Grain quality traits within the wheat (Triticum spp.) genepool: prospects for improved nutrition through de novo domestication.

BACKGROUND: Wild relatives of wheat (Triticum spp.) harbor beneficial alleles for potential improvement and de novo domestication of selected genotypes with advantageous traits. We analyzed the nutrient composition in wild diploid and tetraploid wheats and their domesticated diploid, tetraploid and hexaploid relatives under field conditions in Germany and compared them with modern Triticum aestivum and Triticum durum cultivars. Grain iron (Fe) and zinc (Zn) concentrations, phytate:mineral molar ratios, grain protein content (GPC) and antioxidant activity were analyzed across 125 genotypes. RESULTS: Grain Fe and Zn concentrations in wild wheats were 72 mg kg-1 and 59 mg kg-1, respectively, with improved bioavailability indicated by Phytate:Fe and Phytate:Zn molar ratios (11.7 and 16.9, respectively) and GPC (231 g kg-1). By comparison, grain Fe and Zn concentrations in landrace taxa were 54 mg kg-1 and 55 mg kg-1, respectively, with lower Phytate:Fe and Phytate:Zn molar ratios (15.1 and 17.5, respectively) and GPC (178 g kg-1). Average grain Fe accumulation in Triticum araraticum was 73 mg kg-1, reaching 116 mg kg-1, with high Fe bioavailability (Phyt:Fe: 11.7; minimum: 7.2). Wild wheats, landraces and modern cultivars showed no differences in antioxidant activity. Triticum zhukovskyi stood out with high grain micronutrient concentrations and favorable molar ratios. It was also the only taxon with elevated antioxidant activity. CONCLUSION: Our results indicate alteration of grain quality during domestication. T. araraticum has promising genotypes with advantageous grain quality characteristics that could be selected for de novo domestication. Favorable nutritional traits in the GGAA wheat lineage (T. araraticum and T. zhukovskyi) hold promise for improving grain quality traits. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

The grain quality of wheat wild relatives in the evolutionary context.

KEY MESSAGE: We evaluated the potential of wheat wild relatives for the improvement in grain quality characteristics including micronutrients (Fe, Zn) and gluten and identified diploid wheats and the timopheevii lineage as the most promising resources. Domestication enabled the advancement of civilization through modification of plants according to human requirements. Continuous selection and cultivation of domesticated plants induced genetic bottlenecks. However, ancient diversity has been conserved in crop wild relatives. Wheat (Triticum aestivum L.; Triticum durum Desf.) is one of the most important staple foods and was among the first domesticated crop species. Its evolutionary diversity includes diploid, tetraploid and hexaploid species from the Triticum and Aegilops taxa and different genomes, generating an AA, BBAA/GGAA and BBAADD/GGAAAmAm genepool, respectively. Breeding and improvement in wheat altered its grain quality. In this review, we identified evolutionary patterns and the potential of wheat wild relatives for quality improvement regarding the micronutrients Iron (Fe) and Zinc (Zn), the gluten storage proteins α-gliadins and high molecular weight glutenin subunits (HMW-GS), and the secondary metabolite phenolics. Generally, the timopheevii lineage has been neglected to date regarding grain quality studies. Thus, the timopheevii lineage should be subject to grain quality research to explore the full diversity of the wheat gene pool.

Chromosomal introgressions from Oryza meridionalis into domesticated rice Oryza sativa result in iron tolerance.

Iron (Fe) toxicity is one of the most common mineral disorders affecting rice (Oryza sativa) production in flooded lowland fields. Oryza meridionalis is indigenous to northern Australia and grows in regions with Fe-rich soils, making it a candidate for use in adaptive breeding. With the aim of understanding tolerance mechanisms in rice, we screened a population of interspecific introgression lines from a cross between O. sativa and O. meridionalis for the identification of quantitative trait loci (QTLs) contributing to Fe-toxicity tolerance. Six putative QTLs were identified. A line carrying one introgression from O. meridionalis on chromosome 9 associated with one QTL was highly tolerant despite very high shoot Fe concentrations. Physiological, biochemical, ionomic, and transcriptomic analyses showed that the tolerance of the introgression lines could partly be explained by higher relative Fe retention in the leaf sheath and culm. We constructed the interspecific hybrid genome in silico for transcriptomic analysis and identified differentially regulated introgressed genes from O. meridionalis that could be involved in shoot-based Fe tolerance, such as metallothioneins, glutathione S-transferases, and transporters from the ABC and MFS families. This work demonstrates that introgressions of O. meridionalis into the O. sativa genome can confer increased tolerance to excess Fe.

Exogenous application of melatonin to plants, algae, and harvested products to sustain agricultural productivity and enhance nutritional and nutraceutical value: A meta-analysis.

Melatonin is produced by plants, algae, and animals. Worldwide studies show diverse positive effects of exogenous melatonin on plants, edible plant products, and algae, but the potential of melatonin to enhance food and feed systems through these positive effects remains largely unexplored. Through a meta-analysis of about 25,000 observations, we show for the first time that exogenous application of melatonin significantly increases crop productivity and yields, and enhances the nutritional and nutraceutical value of edible plant products and algae by regulating diverse biological functions. We demonstrate that melatonin can improve plants, edible plant products, and algae under various current climate change scenarios, environmental pollution factors, and other stresses by about 7% to nearly 30%, on average, depending on the stressor. We also analyze various technical/methodological factors influencing the desired outcomes and identify conditions that offer optimal enhancement. We show that the positive effect of melatonin on plants and edible plant products varies among species, genera, and families, and strongly depends on the concentration of melatonin and treatment duration. The effect of melatonin is slightly lower on the monocot clade Commelinids than on the eudicot clades Asterids and Rosids. We also show that its stimulatory effect on plants depends on cultivation system, with a larger effect obtained in hydroponic systems. However, it does not depend on application stage (seed or vegetative), application route (foliage, roots, or seed), and whether the cultivation system is ex vivo or in vivo. This is the first meta-analysis examining the effects of melatonin on plants, edible plant products, and algae, and offers a scientific and technical roadmap facilitating sustainable food and feed production through the application of exogenous melatonin.

Genetic dissection of bread wheat diversity and identification of adaptive loci in response to elevated tropospheric ozone.

Rising tropospheric ozone affects the performance of important cereal crops thus threatening global food security. In this study, genetic variation of wheat regarding its physiological and yield responses to ozone was explored by exposing a diversity panel of 150 wheat genotypes to elevated ozone and control conditions throughout the growing season. Differential responses to ozone were observed for foliar symptom formation quantified as leaf bronzing score (LBS), vegetation indices and yield components. Vegetation indices representing the carotenoid to chlorophyll pigment ratio (such as Lic2) were particularly ozone-responsive and were thus considered suitable for the non-invasive diagnosing of ozone stress. Genetic variation in ozone-responsive traits was dissected by a genome-wide association study (GWAS). Significant marker-trait associations were identified for LBS on chromosome 5A and for vegetation indices (NDVI and Lic2) on chromosomes 6B and 6D. Analysis of linkage disequilibrium (LD) in these chromosomal regions revealed distinct LD blocks containing genes with a putative function in plant redox biology such as cytochrome P450 proteins and peroxidases. This study gives novel insight into the natural genetic variation in wheat ozone response, and lays the foundation for the molecular breeding of tolerant wheat varieties.

Ascorbate oxidation activates systemic defence against root-knot nematode Meloidogyne graminicola in rice.

Ascorbic acid (AA) is the major antioxidant buffer produced in the shoot tissue of plants. Previous studies on root-knot nematode (RKN; Meloidogyne graminicola)-infected rice (Oryza sativa) plants showed differential expression of AA-recycling genes, although their functional role was unknown. Our results confirmed increased dehydroascorbate (DHA) levels in nematode-induced root galls, while AA mutants were significantly more susceptible to nematode infection. External applications of ascorbate oxidase (AO), DHA, or reduced AA, revealed systemic effects of ascorbate oxidation on rice defence versus RKN, associated with a primed accumulation of H2O2 upon nematode infection. To confirm and further investigate these systemic effects, a transcriptome analysis was done on roots of foliar AO-treated plants, revealing activation of the ethylene (ET) response and jasmonic acid (JA) biosynthesis pathways in roots, which was confirmed by hormone measurements. Activation of these pathways by methyl-JA, or ethephon treatment can complement the susceptibility phenotype of the rice Vitamin C (vtc1) mutant. Experiments on the jasmonate signalling (jar1) mutant or using chemical JA/ET inhibitors confirm that the effects of ascorbate oxidation are dependent on both the JA and ET pathways. Collectively, our data reveal a novel pathway in which ascorbate oxidation induces systemic defence against RKNs.

Ethylenediurea (EDU) mitigates the negative effects of ozone in rice: Insights into its mode of action.

Monitoring of ozone damage to crops plays an increasingly important role for the food security of many developing countries. Ethylenediurea (EDU) could be a tool to assess ozone damage to vegetation on field scale, but its physiological mode of action remains unclear. This study investigated mechanisms underlying the ozone-protection effect of EDU in controlled chamber experiments. Ozone sensitive and tolerant rice genotypes were exposed to ozone (108 ppb, 7 hr day-1 ) and control conditions. EDU alleviated ozone effects on plant morphology, foliar symptoms, lipid peroxidation, and photosynthetic parameters in sensitive genotypes. Transcriptome profiling by RNA sequencing revealed that thousands of genes responded to ozone in a sensitive variety, but almost none responded to EDU. Significant interactions between ozone and EDU application occurred mostly in ozone responsive genes, in which up-regulation was mitigated by EDU application. Further experiments documented ozone degrading properties of EDU, as well as EDU deposits on leaf surfaces possibly related to surface protection. EDU application did not mitigate the reaction of plants to other abiotic stresses, including iron toxicity, zinc deficiency, and salinity. This study provided evidence that EDU is a surface protectant that specifically mitigates ozone stress without interfering directly with the plants' stress response systems.

Closing the global ozone yield gap: Quantification and cobenefits for multistress tolerance.

Increasing both crop productivity and the tolerance of crops to abiotic and biotic stresses is a major challenge for global food security in our rapidly changing climate. For the first time, we show how the spatial variation and severity of tropospheric ozone effects on yield compare with effects of other stresses on a global scale, and discuss mitigating actions against the negative effects of ozone. We show that the sensitivity to ozone declines in the order soybean > wheat > maize > rice, with genotypic variation in response being most pronounced for soybean and rice. Based on stomatal uptake, we estimate that ozone (mean of 2010-2012) reduces global yield annually by 12.4%, 7.1%, 4.4% and 6.1% for soybean, wheat, rice and maize, respectively (the "ozone yield gaps"), adding up to 227 Tg of lost yield. Our modelling shows that the highest ozone-induced production losses for soybean are in North and South America whilst for wheat they are in India and China, for rice in parts of India, Bangladesh, China and Indonesia, and for maize in China and the United States. Crucially, we also show that the same areas are often also at risk of high losses from pests and diseases, heat stress and to a lesser extent aridity and nutrient stress. In a solution-focussed analysis of these results, we provide a crop ideotype with tolerance of multiple stresses (including ozone) and describe how ozone effects could be included in crop breeding programmes. We also discuss altered crop management approaches that could be applied to reduce ozone impacts in the shorter term. Given the severity of ozone effects on staple food crops in areas of the world that are also challenged by other stresses, we recommend increased attention to the benefits that could be gained from addressing the ozone yield gap.

Shoot tolerance mechanisms to iron toxicity in rice (Oryza sativa L.).

Iron toxicity frequently affects lowland rice and leads to oxidative stress via the Fenton reaction. Tolerance mechanisms were investigated in contrasting genotypes: the intolerant IR29 and the tolerant recombinant inbred line FL483. Seedlings were exposed to 1000 mg L-1 ferrous iron, and the regulation of genes involved in three hypothetical tolerance mechanisms was investigated (I) Iron uptake, partitioning and storage. The iron concentration and speciation in different plant tissues did not differ significantly between genotypes. Sub-cellular iron partitioning genes such as vacuolar iron transporters or ferritin showed no genotypic differences. (II) Antioxidant biosynthesis. Only one gene involved in carotenoid biosynthesis showed genotypic differences, but carotenoids are unlikely to scavenge the reactive oxygen species (ROS) involved in Fe toxicity, i.e. H2 O2 and hydroxyl radicals. (III) Enzymatic activities for ROS scavenging and antioxidants turnover. In shoots, glutathione-S-transferase and ascorbate oxidase genes showed genotypic differences, and consistently, the tolerant FL483 had lower dehydroascorbate reductase and higher ascorbate oxidase activity, suggesting that high rates ascorbate reduction confer sensitivity. This hypothesis was confirmed by application of exogenous reduced ascorbate or L-galactono-1,4-lactone, which increased lipid peroxidation under iron toxic conditions. Our results demonstrate in planta pro-oxidant activity of reduced ascorbate in the presence of iron.

Genetic factors underlying boron toxicity tolerance in rice: genome-wide association study and transcriptomic analysis.

Boron (B) toxicity is a nutritional disorder affecting crop production in many parts of the world. This study explored genetic factors associated with B tolerance in rice (Oryza sativa L.) through an integrated genome mapping and transcriptomic approach. Variation in B tolerance was first evaluated by screening a panel of 137 indica genotypes in B toxic conditions (+2 mM B), followed by genome-wide association study (GWAS). Leaf bronzing and greenness were significantly correlated with shoot and root dry weight, but B uptake was not correlated with any stress phenotype. Single nucleotide polymorphism (SNP) markers exceeding a significance value of ­log10P>4.0 were obtained for four traits, namely leaf bronzing, shoot dry weight, root dry weight, and root length. Linkage disequilibrium block analysis of the corresponding chromosomal regions revealed candidate loci containing 75 gene models. Two contrasting genotypes from the panel were selected for transcriptomic analysis, which included gene ontology enrichment analysis of differentially regulated genes and investigating transcriptional responses of GWAS candidate genes. Characteristic expression patterns associated with tolerance or sensitivity were seen in genes related to biochemical binding, transport, transcriptional regulation, and redox homeostasis. These results advance the understanding of genetic and physiological factors associated with B tolerance in rice.

Demographic, Clinical and Polysomnographic Characteristics of Childhood- and Adult-Onset Sleepwalking in Adults.

BACKGROUND: Sleepwalking (SW) is found to affect children predominantly, but it can persist or appear de novo even among adults. In this study, we assessed the demographic, clinical and polysomnographic profile, trigger factors and associated comorbidities of adult-onset (AO-SW) and childhood-onset (CO-SW) adult sleepwalkers. METHODS: In adult sleepwalkers, a structured clinical interview, a battery of questionnaires, video-polysomnography (v-PSG) and standard electroencephalography (EEG) were performed. RESULTS: Among 63 sleepwalkers, 45% had ≥1 episodes/month, 54% had partial recall of the episodes and 36% reported trigger factors for SW. Almost all subjects reported co-occurring parasomnias. In v-PSG, 4% exhibited episodes of SW, 17% confusional arousals, 21% had an increased apnea-hypopnea-index and 6% exhibited features of an overlap parasomnia disorder. In our cohort, 73% reported CO-SW and 27% AO-SW. In subjects with AO-SW, positive family history for parasomnias was found in 33% (vs. 49% in CO-SW), neurological comorbidities in 44% (vs. 14%), psychiatric comorbidities in 25% (vs. 33%), EEG abnormalities in 50% (vs. 29%). Violence during SW episodes was more frequent in males and in subjects with CO-SW (45% for self-injury and 44% for violent behaviour vs. 33 and 29% respectively in the AO-SW group). CONCLUSIONS: Adult SW represents a complex and potentially dangerous condition. The characteristics of AO-SW often differ from those of CO-SW.

A Novel Gene, OZONE-RESPONSIVE APOPLASTIC PROTEIN1, Enhances Cell Death in Ozone Stress in Rice.

A novel protein, OZONE-RESPONSIVE APOPLASTIC PROTEIN1 (OsORAP1), was characterized, which was previously suggested as a candidate gene underlying OzT9, a quantitative trait locus for ozone stress tolerance in rice (Oryza sativa). The sequence of OsORAP1 was similar to that of ASCORBATE OXIDASE (AO) proteins. It was localized in the apoplast, as shown by transient expression of an OsORAP1/green fluorescent protein fusion construct in Nicotiana benthamiana leaf epidermal and mesophyll cells, but did not possess AO activity, as shown by heterologous expression of OsORAP1 in Arabidopsis (Arabidopsis thaliana) mutants with reduced background AO activity. A knockout rice line of OsORAP1 showed enhanced tolerance to ozone stress (120 nL L(-1) average daytime concentration, 20 d), as demonstrated by less formation of leaf visible symptoms (i.e. cell death), less lipid peroxidation, and lower NADPH oxidase activity, indicating reduced active production of reactive oxygen species. In contrast, the effect of ozone on chlorophyll content was not significantly different among the lines. These observations suggested that OsORAP1 specifically induced cell death in ozone stress. Significantly enhanced expression of jasmonic acid-responsive genes in the knockout line implied the involvement of the jasmonic acid pathway in symptom mitigation. Sequence analysis revealed extensive polymorphisms in the promoter region of OsORAP1 between the ozone-susceptible cv Nipponbare and the ozone-tolerant cv Kasalath, the OzT9 donor variety, which could be responsible for the differential regulation of OsORAP1 reported earlier. These pieces of evidence suggested that OsORAP1 enhanced cell death in ozone stress, and its expression levels could explain the effect of a previously reported quantitative trait locus.

Ascorbate biosynthesis and its involvement in stress tolerance and plant development in rice (Oryza sativa L.).

Ascorbic acid (AsA) biosynthesis and its implications for stress tolerance and plant development were investigated in a set of rice knock-out (KO) mutants for AsA biosynthetic genes and their wild-types. KO of two isoforms of GDP-D-mannose epimerase (OsGME) reduced the foliar AsA level by 20-30%, and KO of GDP-L-galactose phosphorylase (OsGGP) by 80%, while KO of myo-inositol oxygenase (OsMIOX) did not affect foliar AsA levels. AsA concentration was negatively correlated with lipid peroxidation in foliar tissue under ozone stress and zinc deficiency, but did not affect the sensitivity to iron toxicity. Lack of AsA reduced the photosynthetic efficiency as represented by the maximum carboxylation rate of Rubisco (Vmax), the maximum electron transport rate (Jmax) and the chlorophyll fluorescence parameter ΦPSII. Mutants showed lower biomass production than their wild-types, especially when OsGGP was lacking (around 80% reductions). All plants except for KO mutants of OsGGP showed distinct peaks in foliar AsA concentrations during the growth, which were consistent with up-regulation of OsGGP, suggesting that OsGGP plays a pivotal role in regulating foliar AsA levels during different growth stages. In conclusion, our data demonstrate multiple roles of AsA in stress tolerance and development of rice.

Genetic dissection of ozone tolerance in rice (Oryza sativa L.) by a genome-wide association study.

Tropospheric ozone causes various negative effects on plants and affects the yield and quality of agricultural crops. Here, we report a genome-wide association study (GWAS) in rice (Oryza sativa L.) to determine candidate loci associated with ozone tolerance. A diversity panel consisting of 328 accessions representing all subgroups of O. sativa was exposed to ozone stress at 60 nl l(-1) for 7h every day throughout the growth season, or to control conditions. Averaged over all genotypes, ozone significantly affected biomass-related traits (plant height -1.0%, shoot dry weight -15.9%, tiller number -8.3%, grain weight -9.3%, total panicle weight -19.7%, single panicle weight -5.5%) and biochemical/physiological traits (symptom formation, SPAD value -4.4%, foliar lignin content +3.4%). A wide range of genotypic variance in response to ozone stress were observed in all phenotypes. Association mapping based on more than 30 000 single-nucleotide polymorphism (SNP) markers yielded 16 significant markers throughout the genome by applying a significance threshold of P<0.0001. Furthermore, by determining linkage disequilibrium blocks associated with significant SNPs, we gained a total of 195 candidate genes for these traits. The following sequence analysis revealed a number of novel polymorphisms in two candidate genes for the formation of visible leaf symptoms, a RING and an EREBP gene, both of which are involved in cell death and stress defence reactions. This study demonstrated substantial natural variation of responses to ozone in rice and the possibility of using GWAS in elucidating the genetic factors underlying ozone tolerance.

Loci, genes, and mechanisms associated with tolerance to ferrous iron toxicity in rice (Oryza sativa L.).

KEY MESSAGE: A genome-wide association study in rice yielded loci and candidate genes associated with tolerance to iron toxicity, and revealed biochemical mechanisms associated with tolerance in contrasting haplotypes. Iron toxicity is a major nutrient disorder affecting rice. Therefore, understanding the genetic and physiological mechanisms associated with iron toxicity tolerance is crucial in adaptive breeding and biofortification. We conducted a genome-wide association study (GWAS) by exposing a population of 329 accessions representing all subgroups of rice to ferrous iron stress (1000 ppm, 5 days). Expression patterns and sequence polymorphisms of candidate genes were investigated, and physiological hypotheses related to candidate loci were tested using a subset of contrasting haplotypes. Both iron including and excluding tolerant genotypes were observed, and shoot iron concentrations explained around 15.5 % of the variation in foliar symptom formation. GWAS for seven traits yielded 20 SNP markers exceeding a significance threshold of -log10 P > 4.0, which represented 18 distinct loci. One locus mapped for foliar symptom formation on chromosome 1 contained two putative glutathione-S-transferases, which were strongly expressed under iron stress and showed sequence polymorphisms in complete linkage disequilibrium with the most significant SNP. Contrasting haplotypes for this locus showed significant differences in dehydroascorbate reductase activity, which affected the plants' redox status under iron stress. We conclude that maintaining foliar redox homeostasis under iron stress represented an important tolerance mechanism associated with a locus identified through GWAS.

Ascorbate metabolism in rice genotypes differing in zinc efficiency.

Effects of zinc (Zn) deficiency on shoot metabolites were investigated in contrasting rice (Oryza sativa L.) genotypes with special focus on ascorbic acid (AsA) biosynthesis, recycling, and catabolism. The genotypes IR74 (sensitive) and RIL46 (tolerant) were subjected to -Zn and control treatments for 3 weeks, and samples were taken at three different stages representing the pre-stress phase, emergence of visible stress, and severe visible stress. The emergence of visible symptoms was paralleled by an increase in lipid peroxidation and a decrease in AsA concentration in the sensitive, but not in the tolerant genotype. The tolerant RIL46 showed enhanced transcript levels of several genes involved in the mannose/L-galactose pathway to AsA biosynthesis, and significant up-regulation of a gene involved in the putative alternative myo-inositol pathway under low Zn stress. The level of most AsA precursors was negatively affected by Zn deficiency, but RIL46 had a constitutively higher level of non-phosphorylated precursors. Products of AsA catabolism such as oxalate and threonate did not accumulate in either genotype, suggesting that AsA degradation did not contribute to the stress-induced decline of the AsA pool in IR74. Further factors possibly contributing to tolerance in RIL46 included an almost fivefold higher proline level under -Zn stress and significantly higher trehalose content. The implications of these compounds in AsA metabolism and Zn efficiency thus deserve further attention.

Alteration of carbon and nitrogen allocation in winter wheat under elevated ozone.

Tropospheric ozone accelerates senescence and shortens grain filling, consequently affecting the remobilization and allocation efficiency of aboveground biomass and nutrients into grains in cereal crops. This study investigated carbon (C) and nitrogen (N) concentrations repeatedly in shoot biomass during the growth period and in grain after the harvest in eighteen wheat genotypes under control and ozone treatments in open-top chambers. Season-long ozone fumigation was conducted at an average ozone concentration of 70 ppb with three additional acute ozone episodes of around 150 ppb. Although there were no significant differences in straw C and N concentrations between the two treatments, the straw C:N ratio was significantly increased after long-term ozone fumigation, and the grain C:N ratio decreased under elevated ozone without significance. Grain N concentrations increased significantly under ozone stress, whereas N yield declined significantly due to grain yield losses induced by ozone. Moreover, different indicators of N use efficiency were significantly reduced with the exception of N utilization efficiency (NUtE), indicating that elevated ozone exposure reduced the N absorption from soil and allocation from vegetative to reproductive organs. The linear regression between straw C:N ratio and productivity indicated that straw C:N was not a suitable trait for predicting wheat productivity due to the low coefficient of determination (R2). Nitrogen harvest index (NHI) was not significantly affected by ozone stress among all genotypes. However, elevated ozone concentration changed the relationship between harvest index (HI) and NHI, and the reduced regression slope between them indicated that ozone exposure significantly affected the relationship of N and biomass allocation into wheat grains. The cultivar "Jenga" showed optimal ozone tolerance due to less yield reduction and higher NUE after ozone exposure. The genotypes with higher nutrient use efficiencies are promising to cope with ozone-induced changes in nitrogen partitioning.

Van der Waals interactions at metal/organic interfaces at the single-molecule level.

Van der Waals (vdW) interaction, and its subtle interplay with chemically specific interactions and surface roughness at metal/organic interfaces, is critical to the understanding of structure-function relations in diverse areas, including catalysis, molecular electronics and self-assembly. However, vdW interactions remain challenging to characterize directly at the fundamental, single-molecule level both in experiments and in first principles calculations with accurate treatment of the non-local, London dispersion interactions. In particular, for metal/organic interfaces, efforts so far have largely focused on model systems consisting of adsorbed molecules on flat metallic surfaces with minimal specific chemical interaction. Here we show, through measurements of single-molecule mechanics, that pyridine derivatives can bind to nanostructured Au electrodes through an additional binding mechanism beyond the chemically specific N-Au donor-acceptor bond. Using density functional theory simulations we show that vdW interactions between the pyridine ring and Au electrodes can play a key role in the junction mechanics. These measurements thus provide a quantitative characterization of vdW interactions at metal/organic interfaces at the single-molecule level.

Lignin: characterization of a multifaceted crop component.

Lignin is a plant component with important implications for various agricultural disciplines. It confers rigidity to cell walls, and is therefore associated with tolerance to abiotic and biotic stresses and the mechanical stability of plants. In animal nutrition, lignin is considered an antinutritive component of forages as it cannot be readily fermented by rumen microbes. In terms of energy yield from biomass, the role of lignin depends on the conversion process. It contains more gross energy than other cell wall components and therefore confers enhanced heat value in thermochemical processes such as direct combustion. Conversely, it negatively affects biological energy conversion processes such as bioethanol or biogas production, as it inhibits microbial fermentation of the cell wall. Lignin from crop residues plays an important role in the soil organic carbon cycling, as it constitutes a recalcitrant carbon pool affecting nutrient mineralization and carbon sequestration. Due to the significance of lignin in several agricultural disciplines, the modification of lignin content and composition by breeding is becoming increasingly important. Both mapping of quantitative trait loci and transgenic approaches have been adopted to modify lignin in crops. However, breeding goals must be defined considering the conflicting role of lignin in different agricultural disciplines.

Diproline-induced resistance to parasitic nematodes in the same and subsequent rice generations: Roles of iron, nitric oxide and ethylene.

Induced resistance (IR) is a plant phenotype characterized by lower susceptibility to biotic challenges upon elicitation by so-called IR stimuli. Earlier, we identified diproline (cyclo(l-Pro-l-Pro)) as IR stimulus that protects rice (Oryza sativa) against the root-knot nematode Meloidogyne graminicola (Mg). In the current study, detailed transcriptome analyses at different time points, and under uninfected and nematode-infected conditions revealed that this rice IR phenotype is correlated with induction of genes related to iron (Fe), ethylene (ET) and reactive oxygen species (ROS)/reactive nitrogen species (RNS) metabolism. An infection experiment under Fe limiting conditions confirmed that diproline-IR is only effective under optimal Fe supply. Although total root Fe levels were not affected in diproline-treated plants, phytosiderophore secretion was found to be induced by this treatment. Experiments on mutant and transgenic rice lines impaired in ET or ROS/RNS metabolism confirmed that these metabolites are involved in diproline-IR. Finally, we provide evidence for transgenerational inheritance of diproline-IR (diproline-TIR), as two successive generations of diproline-treated ancestors exhibited an IR phenotype while themselves never being exposed to diproline. Transcriptome analyses on the offspring plants revealed extensive overlap between the pathways underpinning diproline-IR and diproline-TIR. Although diproline induces significant systemic changes in global DNA methylation levels early after treatment, such changes in DNA methylation were not detected in the descendants of these plants. To our knowledge, this is the first report of TIR in rice and the first transcriptional assessment of TIR in monocots.