Mycorrhizal Symbiosis Increases Plant Phylogenetic Diversity and Regulates Community Assembly in Grasslands.

The intricate mechanisms controlling plant diversity and community composition are cornerstone of ecological understanding. Yet, the role of mycorrhizal symbiosis in influencing community composition has often been underestimated. Here, we use extensive species survey data from 1315 grassland sites in China to elucidate the influence of mycorrhizal symbiosis on plant phylogenetic diversity and community assembly. We show that increasing mycorrhizal symbiotic potential leads to greater phylogenetic dispersion within plant communities. Mycorrhizal species predominantly influence deterministic processes, suggesting a role in niche-based community assembly. Conversely, non-mycorrhizal species exert a stronger influence on stochastic processes, highlighting the importance of random events in shaping community structure. These results underscore the crucial but often hidden role of mycorrhizal symbiosis in driving plant community diversity and assembly. This study provides valuable insights into the mechanisms shaping ecological communities and the way for more informed conservation that acknowledges the complex interplay between symbiosis and community dynamics.

C─H Activation Enables the Construction of New Bis-Polyaryl Phenylpyridine Ruthenium Complexes: Conjugation and Rigidity Synergistic Effect for Advanced Electrochemiluminescence.

The access to bench-stable organometallic compounds unfolds new chemical space for medicinal and material sciences. In particular, stable organoruthenium compounds with constitutional and stereoisomeric forms for subtle regulation of electrochemiluminescence are intriguing and challenging. Here, coordination of polycyclic aromatic hydrocarbons on (2-phenylpyridine)2(CO)2Ru complex allows access to bis-polyaryl phenylpyridine (BPP) Ruthenium complex through C─H activation strategy and coupling reactions for installation of the functionalities with steric and electronic purposes. The photoluminescence and electrochemiluminescence of BPP Ru complexes are affected by the actual polycyclic aromatic hydrocarbons inherent properties. The anthracene derivatized BPP Ru complex (BPP-Ant) shows the best ECL performance and reveals an enormous ECL quantum efficiency of 1.6-fold higher than the golden standard Ru(bpy)3 2+. The unprecedentedly high efficiency is due to the best compromise between the structural conjugation and molecular rigidity from BPP-Ant providing a providential energy gap that facilitated the feasibility of electron transfer and favored the radiative energy release by experimentally and DFT calculations. Moreover, PL and spooling ECL spectroscopies are used to track and link multiple emission peaks of BPP-Ant at 445, 645, and 845 nm to different emissive species. These discoveries will add a new member to the efficient ECL ruthenium complex family and bring more potentials.

Changes in productivity partitioning induced by precipitation extremes increase inaccuracy of grassland carbon estimation.

The fraction of net primary productivity (NPP) allocated to belowground organs (fBNPP) in grasslands is a critical parameter in global carbon cycle models; moreover, understanding the effect of precipitation changes on this parameter is vital to accurately estimating carbon sequestration in grassland ecosystems. However, how fBNPP responds to temporal precipitation changes along a gradient from extreme drought to extreme wetness, remains unclear, mainly due to the lack of long-term data of belowground net primary productivity (BNPP) and the fact that most precipitation experiments did not have a gradient from extreme drought to extreme wetness. Here, by conducting both a precipitation gradient experiment (100-500 mm) and a long-term observational study (34 years) in the Inner Mongolia grassland, we showed that fBNPP decreased linearly along the precipitation gradient from extreme drought to extreme wetness due to stronger responses in aboveground NPP to drought and wet conditions than those of BNPP. Our further meta-analysis in grasslands worldwide also indicated that fBNPP increased when precipitation decreased, and the vice versa. Such a consistent pattern of fBNPP response suggests that plants increase the belowground allocation with decreasing precipitation, while increase the aboveground allocation with increasing precipitation. Thus, the linearly decreasing response pattern in fBNPP should be incorporated into models that forecast carbon sequestration in grassland ecosystems; failure to do so will lead to underestimation of the carbon stock in drought years and overestimation of the carbon stock in wet years in grasslands.

Sparteine Thiourea: The Synthesis of an N Chiral Bispidine-Quinolizidine-Derived Organocatalyst and Applications in Asymmetric Synthesis of Dihydropyrano[c]chromenes.

Bispidine, a bridged bicyclic diamine, has been widely utilized as a rigid scaffold in chiral chelating ligands in asymmetric synthesis. In particular, a chiral bispidine-quinolizidine hybrid, such as sparteine, was utilized in asymmetric synthesis involving a metal, exhibiting superior catalytic activity. In this study, we report the design and synthesis of a series of sparteine-derived organocatalysts and the utilization of these catalysts in tandem Michael addition-cyclization reactions. These catalysts have shown excellent catalytic reactivity and enantioselectivity, and the corresponding dihydropyrano[c]chromenes have been prepared in ≤99% yield and ≤99% ee with a low catalyst loading. The recycled catalysts maintain a good catalytic performance even after four cycles, and a gram-scale reaction with a 1% catalyst loading is also performed, providing the product in 96% yield and 98% ee.

Structure-Based Identification of Organoruthenium Compounds as Nanomolar Antagonists of Cannabinoid Receptors.

Metal complexes exhibit a diverse range of coordination geometries, representing novel privileged scaffolds with convenient click types of preparation inaccessible for typical carbon-centered organic compounds. Herein, we explored the opportunity to identify biologically active organometallic complexes by reverse docking of a rigid, minimum-size octahedral organoruthenium scaffold against thousands of protein-binding pockets. Interestingly, cannabinoid receptor type 1 (CB1) was identified based on the docking scores and the degree of overlap between the docked organoruthenium scaffold and the hydrophobic scaffold of the cocrystallized ligand. Further structure-based optimization led to the discovery of organoruthenium complexes with nanomolar binding affinities and high selectivity toward CB2. Our work indicates that octahedral organoruthenium scaffolds may be advantageous for targeting the large and hydrophobic binding pockets and that the reverse docking approach may facilitate the discovery of novel privileged scaffolds, such as organometallic complexes, for exploring chemical space in lead discovery.

Enhanced foliar 15 N enrichment with increasing nitrogen addition rates: Role of plant species and nitrogen compounds.

Determining the abundance of N isotope (δ15 N) in natural environments is a simple but powerful method for providing integrated information on the N cycling dynamics and status in an ecosystem under exogenous N inputs. However, whether the input of different N compounds could differently impact plant growth and their 15 N signatures remains unclear. Here, the response of 15 N signatures and growth of three dominant plants (Leymus chinensis, Carex duriuscula, and Thermopsis lanceolata) to the addition of three N compounds (NH4 HCO3 , urea, and NH4 NO3 ) at multiple N addition rates were assessed in a meadow steppe in Inner Mongolia. The three plants showed different initial foliar δ15 N values because of differences in their N acquisition strategies. Particularly, T. lanceolata (N2 -fixing species) showed significantly lower 15 N signatures than L. chinensis (associated with arbuscular mycorrhizal fungi [AMF]) and C. duriuscula (associated with AMF). Moreover, the foliar δ15 N of all three species increased with increasing N addition rates, with a sharp increase above an N addition rate of ~10 g N m-2  year-1 . Foliar δ15 N values were significantly higher when NH4 HCO3 and urea were added than when NH4 NO3 was added, suggesting that adding weakly acidifying N compounds could result in a more open N cycle. Overall, our results imply that assessing the N transformation processes in the context of increasing global N deposition necessitates the consideration of N deposition rates, forms of the deposited N compounds, and N utilization strategies of the co-existing plant species in the ecosystem.

Nitrogen addition and mowing had only weak interactive effects on macronutrients in plant-soil systems of a typical steppe in Inner Mongolia.

Effective management of macronutrients is pivotal in the optimization and provisioning of ecosystem services in grassland areas, particularly in degraded grasslands. In such instances where mowing and nitrogen (N) fertilization have emerged as predominant management strategies, nutrient management is especially important. However, the precise effects of these concurrent practices on the distribution of macronutrients in plant-soil systems remain unclear. Here we evaluated the effects of 12 years of N addition (2, 10, and 50 g N m-2 year-1) and mowing on the concentrations and pools of six macronutrients (i.e., N; phosphorus P; sulfur S, calcium Ca, magnesium Mg, and potassium K) in three plant components (aboveground plants, litter, and belowground roots) at the community level and in the soil in a typical steppe in Inner Mongolia. Our results revealed that N addition generally raised the N concentration in the entire plant-soil system, regardless of whether plots were mowed. Higher N addition (10 and 50 g N m-2 year-1) also led to higher concentrations of P (+22%, averaging two N addition rates), S (+16%), K (+22%), Ca (+22%), and Mg (+24%) in plants but lower concentrations of these nutrients in the litter. Similar decreases in K (-9%), Ca (-46%), and Mg (-8%) were observed in the roots. In light of the observed increases in vegetation biomass and the lack of pronounced changes in soil bulk density, we found that the ecosystem N enrichment resulted in increased pools of all measured macronutrients in plants, litter, and roots (with the exception of Ca in the roots) while concurrently decreased the pools of P (-20%, averaging two higher N addition rates), S (-12%), K (-10%), Ca (-37%), and Mg (-19%) in the soil, with no obvious effect of the mowing practice. Overall, mowing exhibited a very limited capacity to alleviate the effects of long-term N addition on macronutrients in the plant-soil system. These findings highlight the importance of considering the distribution of macronutrients across distinct plant organs and the dynamic nutrient interplay between plants and soil, particularly in the context of long-term fertilization and mowing practices, when formulating effective grassland management strategies.

Applied phosphorus is maintained in labile and moderately occluded fractions in a typical meadow steppe with the addition of multiple nutrients.

Phosphorus (P) is a limiting nutrient second only to nitrogen (N) in the drylands of the world. Most previous studies have focused on N transformation processes in grassland ecosystems, particularly under artificial fertilization with N and atmospheric N deposition. However, P cycling processes under natural conditions and when P is applied as an inorganic P fertilizer have been understudied. Therefore, it is essential to examine the fate of applied P in grassland ecosystems that have experienced long-term grazing and, under certain circumstances, continuous hay harvest. We conducted a 3-year field experiment with the addition of multiple nutrient elements in a typical meadow steppe to investigate the fate of the applied P in various fractions of P pools in the top soil. We found that the addition of multiple nutrients significantly increased P concentrations in the labile inorganic P (Lab-Pi) and moderately occluded inorganic P (Mod-Pi) fractions but not in the recalcitrant inorganic P (Rec-Pi) fraction. An increase in the concentration of total inorganic P was found only when P and N were applied together. However, the addition of other nutrients did not change P concentrations in any fraction of the mineral soil. The addition of P and N significantly increased the total amount of P taken up by the aboveground plants but had no effect on the levels of organic and microbial P in the soil. Together, our results indicate that the P applied in this grassland ecosystem is taken up by plants, leaving most of the unutilized P as Lab-Pi and Mod-Pi rather than being immobilized in Rec-Pi or by microbial biomass. This implies that the grassland ecosystem that we studied has a relatively low P adsorption capacity, and the application of inorganic P to replenish soil P deficiency in degraded grasslands due to long-term grazing of livestock or continuous harvest of forage in the region could be a practical management strategy to maintain soil P fertility.

Natural Product-Inspired Chiral Ligand Design: Aloperine and N-Substituted Aloperines-Induced Pd-Catalyzed Asymmetric Hydroarylation of Ketimines.

A naturally occurring alkaloid aloperine was utilized as a chiral skeleton for the development of new ligands/catalysts in asymmetric synthesis. A number of N-substituted aloperines have been prepared, and a Pd-catalyzed asymmetric hydroarylation of ketimines using these chiral 1,3-diamine ligands was reported. A range of chiral sulfonyl amides were prepared in high yields and enantioselectivities. The stereoselectivity and structure relationships of aloperines have been studied. In addition, preliminary studies on the desymmetrization of meso-anhydride have also shown that these diamines have good potential in organocatalysis. These discoveries would provide a new future development for natural product-inspired chiral ligand design and developments.

Construction of aziridine, azetidine, indole and quinoline-like heterocycles via Pd-mediated C-H activation/annulation strategies.

N-Heterocycles can be found in natural products and drug molecules and are indispensable components in the area of organic synthesis, medicinal chemistry and materials science. The construction of these N-containing heterocycles by traditional methods usually requires the preparation of reactive intermediates. In the past decades, with the rapid growth of transition metal catalysed coupling reactions, syntheses of heterocycles from precursors with inert chemical bonds have become a challenge. More recently, in the field of transition metal associated C-H direct functionalization, efficient methods have been developed for the syntheses of N-heterocyclic compounds such as aziridines, azetidines, indoles and quinolines under the click type of reaction mode. In this review, representative synthetic methodologies developed in the recent 10 years for the preparation of this small class of N-heterocycles via the Pd-catalysed C-H activation and C-N bond formation pathway are discussed. We hope this article will provide new insights from the strategies highlighted into future molecular design, synthesis and applications in medical and materials sciences.