Masting promotes transformation from predation to mutualism in an oak-weevil-rodent system.

The significance of ecological non-monotonicity (a function whose first derivative changes signs) in shaping the structure and functions of the ecosystem has recently been recognized, but such studies involving high-order interactions are rare. Here, we have proposed a three-trophic conceptual diagram on interactions among trees, rodents, and insects in mast and non-mast years and tested the hypothesis that oak (Quercus wutaishanica) masting could result in increased mutualism and less predation in an oak-weevil-rodent system in a warm temperate forest of China. Our 14-year dataset revealed that mast years coincided with a relatively low rodent abundance but a high weevil abundance. Masting not only benefited seedling recruitment of oaks through increased dispersal by rodents but also a decrease in predation by rodents and weevils, as well as an increase in the overwintering survival of rodents. Masting appeared to have increased weevil survival by reducing predation of infested acorns by rodents. These results suggest that masting benefits all participants in the plant-insect-rodent system by increasing mutualism and reducing predation behavior (i.e., a non-monotonic function). Our study highlights the significance of masting in maintaining the diversity and function of the forest ecosystem by facilitating the transformation from predation to mutualism among trophic species.

Novel host plant use by a specialist insect depends on geographic variation in both the host and herbivore species.

Understanding the circumstances under which insect herbivores will adopt a novel host plant is a longstanding question in basic and applied ecology. While geographic variation in host use can arise through differences in both herbivore preference and plant characteristics, there is a tendency to attribute geographic variation in host use to regional differences in herbivore preference alone. This is especially true for herbivores specialized to one or a few plant species. We compared how geographic variation in herbivore preference and host plant origin shape regional differences in host plant use by the specialized herbivore, Euphydryas phaeton. In parts of its range, E. phaeton uses only a native host, Chelone glabra, while in others, it also uses an introduced host, Plantago lanceolata. We offered female butterflies from each region the non-native host plant sourced from both regions and compared their oviposition behavior. The non-native host was almost universally rejected by butterflies in the region where only the native plant is used. In the region where butterflies use both hosts, females accepted non-native plants from their natal region twice as often as non-native plants from the other region where they are not used. Acceptance differed substantially among individual butterflies within regions but not among plants within regions. Thus, both individual preference and regional differences in both the insect and non-native host contributed to the geographic variation in different ways. These results highlight that, in addition to herbivore preference, regional differences in perceived plant suitability may be an important driver of diet breadth.

Phylogeny more than plant height and leaf area explains variance in seed mass.

Although variation in seed mass can be attributed to other plant functional traits such as plant height, leaf size, genome size, growth form, leaf N and phylogeny, until now, there has been little information on the relative contributions of these factors to variation in seed mass. We compiled data consisting of 1071 vascular plant species from the literature to quantify the relationships between seed mass, explanatory variables and phylogeny. Strong phylogenetic signals of these explanatory variables reflected inherited ancestral traits of the plant species. Without controlling phylogeny, growth form and leaf N are associated with seed mass. However, this association disappeared when accounting for phylogeny. Plant height, leaf area, and genome size showed consistent positive relationship with seed mass irrespective of phylogeny. Using phylogenetic partial R2s model, phylogeny explained 50.89% of the variance in seed mass, much more than plant height, leaf area, genome size, leaf N, and growth form explaining only 7.39%, 0.58%, 1.85%, 0.06% and 0.09%, respectively. Therefore, future ecological work investigating the evolution of seed size should be cautious given that phylogeny is the best overall predictor for seed mass. Our study provides a novel avenue for clarifying variation in functional traits across plant species, improving our better understanding of global patterns in plant traits.

Spectroscopically Visualizing the Evolution of Hydrogen-Bonding Interactions.

Understanding chemical bond variations is the soul of chemistry as it is essential for any chemical process. The evolution of hydrogen bonds is one of the most fundamental and emblematic events during proton transfer; however, its experimental visualization remains a formidable challenge because of the transient timescales. Herein, by subtly regulating the proton-donating ability of distinct proton donors (zeolites or tungstophosphoric acid), a series of different hydrogen-bonding configurations were precisely manipulated. Then, an advanced two-dimensional (2D) heteronuclear correlation nuclear magnetic resonance (NMR) spectroscopic technique was utilized to simultaneously monitor the electronic properties of proton donors and acceptors (2-13C-acetone or trimethylphosphine oxide) through chemical shifts. Parabolic 1H-13C NMR relationships combined with single-well and double-well potential energy surfaces derived from theoretical simulations quantitatively identified the hydrogen bond types and allowed the evolution of hydrogen bonds to be visualized in diverse acid-base interaction complexes during proton transfer. Our findings provide a new perspective to reveal the nature and evolution of hydrogen bonds and confirm the superiority of 2D NMR techniques in identifying the subtle distinctions of various hydrogen-bonding configurations.

Controlling Metal-Oxide Reducibility for Efficient C-H Bond Activation in Hydrocarbons.

Knowing the structure of catalytically active species/phases and providing methods for their purposeful generation are two prerequisites for the design of catalysts with desired performance. Herein, we introduce a simple method for precise preparation of supported/bulk catalysts. It utilizes the ability of metal oxides to dissolve and to simultaneously precipitate during their treatment in an aqueous ammonia solution. Applying this method for a conventional VOx -Al2 O3 catalyst, the concentration of coordinatively unsaturated Al sites was tuned simply by changing the pH value of the solution. These sites affect the strength of V-O-Al bonds of isolated VOx species and thus the reducibility of the latter. This method is also applicable for controlling the reducibility of bulk catalysts as demonstrated for a CeO2 -ZrO2 -Al2 O3 system. The application potential of the developed catalysts was confirmed in the oxidative dehydrogenation of ethylbenzene to styrene with CO2 and in the non-oxidative propane dehydrogenation to propene. Our approach is extendable to the preparation of any metal oxide catalysts dissolvable in an ammonia solution.

Modulating the Microenvironment of Silanols in Pure-Silicon Zeolites for Boosting Vapor-phase Beckmann Rearrangement of Cyclohexanone Oxime.

Vapor-phase Beckmann rearrangement of cyclohexanone oxime (CHO) to ε-caprolactam (CPL) is still difficult to commercialize at the industrial scale due to its relatively low catalytic activity and poor lifetime. Herein, we synthesized a series of pure-silicon zeolites (including MFI, MEL, and -SVR) with three-dimensional 10-member-ring topolgies, diverse silanol status, and hierarchical porosity to investigate the synergistic effects of inner diffusivity and reactivity. S-1 zeolite of MFI-type topology with plentiful silanol nests exhibits a more preferable catalytic performance in terms of CHO conversion (99.7%) and CPL selectivity (89.7%), much higher than those of MEL- and -SVR-type zeolites mainly due to their diverse silanol distribution. With the construction of hierarchical porosity, S-1-P shows improved CPL selectivity of 94.1% owing to the enhanced diffusivity to shorten the retention time of the reactant and product molecules. The reaction mechanism and network have been further revealed by density functional theory (DFT) calculations and experimental designs, which indicate that silanol nests are major active sites due to their suitable interaction with CHO rather than terminal silanols. Particularly, the microenvironments of silanols can be modulated by alcohol solvents, ascribed to their different charge transfer and steric hindrance. Consequently, S-1-P shows superior CPL selectivity of 97.3% in ethonal solvents, which have higher adsorb energy of -0.627 eV with silanol nests than other alcohols. The present study not only provides a fundamental guide for the design of zeolite catalysts but also provides a reference for modulating the microenvironment of active sites according to the catalytic mechanism.

Versatile Synthesis of Hollow-Structured Mesoporous Carbons by Enhanced Surface Interaction for High-Performance Lithium-Ion Batteries.

Nanoporous carbons are very attractive for various applications including energy storage. Templating methods with assembled amphiphilic molecules or porous inorganic templates are typically used for the synthesis. Amongst the different members of this family, CMK-5-like structures that are constructed to consist of sub-10 nm amorphous carbon nanotubes and ultrahigh specific surface area due to their thin pore walls, have the best properties in various respects. However, the fabrication of such hollow-structured mesoporous carbons entails elaborately tailoring the surface properties of the template pore walls and selecting specific carbon precursors. Thus, very limited cases are successful. Herein, a versatile and general silanol-assisted surface-casting method to create hollow-structured mesoporous carbons and heteroatom-doped derivatives with numerous organic molecules (e.g., furfuryl alcohol, resol, 2-thiophene methanol, dopamine, tyrosine) and different structural templates is reported. These carbon materials exhibit ultrahigh surface area (2400 m2  g-1 ), large pore volume (4.0 cm3  g-1 ), as well as satisfactory lithium-storage capacity (1460 mAh g-1 at 0.1 A g-1 ), excellent rate capability (320 mAh g-1 at 5 A g-1 ), and very outstanding cycling performance (2000 cycles at 5 A g-1 ).

Behavioral adaptation of sympatric rodents to early germination of oak acorns: radicle pruning and embryo excision.

The seed germination schedule is a key factor affecting the food-hoarding behavior of animals and the seedling regeneration of plants. However, little is known about the behavioral adaptation of rodents to the rapid germination of acorns. In this study, we provided Quercus variabilis acorns to several rodent species to investigate how food-hoarding animals respond to seed germination. We found that only Apodemus peninsulae adopted embryo excision behavior to counteract seed germination, which is the first report of embryo excision in nonsquirrel rodents. We speculated that this species may be at an early stage of the evolutionary response to seed perishability in rodents, given the low rate of embryo excision in this species. On the contrary, all rodent species preferred to prune the radicles of germinating acorns before caching, suggesting that radicle pruning is a stable and more general foraging behavior strategy for food-hoarding rodents. Furthermore, scatter-hoarding rodents preferred to scatter-hoard and prune more germinating acorns, whereas they consumed more nongerminating acorns. Acorns with embryos excised rather than radicles pruned were much less likely to germinate than intact acorns, suggesting a behavioral adaptation strategy by rodents to the rapid germination of recalcitrant seeds. This study provides insight into the impact of early seed germination on plant-animal interactions.

Rhodium nanoparticles supported on silanol-rich zeolites beyond the homogeneous Wilkinson's catalyst for hydroformylation of olefins.

Hydroformylation is one of the largest industrially homogeneous processes that strongly relies on catalysts with phosphine ligands such as the Wilkinson's catalyst (triphenylphosphine coordinated Rh). Heterogeneous catalysts for olefin hydroformylation are highly desired but suffer from poor activity compared with homogeneous catalysts. Herein, we demonstrate that rhodium nanoparticles supported on siliceous MFI zeolite with abundant silanol nests are very active for hydroformylation, giving a turnover frequency as high as ~50,000 h-1 that even outperforms the classical Wilkinson's catalyst. Mechanism study reveals that the siliceous zeolite with silanol nests could efficiently enrich olefin molecules to adjacent rhodium nanoparticles, enhancing the hydroformylation reaction.

High rodent abundance increases seed removal but decreases scatter-hoarding and seedling recruitment along an elevational gradient.

The distributions of small rodents in mountainous environments across different elevations can provide important information regarding the effects of climate change on the dispersal of plant species. However, few studies of oak forest ecosystems have compared the elevational patterns of sympatric rodent diversity, seed dispersal, seed bank, and seedling abundance. Thus, we tested the differences in the seed disperser composition and abundance, seed dispersal, seed bank abundance, and seedling recruitment for Quercus wutaishanica along 10 elevation levels in the Taihang Mountains, China. Our results provide strong evidence that complex asymmetric seed dispersal and seedling regeneration exist along an elevational gradient. The abundance of rodents had a significant negative correlation with the elevation and the seed removal rates peaked and then declined with increasing elevation. The seed removal rates were higher at middle and lower elevations than higher elevations but acorns were predated by 5 species of seed predators at middle and lower elevations, and thus, there was a lower likelihood of recruitment compared with those dropped beneath mother oaks at higher elevations. More importantly, the number of individual seeds in the seed bank and seedlings increased with the elevation, although dispersal services were reduced at sites lacking rodents. As conditional mutualists, the rodents could possibly act as antagonistic seed predators rather than mutualistic seed dispersers at low and middle elevations, thereby resulting in the asymmetric pattern of rodent and seedling abundance with increasing elevation to affect the community assembly and ecosystem functions on a large spatial scale.

Comparison of gut bacterial communities of Hyphantriacunea Drury (Lepidoptera, Arctiidae), based on 16S rRNA full-length sequencing.

There are a large number of microorganisms in the gut of insects, which form a symbiotic relationship with the host during the long-term co-evolution process and have a significant impact on the host's nutrition, physiology, development, immunity, stress tolerance and other aspects. However, the composition of the gut microbes of Hyphantriacunea remains unclear. In order to investigate the difference and diversity of intestinal microbiota of H.cunea larvae feeding on different host plants, we used PacBio sequencing technology for the first time to sequence the 16S rRNA full-length gene of the intestinal microbiota of H.cunea. The species classification, ß diversity and function of intestinal microflora of the 5th instar larvae of four species of H.cunea feeding on apricot, plum, redbud and Chinese ash were analysed. The results showed that a total of nine phyla and 65 genera were identified by PacBio sequencing, amongst which Firmicutes was the dominant phylum and Enterococcus was the dominant genus, with an average relative abundance of 59.29% and 52.16%, respectively. PERMANOVA analysis and cluster heat map showed that the intestinal microbiomes of H.cunea larvae, fed on different hosts, were significantly different. LEfSe analysis confirmed the effect of host diet on intestinal community structure and PICRUSt2 analysis showed that most of the predictive functions were closely related to material transport and synthetic, metabolic and cellular processes. The results of this study laid a foundation for revealing the interaction between the intestinal microorganisms of H.cunea and its hosts and provided ideas for exploring new green prevention and control strategies of H.cunea.

Chromosome-level genome assembly of the Siberian chipmunk (Tamias sibiricus).

Tamias sibiricus is regarded as one predominant scatter-hoarder that stores their food items both in small scattered caches and underground larder-hoards. This unique behavior, though providing essential seed dispersal services for many plant species worldwide, relies highly on accurate spatial memory and acute sense of olfaction. Here, we assembled a chromosome-scale genome of T. sibiricus using Illumina sequencing, PacBio sequencing and chromosome structure capture technique. The genome was 2.64 Gb in size with scaffold N50 length of 172.61 Mb. A total of 2.59 Gb genome data was anchored and orientated onto 19 chromosomes (ranging from 28.70 to 222.90 Mb) with a mounting rate of up to 98.03%. Meanwhile, 25,311 protein-coding genes were predicted with an average gene length of 32,936 bp, and 94.73% of these genes were functionally annotated. This reference genome will be a valuable resource for in-depth studies on basic biological possess and environmental adaptation of the Siberian chipmunk, as well as promoting comparative genomic analyses with other species within Rodentia.

The influence of species identity and geographic locations on gut microbiota of small rodents.

Although the correlation between gut microbiota, species identity and geographic locations has long attracted the interest of scientists, to what extent species identity and geographic locations influence the gut microbiota assemblages in granivorous rodents needs further investigation. In this study, we performed a survey of gut microbial communities of four rodent species (Apodemus agrarius, A. peninsulae, Tamias sibiricus and Clethrionomys rufocanus) distributed in two areas with great distance (> 600 km apart), to assess if species identity dominates over geographic locations in shaping gut microbial profiles using 16S rRNA gene sequencing. We found that gut microbiota composition varied significantly across host species and was closely correlated with host genetics. We identified strong species identity effects on gut microbial composition, with a comparatively weaker signal of geographic provenance on the intestinal microbiota. Specifically, microbiota of one species was on average more similar to that of conspecifics living in separate sites than to members of a closely related species living in the same location. Our study suggests that both host genetics and geographical variations influence gut microbial diversity of four rodent species, which merits further investigation to reveal the patterns of phylogenetic correlation of gut microbial community assembly in mammals across multiple habitats.

Charge-separation driven mechanism via acylium ion intermediate migration during catalytic carbonylation in mordenite zeolite.

By employing ab initio molecular dynamic simulations, solid-state NMR spectroscopy, and two-dimensional correlation analysis of rapid scan Fourier transform infrared spectroscopy data, a new pathway is proposed for the formation of methyl acetate (MA) via the acylium ion (i.e.,CH3 - C ≡ O+) in 12-membered ring (MR) channel of mordenite by an integrated reaction/diffusion kinetics model, and this route is kinetically and thermodynamically more favorable than the traditional viewpoint in 8MR channel. From perspective of the complete catalytic cycle, the separation of these two reaction zones, i.e., the C-C bond coupling in 8MR channel and MA formation in 12MR channel, effectively avoids aggregation of highly active acetyl species or ketene, thereby reducing undesired carbon deposit production. The synergistic effect of different channels appears to account for the high carbonylation activity in mordenite that has thus far not been fully explained, and this paradigm may rationalize the observed catalytic activity of other reactions.

Structural and Acidic Characteristics of Multiple Zr Defect Sites in UiO-66 Metal-Organic Frameworks.

Although defects are prevalent in metal-organic frameworks (MOFs) and usually play a crucial role in modulating their performance in various applications, detailed structural characterizations of various defects remain a challenging task mainly due to their disordered, heterogeneous, and local nature. In this work, by using solid-state nuclear magnetic resonance spectroscopy (SSNMR) techniques in conjunction with density functional theory (DFT) calculations, it is clearly elucidated that the trimethylphosphine (TMP)-assisted 31P NMR strategy is capable of greatly facilitating the qualitative and quantitative description of the detailed structural and acidic characteristics as well as the evolution process of various Zr defects with subtle distinctions in UiO-66 upon moderate thermal treatment, hence surpassing most conventional analytical techniques. These results offer a fundamental understanding of the defect chemistry in MOFs.

Molecular identification and quantification of defect sites in metal-organic frameworks with NMR probe molecules.

The defects in metal-organic frameworks (MOFs) can dramatically alter their pore structure and chemical properties. However, it has been a great challenge to characterize the molecular structure of defects, especially when the defects are distributed irregularly in the lattice. In this work, we applied a characterization strategy based on solid-state nuclear magnetic resonance (NMR) to assess the chemistry of defects. This strategy takes advantage of the coordination-sensitive phosphorus probe molecules, e.g., trimethylphosphine (TMP) and trimethylphosphine oxide (TMPO), that can distinguish the subtle differences in the acidity of defects. A variety of local chemical environments have been identified in defective and ideal MOF lattices. The geometric dimension of defects can also be evaluated by using the homologs of probe molecules with different sizes. In addition, our method provides a reliable way to quantify the density of defect sites, which comes together with the molecular details of local pore environments. The comprehensive solid-state NMR strategy can be of great value for a better understanding of MOF structures and for guiding the design of MOFs with desired catalytic or adsorption properties.

Coking-Resistant Polyethylene Upcycling Modulated by Zeolite Micropore Diffusion.

Although the mass production of synthetic plastics has transformed human lives, it has resulted in waste accumulation on the earth. Here, we report a low-temperature conversion of polyethylene into olefins. By mixing the polyethylene feed with rationally designed ZSM-5 zeolite nanosheets at 280 °C in flowing hydrogen as a carrier gas, light hydrocarbons (C1-C7) were produced with a yield of up to 74.6%, where 83.9% of these products were C3-C6 olefins with almost undetectable coke formation. The reaction proceeds in multiple steps, including polyethylene melting, flowing to access the zeolite surface, cracking on the zeolite surface, formation of intermediates to diffuse into the zeolite micropores, and cracking into small molecules in the zeolite micropores. The ZSM-5 zeolite nanosheets kinetically matched the cascade cracking steps on the zeolite external surface and within micropores by boosting the intermediate diffusion. This feature efficiently suppressed the intermediate accumulation on the zeolite surface to minimize coke formation. In addition, we found that hydrogen participation in the cracking process could hinder the formation of polycyclic species within zeolite micropores, which also contributes to the rapid molecule diffusion. The coking-resistant polyethylene upcycling process at a low temperature not only overturns the general viewpoint for facile coke formation in the catalytic cracking over the zeolites but also demonstrates how the polyethylene-based plastics can be upcycled to valuable chemicals. In addition to the model polyethylene, the reaction system worked efficiently for the depolymerization of multiple practically used polyethylene-rich plastics, enabling an industrially and economically viable path for dealing with plastic wastes.

Gut Dysbiosis Has the Potential to Reduce the Sexual Attractiveness of Mouse Female.

Increasing evidence has shown that the gut microbiome has significant effects on mate preferences of insects; however, whether gut microbiota composition affects sexual attractiveness and mate preference in mammals remains largely unknown. Here, we showed that antibiotic treatment significantly restructured the gut microbiota composition of both mouse males and females. Males, regardless of antibiotic treatment, exhibited a higher propensity to interact with the control females than the antibiotic-treated females. The data clearly showed that gut microbiota dysbiosis reduced the sexual attractiveness of females to males, implying that commensal gut microbiota influences female attractiveness to males. The reduced sexual attractiveness of the antibiotic-treated females may be beneficial to discriminating males by avoiding disorders of immunity and sociability in offspring that acquire maternal gut microbiota via vertical transmission. We suggest further work should be oriented to increase our understanding of the interactions between gut microbiota dysbiosis, sexual selection, and mate choice of wild animals at the population level.

Carbocation chemistry confined in zeolites: spectroscopic and theoretical characterizations.

Acid-catalyzed reactions inside zeolites are one type of broadly applied industrial reactions, where carbocations are the most common intermediates of these reaction processes, including methanol to olefins, alkene/aromatic alkylation, and hydrocarbon cracking/isomerization. The fundamental research on these acid-catalyzed reactions is focused on the stability, evolution, and lifetime of carbocations under the zeolite confinement effect, which greatly affects the efficiency, selectivity and deactivation of zeolite catalysts. Therefore, a profound understanding of the carbocations confined in zeolites is not only beneficial to explain the reaction mechanism but also drive the design of new zeolite catalysts with ideal acidity and cages/channels. In this review, we provide both an in-depth understanding of the stabilization of carbocations by the pore confinement effect and summary of the advanced characterization methods to capture carbocations in zeolites, including UV-vis spectroscopy, solid-state NMR, fluorescence microscopy, IR spectroscopy and Raman spectroscopy. Also, we clarify the relationship between the activity and stability of carbocations in zeolite-catalyzed reactions, and further highlight the role of carbocations in various hydrocarbon conversion reactions inside zeolites with diverse frameworks and varying acidic properties.