No abstract

A biphenyl photosensitizer axle was implanted into the cavities of native and capped γ-cyclodextrins through rotaxanation using a cucubit[6]uril-templated azide-alkyne 1,3-dipolar cycloaddition, resulting in the construction of highly defined chiral binding/sensitizing sites. The orientation and interaction of the axle and capping moieties at the ground and excited states were interrogated by NMR, UV-vis, circular dichroism, and fluorescence spectroscopic studies. In situ photoisomerization of (Z,Z)-1,3-cyclooctadiene sensitized in the cavity of these [4]rotaxanes afforded (Z,E)-1,3-cyclooctadiene in up to 15.3% ee, which represents the highest level of enantiodifferentiation obtained to date for this supramolecular photochirogenesis.

Chiral slipped 5,8:9',10'-cyclodimers were preferentially produced over classical 9,10:9',10'-cyclodimers upon supramolecular photocyclodimerization of 2-anthracenecarboxylate (AC) mediated by β-cyclodextrin (β-CD). This photochirogenic route to the slipped cyclodimers, exclusively head-to-tail (HT) and highly enantioselective, has long been overlooked in foregoing studies but is dominant in reality and is absolutely supramolecularly activated by 2:2 complexation of AC with β-CD. The intricate structural and photophysical aspects of this higher-order complexation-triggered process have been comprehensively elucidated, while the absolute configurations of the slipped cyclodimers have been unambiguously assigned by comparing the experimental and theoretical circular dichroism spectra. In the 2:2 complex, two ACs packed in a dual β-CD capsule are not fully overlapped with each other but are only partially stacked in a slipped anti- or syn-HT manner. Hence, they do not spontaneously cyclodimerize upon photoexcitation but instead emit long-lived excimer fluorescence at wavelengths slightly longer than the monomer fluorescence, indicating that the slipped excimer is neither extremely reactive nor completely relaxed in conformation and energy. Because of the slipped conformation of the AC pair in the soft capsule, the subsequent photocyclodimerization becomes manipulable by various internal or external factors, such as temperature, pressure, added salt, and host modification, enabling us to exclusively obtain the slipped cyclodimers with high regio- and enantioselectivities. In this supramolecularly driven photochirogenesis, the dual β-CD capsule functions as a chiral organophotocatalyst to trigger and accelerate the nonclassical photochirogenic route to slipped cyclodimers by preorganizing the conformation of the encapsulated AC pair, formally mimicking a catalytic antibody.

This study was conducted to explore fungal endophyte communities inhabiting a toxic weed (Stellera chamaejasme L.) from meadows of northwestern China. The effects of plant tissue and growth stage on endophyte assemblages were characterized. Endophytes were recovered from 50 % of the samples, with a total of 714 isolates. 41 operational taxonomical units (OTUs) were identified, consisting of 40 OTUs belonging primarily to Ascomycota and 1 OTU belonging to Basidiomycota. Pleosporales and Hypocreales were the orders contributing the most species to the endophytic assemblages. The total colonization frequency and species richness of endophytic fungi were higher in roots than in leaves and stems. In addition, for the plant tissues, the structure of fungal communities differed significantly by growth stages of leaf emergence and dormancy; for the plant growth stages, the structure of fungal communities differed significantly by plant tissues. This study demonstrates that S. chamaejasme serves as a reservoir for a wide variety of fungal endophytes that can be isolated from various plant tissues.