The potential adverse effects of CuO nanoparticles (NPs) have increasingly attracted attention. Combining electron microscopic and toxicological investigations, we determined the adhesion, uptake, and toxicity of CuO NPs to eukaryotic alga Chlorella pyrenoidosa. CuO NPs were toxic to C. pyrenoidosa, with a 72 h EC50 of 45.7 mg/L. Scanning electron microscopy showed that CuO NPs were attached onto the surface of the algal cells and interacted with extracellular polymeric substances (EPS) excreted by the organisms. Transmission electron microscopy (TEM) showed that EPS layer of algae was thickened by nearly 4-fold after CuO NPs exposure, suggesting a possible protective mechanism. In spite of the thickening of EPS layer, CuO NPs were still internalized by endocytosis and were stored in algal vacuoles. TEM and electron diffraction analysis confirmed that the internalized CuO NPs were transformed to Cu2O NPs (d-spacing, ∼0.213 nm) with an average size approximately 5 nm. The toxicity investigation demonstrated that severe membrane damage was observed after attachment of CuO NPs with algae. Reactive oxygen species generation and mitochondrial depolarization were also noted upon exposure to CuO NPs. This work provides useful information on understanding the role of NPs-algae physical interactions in nanotoxicity.

The oocyte cytoplasm can reprogram the somatic cell nucleus into a totipotent state, but with low efficiency. The spatiotemporal chromatin organization of somatic cell nuclear transfer (SCNT) embryos remains elusive. Here, we examine higher order chromatin structures of mouse SCNT embryos using a low-input Hi-C method. We find that donor cell chromatin transforms to the metaphase state rapidly after SCNT along with the dissolution of typical 3D chromatin structure. Intriguingly, the genome undergoes a mitotic metaphase-like to meiosis metaphase II-like transition following activation. Subsequently, weak chromatin compartments and topologically associating domains (TADs) emerge following metaphase exit. TADs are further removed until the 2-cell stage before being progressively reestablished. Obvious defects including stronger TAD boundaries, aberrant super-enhancer and promoter interactions are found in SCNT embryos. These defects are partially caused by inherited H3K9me3, and can be rescued by Kdm4d overexpression. These observations provide insight into chromatin architecture reorganization during SCNT embryo development.

Conspectus The monoterpene indole alkaloids, containing over 3000 known members and more than 40 structural types, represent one of the largest natural product families that have proven to be an important drug source. Their complex chemical structures and significant biological activities have rendered these alkaloids attractive targets in the synthetic community for decades. While chemists have developed many synthetic methodologies and tactics toward this end, general strategies allowing divergent access to a large variety of structural types and members of monoterpene indole alkaloids are still limited and highly desirable. Photoredox catalysis has emerged in recent years as a powerful tool to realize chemical transformations via single electron transfer (SET) processes that would otherwise be inaccessible. In particular, when the radical species generated by the visible light photoinduced approach is involved in well-designed cascade reactions, the formation of multiple chemical bonds and the assembly of structurally complex molecules would be secured in a green and economic manner. This protocol might serve to remodel the way of thinking for the preparation of useful pharmaceuticals and complex natural products. Due to a long-standing interest in the synthesis of diverse indole alkaloids, our group previously developed a cyclopropanation strategy (QinY. Qin, Y. Acc. Chem. Res.201144447) that was versatile to access several intriguing indole alkaloid molecules. With an idea of developing more general synthetic approaches to as many members of various indole alkaloids as possible, we recently disclosed new radical cascade reactions enabled by photoredox catalysis, leading to the collective asymmetric total synthesis of 42 monoterpene indole alkaloids belonging to 7 structural types. Several important discoveries deserve to be highlighted. First, the use of photocatalytic technology allowed us to achieve an unusual reaction pathway that reversed the conventional reactivity between two nucleophilic amine and enamine groups. Second, a crucial nitrogen-centered radical, directly generated from a sulfonamide N–H bond, triggered three types of cascade reactions to deliver indole alkaloid cores with manifold functionalities and controllable diastereoselectivities. Moreover, expansion of this catalytic, scalable, and general methodology permitted the total synthesis of a large collection of indole alkaloids. In this Account, we wish to provide a complete picture of our studies concerning the original synthetic design, method development, and applications in total synthesis. It is anticipated that the visible-light-driven cascade strategy will find further utility in the realm of natural product synthesis.

Insect attack is known to induce a high accumulation of volatile metabolites in tea (Camellia sinensis). However, little information is available concerning the effect of insect attack on tea quality-related nonvolatile specialized metabolites. This study aimed to investigate the formation of characteristic nonvolatile specialized metabolites in tea leaves in response to attack by major tea insects, namely, tea green leafhoppers and tea geometrids, and determine the possible involvement of phytohormones in metabolite formation resulting from insect attack. Both tea green leafhopper and tea geometrid attacks increased the jasmonic acid and salicylic acid contents. The abscisic acid content was only increased under tea green leafhopper attack, perhaps due to special continuous piercing−sucking wounding. Tea green leafhopper attack induced the formation of theaflavins from catechins under the action of polyphenol oxidase, while tea geometrid attack increased the L-theanine content. Exogenous phytohormone treatments can affect the caffeine and catechin contents. These results will help to determine the influence of major tea pest insects on important tea quality-related metabolites and enhance understanding of the relationship of phytohormones and quality-related nonvolatile metabolite formation in tea exposed to tea pest insect attacks.