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ssue engineering and minimally invasive surgery.Desaturation of unactivated alkanes remains a challenging yet desirable strategy to make olefins. The Illicium sesquiterpenes usually possess highly oxygenated cage-like architectures, and some of them exhibit prominent neurotrophic effects. Here, we disclose a unique photochemical desaturation strategy for the efficient, highly stereocontrolled total syntheses of five Illicium sesquiterpenes from inexpensive (R)-pulegone, featuring a 13-step gram-scale synthesis of (-)-merrilactone A. The efficiency of the syntheses derives from an expedient construction of a tetracyclic framework via two annulations, a site-specific photoinduced single-step desaturation in a complex hydrocarbon system, and diverse oxygenation manipulations around the resultant olefin intermediate. This work highlights how late-stage desaturation can dramatically streamline the synthesis of complex terpenes and diverse non-natural analogues for establishing the structure-activity relationship and elucidating their molecular mechanisms of bioactivity.Mitochondrial redox homeostasis plays a vital role in many biological processes. Hydrogen peroxide (H2O2), one of the most important components for the balance between oxidizing species and reducing species, also acts as the messenger of mitochondrial damage. Thus, an accurate in situ quantitative detection of H2O2 in mitochondria is very important for the evaluation of mitochondrial redox homeostasis. Here, we develop robust surface-enhanced Raman spectroscopy (SERS) nanoprobes based on Au nanoparticles as SERS substrate and functionalized carrier, which is further modified with a phenylboronic acid pinacol ester for specific H2O2 response and a location peptides for mitochondrial targeting by creating a robust Au-Se interface. The SERS nanoprobes show good resistance to abundant thiol under biological conditions and superior performance for mitochondria H2O2 monitoring in living cells than the SERS nanoprobes with the traditional Au-S interface, which enables us to achieve in situ quantification of mitochondrial H2O2 and obtain its real-time dynamic change under oxidative stress.The phenomenon of surface electrification upon contact is a long-standing scientific puzzle, with for instance written accounts of charged samples of amber attracting feathers dating back to the 600 B.C. Electrostatic hazards associated with electrical insulators subject to mechanical friction are well documented, and the design of commercial products, such as copiers and laser printers, is based on the static charging of electrical insulators. Nonetheless, the physical-chemical origin of this phenomenon remains debated. This Perspective outlines recent advances in our understanding of the mechanism behind contact electrification, as well as the emerging research area of electrochemistry on insulators. Research is beginning to demonstrate how to exploit static charges present on insulating surfaces, with the goal of driving redox reactivity. These studies have helped to clarify the triboelectrification mechanism and have defined new platforms for electrochemiluminescence, metal nucleation, and mask-free lithography. Sanguinarine This Perspective will help researchers working within electrochemistry, physics, green energy, sensing, and materials to gain an understanding of the implications of contact electrification to their respective fields. Special attention is given to the chemical, electronic, and mechanical factors influencing triboelectrochemical reactions, concluding with the perceived challenges facing further development of this field.In mammals, carotenoids are converted by two carotenoid cleavage oxygenases into apocarotenoids, including vitamin A. Although knowledge about β-carotene oxygenase-1 (BCO1) and vitamin A metabolism has tremendously increased, the function of β-carotene oxygenase-2 (BCO2) remains less well-defined. We here studied the role of BCO2 in the metabolism of long chain β-apocarotenoids, which recently emerged as putative regulatory molecules in mammalian biology. We showed that recombinant murine BCO2 converted the alcohol, aldehyde, and carboxylic acid of a β-apocarotenoid substrate by oxidative cleavage at position C9,C10 into a β-ionone and a diapocarotenoid product. Chain length variation (C20 to C40) and ionone ring site modifications of the apocarotenoid substrate did not impede catalytic activity or alter the regioselectivity of the double bond cleavage by BCO2. Isotope labeling experiments revealed that the double bond cleavage of an apocarotenoid followed a dioxygenase reaction mechanism. Structural modeling and site directed mutagenesis identified amino acid residues in the substrate tunnel of BCO2 that are critical for apocarotenoid binding and catalytic processing. Mice deficient for BCO2 accumulated apocarotenoids in their livers, indicating that the enzyme engages in apocarotenoid metabolism. Together, our study provides novel structural and functional insights into BCO2 catalysis and establishes the enzyme as a key component of apocarotenoid homeostasis in mice.Layered manganese (Mn) oxides, such as birnessite, can reductively transform into other phases and thereby affect the environmental behavior of Mn oxides. Solution chemistry strongly influences the transformation, but the effects of oxyanions remain unknown. We determined the products and rates of Mn(II)-driven reductive transformation of δ-MnO2, a nanoparticulate hexagonal birnessite, in the presence of phosphate or silicate at pH 6-8 and a wide range of Mn(II)/MnO2 molar ratios. Without the oxyanions, δ-MnO2 transforms into triclinic birnessite (T-bir) and 4 × 4 tunneled Mn oxide (TMO) at low Mn(II)/MnO2 ratios (0.09 and 0.13) and into δ-MnOOH and Mn3O4 with minor poorly crystallized α- and γ-MnOOH at high Mn(II)/MnO2 ratios (0.5 and 1). The presence of phosphate or silicate substantially decreases the rate and extent of the above transformation, probably due to adsorption of the oxyanions on layer edges or the formation of Mn(II,III)-oxyanion ternary complexes on vacancies of δ-MnO2, adversely interfering with electron transfer, Mn(III) distribution, and structural rearrangements.