Covalent Organic Frameworks as Single-Site Photocatalysts for Solar-to-Fuel Conversion.

Single-site photocatalysts (SSPCs) are well-established as potent platforms for designing innovative materials to accomplish direct solar-to-fuel conversion. Compared to classical inorganic porous materials, such as zeolites and silica, covalent organic frameworks (COFs)─an emerging class of porous polymers that combine high surface areas, structural diversity, and chemical stability─are attractive candidates for SSPCs due to their molecular-level precision and intrinsic light harvesting ability, both amenable to structural engineering. In this Perspective, we summarize the design concepts and state-of-the-art strategies for the construction of COF SSPCs, and we review the development of COF SSPCs and their applications in solar-to-fuel conversion from their inception. Underlying pitfalls concerning photocatalytic characterization are discussed, and perspectives for the future development of this burgeoning field are given.

Plant Growth Promotion and Heat Stress Amelioration in Arabidopsis Inoculated with Paraburkholderia phytofirmans PsJN Rhizobacteria Quantified with the GrowScreen-Agar II Phenotyping Platform.

High temperatures inhibit plant growth. A proposed strategy for improving plant productivity under elevated temperatures is the use of plant growth-promoting rhizobacteria (PGPR). While the effects of PGPR on plant shoots have been extensively explored, roots-particularly their spatial and temporal dynamics-have been hard to study, due to their below-ground nature. Here, we characterized the time- and tissue-specific morphological changes in bacterized plants using a novel non-invasive high-resolution plant phenotyping and imaging platform-GrowScreen-Agar II. The platform uses custom-made agar plates, which allow air exchange to occur with the agar medium and enable the shoot to grow outside the compartment. The platform provides light protection to the roots, the exposure of it to the shoots, and the non-invasive phenotyping of both organs. Arabidopsis thaliana, co-cultivated with Paraburkholderia phytofirmans PsJN at elevated and ambient temperatures, showed increased lengths, growth rates, and numbers of roots. However, the magnitude and direction of the growth promotion varied depending on root type, timing, and temperature. The root length and distribution per depth and according to time was also influenced by bacterization and the temperature. The shoot biomass increased at the later stages under ambient temperature in the bacterized plants. The study offers insights into the timing of the tissue-specific, PsJN-induced morphological changes and should facilitate future molecular and biochemical studies on plant-microbe-environment interactions.

Impact of Moderate Cold and Salt Stress on the Accumulation of Antioxidant Flavonoids in the Leaves of Two Capsicum Cultivars.

The horticultural production of bell peppers generates large quantities of residual biomass. Abiotic stress stimulates the production of protective flavonoids, so the deliberate application of stress to the plants after fruit harvest could provide a strategy to valorize horticultural residuals by increasing flavonoid concentrations, facilitating their industrial extraction. Here we exposed two Capsicum cultivars, a chilli and a bell pepper, to cold and salt stress and combinations thereof to determine their valorization potential. Noninvasive image-based phenotyping and multiparametric fluorescence measurements indicated that all stress treatments inhibited plant growth and reduced the leaf chlorophyll fluorescence index, with the chilli cultivar showing greater sensitivity. The fluorescence-based FLAV index allowed the noninvasive assessment of foliar luteolin glycosides. High-performance liquid chromatography-mass spectrometry (HPLC-MS) analysis showed that moderate cold increased the levels of two foliar antioxidant luteolin glycosides in both cultivars, with bell pepper containing the highest amounts (induced to maximum 5.5 mg g-1 DW cynaroside and 37.0 mg g-1 DW graveobioside A) after combined stress treatment. These data confirm the potential of abiotic stress for the valorization of residual leaf biomass to enhance the industrial extraction of antioxidant and bioactive flavonoids.

The platform GrowScreen-Agar enables identification of phenotypic diversity in root and shoot growth traits of agar grown plants.

BACKGROUND: Root system architecture and especially its plasticity in acclimation to variable environments play a crucial role in the ability of plants to explore and acquire efficiently soil resources and ensure plant productivity. Non-destructive measurement methods are indispensable to quantify dynamic growth traits. For closing the phenotyping gap, we have developed an automated phenotyping platform, GrowScreen-Agar, for non-destructive characterization of root and shoot traits of plants grown in transparent agar medium. RESULTS: The phenotyping system is capable to phenotype root systems and correlate them to whole plant development of up to 280 Arabidopsis plants within 15 min. The potential of the platform has been demonstrated by quantifying phenotypic differences within 78 Arabidopsis accessions from the 1001 genomes project. The chosen concept 'plant-to-sensor' is based on transporting plants to the imaging position, which allows for flexible experimental size and design. As transporting causes mechanical vibrations of plants, we have validated that daily imaging, and consequently, moving plants has negligible influence on plant development. Plants are cultivated in square Petri dishes modified to allow the shoot to grow in the ambient air while the roots grow inside the Petri dish filled with agar. Because it is common practice in the scientific community to grow Arabidopsis plants completely enclosed in Petri dishes, we compared development of plants that had the shoot inside with that of plants that had the shoot outside the plate. Roots of plants grown completely inside the Petri dish grew 58% slower, produced a 1.8 times higher lateral root density and showed an etiolated shoot whereas plants whose shoot grew outside the plate formed a rosette. In addition, the setup with the shoot growing outside the plate offers the unique option to accurately measure both, leaf and root traits, non-destructively, and treat roots and shoots separately. CONCLUSIONS: Because the GrowScreen-Agar system can be moved from one growth chamber to another, plants can be phenotyped under a wide range of environmental conditions including future climate scenarios. In combination with a measurement throughput enabling phenotyping a large set of mutants or accessions, the platform will contribute to the identification of key genes.

Total scattering reveals the hidden stacking disorder in a 2D covalent organic framework.

Interactions between extended π-systems are often invoked as the main driving force for stacking and crystallization of 2D organic polymers. In covalent organic frameworks (COFs), the stacking strongly influences properties such as the accessibility of functional sites, pore geometry, and surface states, but the exact nature of the interlayer interactions is mostly elusive. The stacking mode is often identified as eclipsed based on observed high symmetry diffraction patterns. However, as pointed out by various studies, the energetics of eclipsed stacking are not favorable and offset stacking is preferred. This work presents lower and higher apparent symmetry modifications of the imine-linked TTI-COF prepared through high- and low-temperature reactions. Through local structure investigation by pair distribution function analysis and simulations of stacking disorder, we observe random local layer offsets in the low temperature modification. We show that while stacking disorder can be easily overlooked due to the apparent crystallographic symmetry of these materials, total scattering methods can help clarify this information and suggest that defective local structures could be much more prevalent in COFs than previously thought. A detailed analysis of the local structure helps to improve the search for and design of highly porous tailor-made materials.

Evaluation and application of molecular denitrification monitoring methods in the northern Lake Tai, China.

Worldwide, excessive reactive nitrogen in groundwater and surface waters is a growing problem, especially in areas that face rapid urbanization and industrialization. One example for environmental nitrogen pollution is the Lake Tai, China's third largest freshwater Lake, located in the Yangtze River basin. Due to the rapid development of the surrounding area, nitrogen compounds like nitrate are discharged into the Lake. Consequently, eutrophication and harmful algae blooms increased and led to the production of toxins directly affecting water consumers through the water supply chain. Denitrification is the main process that attenuates nitrate by converting it into atmospheric nitrogen and represents an intrinsic natural process to compensate the excess reactive nitrogen. In this study, the methodology to detect nitrate reducing bacteria on a functional gene and transcriptional level was optimized and verified in laboratory experiments with a pure culture of Pseudomonas veronii, isolated from Lake Tai. We demonstrated that transcripts analysis (mRNA) did correspond with nitrate reduction activity. Subsequently, the abundance and the activity of nitrate reducing bacteria in Lake Tai were assessed using the developed methods. We demonstrated that nitrate reducing bacteria can be found throughout all sediment and water samples taken from the northern Lake Tai in September 2017. Measurements of narG transcripts also indicated the activity of the membrane-bound nitrate reductase in the water samples. However, the bioinformatic analysis of narG sequences showed varying binding efficiency of primer and gene sites in dependence of phylogenetic groups, which may lead to an underestimation in the qPCR method. Thus, it is important to point out the precautions and limitations of primer systems to monitor nitrogen transformation by qPCR in the environment. Based on this study, mRNA detection methods are suitable for improved microbiological monitoring of denitrification, as an intrinsic process in Lake Tai to mitigate the inflowing reactive nitrogen compounds.

Aminopyridine-Borane Complexes as Hydrogen Atom Donor Reagents: Reaction Mechanism and Substrate Selectivity.

Lewis base-borane complexes are shown to be potent hydrogen atom donors in radical chain reduction reactions. Results obtained in 1 H, 11 B, and 13 C NMR measurements and kinetic experiments support a complex reaction mechanism involving the parent borane as well as its initial reaction products as active hydrogen atom donors. Efficient reduction reactions of iodides, bromides, and xanthates in apolar solvents rely on initiator systems generating oxygen-centered radicals under thermal conditions and pyridine-borane complexes carrying solubilizing substituents. In contrast to tin hydride reagents, the pyridine-boranes reduce xanthates faster than the corresponding iodides.

GrowScreen-PaGe, a non-invasive, high-throughput phenotyping system based on germination paper to quantify crop phenotypic diversity and plasticity of root traits under varying nutrient supply.

New techniques and approaches have been developed for root phenotyping recently; however, rapid and repeatable non-invasive root phenotyping remains challenging. Here, we present GrowScreen-PaGe, a non-invasive, high-throughput phenotyping system (4 plants min-1) based on flat germination paper. GrowScreen-PaGe allows the acquisition of time series of the developing root systems of 500 plants, thereby enabling to quantify short-term variations in root system. The choice of germination paper was found to be crucial and paper☓root interaction should be considered when comparing data from different studies on germination paper. The system is suitable for phenotyping dicot and monocot plant species. The potential of the system for high-throughput phenotyping was shown by investigating phenotypic diversity of root traits in a collection of 180 rapeseed accessions and of 52 barley genotypes grown under control and nutrient-starved conditions. Most traits showed a large variation linked to both genotype and treatment. In general, root length traits contributed more than shape and branching related traits in separating the genotypes. Overall, results showed that GrowScreen-PaGe will be a powerful resource to investigate root systems and root plasticity of large sets of plants and to explore the molecular and genetic root traits of various species including for crop improvement programs.

Rapid determination of leaf area and plant height by using light curtain arrays in four species with contrasting shoot architecture.

BACKGROUND: Light curtain arrays (LC), a recently introduced phenotyping method, yield a binary data matrix from which a shoot silhouette is reconstructed. We addressed the accuracy and applicability of LC in assessing leaf area and maximum height (base to the highest leaf tip) in a phenotyping platform. LC were integrated to an automated routine for positioning, allowing in situ measurements. Two dicotyledonous (rapeseed, tomato) and two monocotyledonous (maize, barley) species with contrasting shoot architecture were investigated. To evaluate if averaging multiple view angles helps in resolving self-overlaps, we acquired a data set by rotating plants every 10° for 170°. To test how rapid these measurements can be without loss of information, we evaluated nine scanning speeds. Leaf area of overlapping plants was also estimated to assess the possibility to scale this method for plant stands. RESULTS: The relation between measured and calculated maximum height was linear and nearly the same for all species. Linear relations were also found between plant leaf area and calculated pixel area. However, the regression slope was different between monocotyledonous and dicotyledonous species. Increasing the scanning speed stepwise from 0.9 to 23.4 m s-1 did not affect the estimation of maximum height. Instead, the calculated pixel area was inversely proportional to scanning speed. The estimation of plant leaf area by means of calculated pixel area became more accurate by averaging consecutive silhouettes and/or increasing the angle between them. Simulations showed that decreasing plant distance gradually from 20 to 0 cm, led to underestimation of plant leaf area owing to overlaps. This underestimation was more important for large plants of dicotyledonous species and for small plants of monocotyledonous ones. CONCLUSIONS: LC offer an accurate estimation of plant leaf area and maximum height, while the number of consecutive silhouettes that needs to be averaged is species-dependent. A constant scanning speed is important for leaf area estimations by using LC. Simulations of the effect of varying plant spacing gave promising results for method application in sets of partly overlapping plants, which applies also to field conditions during and after canopy closure for crops sown in rows.

GROWSCREEN-Rhizo is a novel phenotyping robot enabling simultaneous measurements of root and shoot growth for plants grown in soil-filled rhizotrons.

Root systems play an essential role in ensuring plant productivity. Experiments conducted in controlled environments and simulation models suggest that root geometry and responses of root architecture to environmental factors should be studied as a priority. However, compared with aboveground plant organs, roots are not easily accessible by non-invasive analyses and field research is still based almost completely on manual, destructive methods. Contributing to reducing the gap between laboratory and field experiments, we present a novel phenotyping system (GROWSCREEN-Rhizo), which is capable of automatically imaging roots and shoots of plants grown in soil-filled rhizotrons (up to a volume of ~18L) with a throughput of 60 rhizotrons per hour. Analysis of plants grown in this setup is restricted to a certain plant size (up to a shoot height of 80cm and root-system depth of 90cm). We performed validation experiments using six different species and for barley and maize, we studied the effect of moderate soil compaction, which is a relevant factor in the field. First, we found that the portion of root systems that is visible through the rhizotrons' transparent plate is representative of the total root system. The percentage of visible roots decreases with increasing average root diameter of the plant species studied and depends, to some extent, on environmental conditions. Second, we could measure relatively minor changes in root-system architecture induced by a moderate increase in soil compaction. Taken together, these findings demonstrate the good potential of this methodology to characterise root geometry and temporal growth responses with relatively high spatial accuracy and resolution for both monocotyledonous and dicotyledonous species. Our prototype will allow the design of high-throughput screening methodologies simulating environmental scenarios that are relevant in the field and will support breeding efforts towards improved resource use efficiency and stability of crop yields.

An MCBJ case study: The influence of π-conjugation on the single-molecule conductance at a solid/liquid interface.

π-Conjugation plays an important role in charge transport through single molecular junctions. We describe in this paper the construction of a mechanically controlled break-junction setup (MCBJ) equipped with a highly sensitive log I-V converter in order to measure ultralow conductances of molecular rods trapped between two gold leads. The current resolution of the setup reaches down to 10 fA. We report single-molecule conductance measurements of an anthracene-based linearly conjugated molecule (AC), of an anthraquinone-based cross-conjugated molecule (AQ), and of a dihydroanthracene-based molecule (AH) with a broken conjugation. The quantitative analysis of complementary current-distance and current-voltage measurements revealed details of the influence of π-conjugation on the single-molecule conductance.