4 versus 0.8 gigapascals) compared to the traditional polyamide membrane.

Ultrafast Interfacial Self-Assembly toward Bioderived Polyester COF Membranes with Microstructure Optimization.

The precise manipulation of the microstructure (pore size, free volume distribution, and connectivity of the free-volume elements), thickness, and mechanical characteristics of membranes holds paramount significance in facilitating the effective utilization of self-standing membranes. In this contribution, the synthesis of two innovative ester-linked covalent-organic framework (COF) membranes is first reported, which are generated through the selection of plant-derived ellagic acid and quercetin phenolic monomers in conjunction with terephthaloyl chloride as a building block. The optimization of the microstructure of these two COF membranes is systematically achieved through the application of three different interfacial electric field systems: electric neutrality, positive electricity, and negative electricity. It is observed that the positively charged system facilitates a record increase in the rate of membrane formation, resulting in a denser membrane with a uniform pore size and enhanced flexibility. In addition, a correlation is identified wherein an increase in the alkyl chain length of the surfactants leads to a more uniform pore size and a decrease in the molecular weight cutoff of the COF membrane. The resulting COF membrane exhibits an unprecedented combination of high water permeance, superior sieving capability, robust mechanical strength, chemical robustness for promising membrane-based separation science and technology.

Schottky Junction and D-A1 -A2 System Dual Regulation of Covalent Triazine Frameworks for Highly Efficient CO2 Photoreduction.

Covalent triazine frameworks (CTFs) are emerging as a promising molecular platform for photocatalysis. Nevertheless, the construction of highly effective charge transfer pathways in CTFs for oriented delivery of photoexcited electrons to enhance photocatalytic performance remains highly challenging. Herein, a molecular engineering strategy is presented to achieve highly efficient charge separation and transport in both the lateral and vertical directions for solar-to-formate conversion. Specifically, a large π-delocalized and π-stacked Schottky junction (Ru-Th-CTF/RGO) that synergistically knits a rebuilt extended π-delocalized network of the D-A1 -A2 system (multiple donor or acceptor units, Ru-Th-CTF) with reduced graphene oxide (RGO) is developed. It is verified that the single-site Ru units in Ru-Th-CTF/RGO act as effective secondary electron acceptors in the lateral direction for multistage charge separation/transport. Simultaneously, the π-stacked and covalently bonded graphene is regarded as a hole extraction layer, accelerating the separation/transport of the photogenerated charges in the vertical direction over the Ru-Th-CTF/RGO Schottky junction with full use of photogenerated electrons for the reduction reaction. Thus, the obtained photocatalyst has an excellent CO2 -to-formate conversion rate (≈11050 µmol g-1 h-1 ) and selectivity (≈99%), producing a state-of-the-art catalyst for the heterogeneous conversion of CO2 to formate without an extra photosensitizer.

Flexible Covalent Organic Network with Ordered Honeycomb Nanoarchitecture for Molecular Separations.

Membranes with precisely defined nanostructure are desirable for energy-efficient molecular separations. The emergence of membranes with honeycomb lattice or topological nanopores is of fundamental importance. The tailor-made nanostructure and morphology may have huge potential to resolve the longstanding bottlenecks in membrane science and technology. Herein, inspired by honeycomb architecture, we demonstrate an effective and scalable route based on interfacial polymerization (IP) to generate flexible and ordered covalent organic network (CON) membranes for liquid-phase molecular separations. The aperture size of a CON membrane can be reasonably designed through the strong covalent bond between molecular building blocks. The fabricated CON membrane formed by IP showed an obviously size-dependent sieving of molecules, yielding a stepwise conversion from low rejection to the expected high rejection. Moreover, the CON membrane was also found to have the sieving capability for tetracycline and ciprofloxacin, ascribed to the effect of size exclusion by an ordered single-nanoscale channel (<1 nm). This approach provides a viable strategy for creating target-sized channels from molecular-level design and demonstrates their potential for accurate molecular separations.

A 2D Soft Covalent Organic Framework Membrane Prepared via a Molecular Bridge.

Highly flexible and robust self-standing covalent organic framework (COF) membranes with rapid preparation are important but technically challenging for achieving precise separation. Herein , a novel imine-based 2D soft covalent organic framework (SCOF) membrane with a large area of 226.9 cm2 , via ingeniously selecting an aldehyde flexible linker and a trigonal building block, is reported. The soft 2D covalent organic framework membrane is rapidly formed (≈5 min) based on the sodium dodecyl sulfate (SDS) molecular channel constructed at the water/dichloromethane (DCM) interface, which is the record-fast SCOF membrane formation and 72 times faster than that in the reported literature. MD simulation and DFT calculation elucidate that the dynamic, self-assembled SDS molecular channel facilitates faster and more homogeneous transfer of amine monomers in the bulk, thereby forming a soft 2D self-standing COF membrane with more uniform pores. The formed SCOF membrane exhibits superb sieving capability for small molecules, robustness in strong alkaline (5 mol L-1 NaOH), acid (0.1 mol L-1 HCl), and various organic solutions, and sufficient flexibility with a large curvature of 2000 m-1 for membrane-based separation science and technology.

Nanoarchitectonics of carbon molecular sieve membranes with graphene oxide and polyimide for hydrogen purification.

Hydrogen is an important energy carrier for the transition to a carbon-neutral society, the efficient separation and purification of hydrogen from gaseous mixtures is a critical step for the implementation of a hydrogen economy. In this work, graphene oxide (GO) tuned polyimide carbon molecular sieve (CMS) membranes were prepared by carbonization, which show an attractive combination of high permeability, selectivity and stability. The gas sorption isotherms indicate that the gas sorption capability increases with the carbonization temperature and follows the order of PI-GO-1.0%-600 °C > PI-GO-1.0%-550 °C > PI-GO-1.0%-500 °C, more micropores would be created under higher temperatures under GO guidance. The synergistic GO guidance and subsequent carbonization of PI-GO-1.0% at 550 °C increased H2 permeability from 958 to 7462 Barrer and H2/N2 selectivity from 14 to 117, superior to state-of-the-art polymeric materials and surpassing Robeson's upper bound line. As the carbonization temperature increased, the CMS membranes gradually changed from the turbostratic polymeric structure to a denser and more ordered graphite structure. Therefore, ultrahigh selectivities for H2/CO2 (17), H2/N2 (157), and H2/CH4 (243) gas pairs were achieved while maintaining moderate H2 gas permeabilities. This research opens up new avenues for GO tuned CMS membranes with desirable molecular sieving ability for hydrogen purification.

AnDHN, a Dehydrin Protein From Ammopiptanthus nanus, Mitigates the Negative Effects of Drought Stress in Plants.

Dehydrins (DHNs) play crucial roles in a broad spectrum of abiotic stresses in model plants. However, the evolutionary role of DHNs has not been explored, and the function of DHN proteins is largely unknown in Ammopiptanthus nanus (A. nanus), an ancient and endangered legume species from the deserts of northwestern China. In this study, we isolated a drought-response gene (c195333_g1_i1) from a drought-induced RNA-seq library of A. nanus. Evolutionary bioinformatics showed that c195333_g1_i1 is an ortholog of Arabidopsis DHN, and we renamed it AnDHN. Moreover, DHN proteins may define a class of proteins that are evolutionarily conserved in all angiosperms that have experienced a contraction during the evolution of legumes. Arabidopsis plants overexpressing AnDHN exhibited morpho-physiological changes, such as an increased germination rate, higher relative water content (RWC), higher proline (PRO) content, increased peroxidase (POD) and catalase (CAT) activities, lower contents of malondialdehyde (MDA), H2O2 and O2 -, and longer root length. Our results showed that the transgenic lines had improved drought resistance with deep root system architecture, excellent water retention, increased osmotic adjustment, and enhanced reactive oxygen species (ROS) scavenging. Furthermore, the transgenic lines also had enhanced salt and cold tolerance. Our findings demonstrate that AnDHN may be a good candidate gene for improving abiotic stress tolerance in crops. Key Message: Using transcriptome analysis in Ammopiptanthus nanus, we isolated a drought-responsive gene, AnDHN, that plays a key role in enhancing abiotic stress tolerance in plants, with strong functional diversification in legumes.

Studies on an ultrasonic atomization feed direct methanol fuel cell.

Direct methanol fuel cell (DMFC) is promising as an energy conversion device for the replacement of conventional chemical cell in future, owing to its convenient fuel storage, high energy density and low working temperature. The development of DMFC technology is currently limited by catalyst poison and methanol crossover. To alleviate the methanol crossover, a novel fuel supply system based on ultrasonic atomization is proposed. Experimental investigations on this fuel supply system to evaluate methanol permeation rates, open circuit voltages (OCVs) and polarization curves under a series of conditions have been carried out and reported in this paper. In comparison with the traditional liquid feed DMFC system, it can be found that the methanol crossover under the ultrasonic atomization feed system was significantly reduced because the DMFC reaches a large stable OCV value. Moreover, the polarization performance does not vary significantly with the liquid feed style. Therefore, the cell fed by ultrasonic atomization can be operated with a high concentration methanol to improve the energy density of DMFC. Under the supply condition of relatively high concentration methanol such as 4M and 8M, the maximum power density fed by ultrasonic atomization is higher than liquid by 6.05% and 12.94% respectively.