Padgettmcmahon8911

Autophagy and endocytosis are essential in regulating cellular homeostasis and cancer immunotherapeutic responses. Existing methods for autophagy and endocytosis imaging are susceptible to cellular micro-environmental changes, and direct fluorogenic visualization of their fluxes remains challenging. We develop a novel strategy via clicking of organelle-enriched probes (COP), which comprises a pair of trans-cyclooctenol (TCO) and tetrazine probes separately enriched in lysosomes and mitochondria (in autophagy) or plasma membrane (in endocytosis). These paired probes are merged and boost a fluorogenic click reaction in response to autophagic or endocytic flux that ultimately fuses mitochondria or plasma membrane into lysosomes. We demonstrate that this strategy enables direct visualization of autophagic and endocytic fluxes, and confer insight into correlation of autophagic or endocytic flux to cell surface expression of immunotherapeutic targets such as MHC-I and PD-L1. The COP strategy provides a new paradigm for imaging autophagic and endocytic fluxes, and affords potential for improved cancer immunotherapy using autophagy or endocytosis inhibitors.Photocatalytic ethane conversion into value-added chemicals is a great challenge especially under visible light irradiation. The production of ethyl hydroperoxide (CH3CH2OOH), which is a promising radical reservoir for regulating the oxidative stress in cells, is even more challenging due to its facile decomposition. Here, we demonstrated a design of a highly efficient visible-light-responsive photocatalyst, Au/WO3, for ethane oxidation into CH3CH2OOH, achieving an impressive yield of 1887 μmol gcat -1 in two hours under visible light irradiation at room temperature for the first time. Furthermore, thermal energy was introduced into the photocatalytic system to increase the driving force for ethane oxidation, enhancing CH3CH2OOH production by six times to 11 233 μmol gcat -1 at 100 °C and achieving a significant apparent quantum efficiency of 17.9% at 450 nm. In addition, trapping active species and isotope-labeling reactants revealed the reaction pathway. These findings pave the way for scalable ethane conversion into CH3CH2OOH as a potential anticancer drug.Designing solid-state electrolytes for proton batteries at moderate temperatures is challenging as most solid-state proton conductors suffer from poor moldability and thermal stability. Crystal-glass transformation of coordination polymers (CPs) and metal-organic frameworks (MOFs) via melt-quenching offers diverse accessibility to unique properties as well as processing abilities. Here, we synthesized a glassy-state CP, [Zn3(H2PO4)6(H2O)3](1,2,3-benzotriazole), that exhibited a low melting temperature (114 °C) and a high anhydrous single-ion proton conductivity (8.0 × 10-3 S cm-1 at 120 °C). Converting crystalline CPs to their glassy-state counterparts via melt-quenching not only initiated an isotropic disordered domain that enhanced H+ dynamics, but also generated an immersive interface that was beneficial for solid electrolyte applications. Finally, we demonstrated the first example of a rechargeable all-solid-state H+ battery utilizing the new glassy-state CP, which exhibited a wide operating-temperature range of 25 to 110 °C.Baeyer-Villiger (BV) oxidation is a fundamental organic reaction, whereas the hetero-BV oxidation is uncharted. Herein, a tellura-BV oxidation is discovered. By oxidizing a tellurophene-embedded and electron-rich polycycle (1) with mCPBA or Oxone, an oxygen atom is inserted into the Te-C bond of the tellurophene to form tellurinate lactone mono-2. This reaction proceeds as follows (i) 1 is oxidized to the tellurophene Te-oxide form (IM-1); (ii) IM-1 undergoes tellura-BV oxidation to give mono-2. Moreover, the hybrid trichalcogenasumanenes 7 and 8 are, respectively, converted to tellurinate lactones mono-9 and mono-10 under the same conditions, indicating that tellura-BV oxidation shows high chemoselectivity. Due to the strong secondary bonding interactions between the Te[double bond, length as m-dash]O groups on tellurinate lactones, mono-2, mono-9, and mono-10 are dimerized to form U-shaped polycycles 2, 9, and 10, respectively. Notably, mono-2, mono-9, mono-10, and their dimers show chirality. This work enables one-step transformation of tellurophene into tellurinate lactone and construction of intricate polycycles.A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. The method exhibits a broad substrate scope for thiols, aryl iodides and amino acid units. Peptide macrocycles of a wide range of size and composition can be readily assembled in high yield from various easily accessible building blocks. This method has been successfully employed to prepare an 8-million-membered tetrameric cyclic peptide DNA-encoded library (DEL). Preliminary screening of the DEL library against protein p300 identified compounds with single digit micromolar inhibition activity.A hetero-dinuclear IrIII-CuII complex with two adjacent sites was employed as a catalyst for the aerobic oxidation of aromatic olefins driven by formate in water. An IrIII-H intermediate, generated through formate dehydrogenation, was revealed to activate terminal aromatic olefins to afford an Ir-alkyl species, and the process was promoted by a hydrophobic [IrIII-H]-[substrate aromatic ring] interaction in water. The Ir-alkyl species subsequently reacted with dioxygen to yield corresponding methyl ketones and was promoted by the presence of the CuII moiety under acidic conditions. The IrIII-CuII complex exhibited cooperative catalysis in the selective aerobic oxidation of olefins to corresponding methyl ketones, as evidenced by no reactivities observed from the corresponding mononuclear IrIII and CuII complexes, as the individual components of the IrIII-CuII complex. The reaction mechanism afforded by the IrIII-CuII complex in the aerobic oxidation was disclosed by a combination of spectroscopic detection of reaction intermediates, kinetic analysis, and theoretical calculations.Graphene or chemically modified graphene, because of its high specific surface area and abundant functional groups, provides an ideal template for the controllable growth of metal-organic framework (MOF) particles. The nanocomposite assembled from graphene and MOFs can effectively overcome the limitations of low stability and poor conductivity of MOFs, greatly widening their application in the field of electrochemistry. Furthermore, it can also be utilized as a versatile precursor due to the tunable structure and composition for various derivatives with sophisticated structures, showing their unique advantages and great potential in many applications, especially energy storage and conversion. SC144 Therefore, the related studies have been becoming a hot research topic and have achieved great progress. This review summarizes comprehensively the latest methods of synthesizing MOFs/graphene and their derivatives, and their application in energy storage and conversion with a detailed analysis of the structure-property relationship. Additionally, the current challenges and opportunities in this field will be discussed with an outlook also provided.Electrogenerated chemiluminescence, also known as electrochemiluminescence (ECL), is an electrochemically induced production of light by excited luminophores generated during redox reactions. It can be used to sense the charge transfer and related processes at electrodes via a simple visual readout; hence, ECL is an outstanding tool in analytical sensing. The traditional ECL approach measures averaged electrochemical quantities of a large ensemble of individual entities, including molecules, microstructures and ions. However, as a real system is usually heterogeneous, the study of single entities holds great potential in elucidating new truths of nature which are averaged out in ensemble assays or hidden in complex systems. We would like to review the development of ECL intensity and imaging based single entity detection and place emphasis on the assays of small entities including single molecules, micro/nanoparticles and cells. The current challenges for and perspectives on ECL detection of single entities are also discussed.Solar-to-fuel conversion through photocatalytic processes is regarded as promising technology with the potential to reduce reliance on dwindling reserves of fossil fuels and to support the sustainable development of our society. However, conventional semiconductor-based photocatalytic systems suffer from unsatisfactory reaction efficiencies due to limited light harvesting abilities. Recent pioneering work from several groups, including ours, has demonstrated that visible and infrared light can be utilized by plasmonic catalysts not only to induce local heating but also to generate energetic hot carriers for initiating surface catalytic reactions and/or modulating the reaction pathways, resulting in synergistically promoted solar-to-fuel conversion efficiencies. In this perspective, we focus primarily on plasmon-mediated catalysis for thermodynamically uphill reactions converting CO2 and/or H2O into value-added products. We first introduce two types of mechanism and their applications by which reactions on plasmonic nanostructures can be initiated either by photo-induced hot carriers (plasmonic photocatalysis) or by light-excited phonons (photothermal catalysis). Then, we emphasize examples where the hot carriers and phonon modes act in concert to contribute to the reaction (plasmonic photothermal catalysis), with special attention given to the design concepts and reaction mechanisms of the catalysts. We discuss challenges and future opportunities relating to plasmonic photothermal processes, aiming to promote an understanding of underlying mechanisms and provide guidelines for the rational design and construction of plasmonic catalysts for highly efficient solar-to-fuel conversion.Gold is noble in bulk but turns out to be a superior catalyst at the nanoscale when supported on oxides, in particular titania. The critical thickness for activity, namely two-layer gold particles on titania, observed two decades ago represents one of the most influential mysteries in the recent history of heterogeneous catalysis. By developing a Bayesian optimization controlled global potential energy surface exploration tool with machine learning potential, here we determine the atomic structures of gold particles within ∼2 nm on a TiO2 surface. We show that the smallest stable Au nanoparticle is Au24 which is pinned on the oxygen-rich TiO2 and exhibits an unprecedented dome architecture made by a single-layer Au sheet but with an apparent two-atomic-layer height. Importantly, this has the highest activity for CO oxidation at room temperature. The physical origin of the high activity is the outstanding electron storage ability of the nano-dome, which activates the lattice oxygen of the oxide. The determined CO oxidation mechanism, the simulated rate and the fitted apparent energy barrier are consistent with known experimental facts, providing key evidence for the presence of both the high-activity Au dome and the low-activity close-packed Au particles in real catalysts. The future direction for the preparation of active and stable Au-based catalysts is thus outlined.