Natural selection on floral traits of Caltha scaposa (Ranunculaceae), an alpine perennial with generalized pollination system from Northwest Yunnan

Floral traits, including those invisible to humans but visible to pollinators, that increase pollination efficiency may be selected by pollinators in plant species with pollen limitation of seed production, but the importance of pollinators as selective agents on different floral traits needs to be further quantified experimentally. In the present study, we examined selective strength on flower diameter, flower height,UV bulls-eye size, sepal size and UV proportion via female fitness in Caltha scaposa, based on openpollinated and hand-pollinated flowers, through which pollinator-mediated selection was calculated for each of floral traits. Our results suggest that seed production of C. scaposa is pollen limited in natural conditions. There was directional selection(△β_(pollinator)=-0.12) for larger flowers in open-pollinated flowers, while no significant selection was found in flower height, UV bulls-eye size, sepal size or UV proportion. Statistically significant selection was found in UV bulls-eye size, sepal size and UV proportion in hand-pollinated flowers, but interactions with pollinators contributed only to flower diameter. We conclude that in C. scaposa, floral traits that are subjected to selection might be driven by multiple selective agents, and suggest the importance of investigating floral traits that are invisible to human but visible to pollinators in measuring pollinator-mediated selection via male fitness.

Single thiolate replacement of metal nanoclusters

Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially single thiolate substitution,is highly desirable for subtly tailoring the structures and properties of metal nanoclusters.However,such a single-thiolate substituting is challenging,and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the singlethiolate-substituted structure.Here,we developed a combined method,concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster,and successfully resolved their structures by single crystal X-ray crystallography,which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile.Interestingly,the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster.The bond length-related stability was also observed.Overall,this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.

Combined synthesis of interconvertible Au11Cd and Au26Cd5 for photocatalytic oxidations involving singlet oxygen

A novel Au11Cd nanocluster was synthesized by developing a combined method and controlling the kinetics, and another Au26Cd5nanocluster was also obtained after the conditions were changed in the same reaction, which could transfer to Au11Cd in a two-way style. Both alloy nanoclusters can photocatalyze the production of singlet oxygen(1O_(2)) and exhibit enhanced efficiencies in photocatalyzing two kinds of organic oxidations involving singlet oxygen compared with their non-alloyed mother nanoclusters, indicating that the Cd-doping might be an efficient way to enhance the photocatalysis performance of gold nanoclusters and metal nanoclusters are promising photocatalysts for organic oxidation involving singlet oxygen.

Atomically Precise Metal Nanoclusters as Single Electron Transferers for Hydroborylation

The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.

Asymmetric catalytic nitrooxylation and azidation of β-keto amides/esters with hypervalent iodine reagents

Chiral Lewis acid-catalyzed enantioselective nitrooxylation of cyclic and acyclicβ-keto amides/esters with hypervalent iodine(III)reagents is reported.A number ofα-nitrooxy-β-keto amides/esters were obtained with good yields and high enantioselectivities by using bench-stable nitratobenziodoxole under mild conditions.

Improving the Catalytic Activity of Au25 Nanocluster by Peeling and Doping

Tuning the nanoclusters＇ compositions and structures is critical for the performance improvement of nanoclusters.Herein,a well-known Au25（SCH2CH2Ph）18 （Au25 for short） nanocluster has been transformed to a rare cadmium doped gold nanocluster [Au13Cd2（PPh3）6（SC2H4Ph）6（NO3）2]2Cd（NO3）4 （Au26Cd5 for short） by peeling and doping.Although Au25 exhibits no catalytic activity toward A3-coupling reaction under the investigated conditions,the novel cadmium doped gold nanocluster Au26Cd5 shows high catalytic activity,as well as good recyclability and substrate tolerance for the same reaction.The high catalytic activity is attributed to the cooperation between the exerted cadmium atoms and the neighbor gold atoms on the surface of Au13 icosahedron.This work has important implication for the tuning of nanoclusters＇ compositions and structures targeting the improvement of catalytic performance by some unusual but effective strategies.

Characterization of 24 microsatellite markers in Primula chungensis(Primulaceae),a distylous-homostylous species,using MiSeq sequencing

Primula chungensis is a species with considerable floral and mating-system variation,including distylous(outcrossing),homostylous(selfing) and mixed populations that contain both outcrossing and selfing forms.We isolated 24 microsatellite markers from P.chungensis using Illumina Mi Seq sequencing.Polymorphism and genetic diversity were then measured based on a sample of 24 individuals from a natural population in southern Tibet.All loci were polymorphic with the number of alleles per locus ranging from 2 to 4.The observed and expected heterozygosity ranged from 0 to 1 and 0.219 to 0.708,respectively.The microsatellite markers we have identified will serve as valuable tools for the investigation of the population genetic structure and phylogeography of P.chungensis and will inform models of the evolutionary history of mating systems in the species.