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Herein, we report the synthesis of seleno-substituted chromenes from selenoalkynes and phenols. In this cascade reaction, the applied gold catalyst not only functions as a p-acid, but also as a Lewis acid, enabling the propargylic substitution in the first step to connect the oxygen carbon bond. Under the optimal reaction condition a total of 26 chromenes were accessible by this modular access. During scale up experiments, the hydrolysis of the vinylselenium substructure to the corresponding chromenones was observed. By revisiting the electron-rich starting materials, four chromenones were produced following a one-pot reaction using a single gold catalyst. To better understand the interaction of gold and selenium, a series of nuclear magnetic resonance studies and high-resolution mass spectrometry studies were performed, which led to the proposal of a mechanism for this transformation.

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Carbene-based bioadhesives have favourable attributes for tissue adhesion, including non-specific bonding to wet and dry tissues, but suffer from relatively weak fracture strength after photocuring. Light irradiation of carbene-precursor (diazirine) also creates inert side products that are absent under thermal activation. Herein, a dual activation method combines light irradiation at elevated temperatures for the evaluation of diazirine depletion and effects on cohesive properties. A customized photo/thermal-rheometer evaluates viscoelastic properties, correlated to the kinetics of carbene:diazoalkane ratios via 19F NMR). The latter exploits the sensitive -CF3 functional group to determine joule-based light/temperature kinetics on trifluoroaryl diazirine consumption. The combination of heat and photoactivation produced bioadhesives that are 3× tougher compared to control. Dual thermal/light irradiation may be a strategy to improve viscoelastic dissipation and toughness of photo-activated adhesive resins.

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Accurate segmentation of the renal cancer structure, including the kidney, renal tumors, veins, and arteries, has great clinical significance, which can assist clinicians in diagnosing and treating renal cancer. For accurate segmentation of the renal cancer structure in contrast-enhanced computed tomography (CT) images, we proposed a novel encoder-decoder structure segmentation network named MDM-U-Net comprising a multi-scale anisotropic convolution block, dual activation attention block, and multi-scale deep supervision mechanism. The multi-scale anisotropic convolution block was used to improve the feature extraction ability of the network, the dual activation attention block as a channel-wise mechanism was used to guide the network to exploit important information, and the multi-scale deep supervision mechanism was used to supervise the layers of the decoder part for improving segmentation performance. In this study, we developed a feasible and generalizable MDM-U-Net model for renal cancer structure segmentation, trained the model from the public KiPA22 dataset, and tested it on the KiPA22 dataset and an in-house dataset. For the KiPA22 dataset, our method ranked first in renal cancer structure segmentation, achieving state-of-the-art (SOTA) performance in terms of 6 of 12 evaluation metrics (3 metrics per structure). For the in-house dataset, our method achieves SOTA performance in terms of 9 of 12 evaluation metrics (3 metrics per structure), demonstrating its superiority and generalization ability over the compared networks in renal structure segmentation from contrast-enhanced CT scans.

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OBJECTIVE: To understand the mechanism of dual activation of the brain and heart in pistol athletes during shooting performances, through synchronized monitoring of electroencephalogram (EEG) and electrocardiogram (ECG). METHODS: Eighteen adolescents air pistol athletes were placed in a simulated competition environment and performed 40 self-paced shooting tasks, and simultaneously monitored the athletes' EEG, ECG, and shooting performance during the preparation period. RESULTS: (1) In the successful performance, the power values of the alpha wave of the athlete's T7 area showed a significant upward trend 6 s before the shot, but there was no significant change in the alpha wave in the T8 area. In the failure performance, the alpha wave in the T7 and T8 areas did not change significantly 6 s before the shot. (2) The Fz theta wave power value of athletes in successful performance showed a significant upward trend in the 6 s before firing, and in the failure performance, it showed an "inverted U-shaped" characteristic of rising first and then decreasing. (3) Regardless of whether it was a success or a failure, the SMR wave power value of the athlete's central area has no significant change before the shot. (4) At 6 s before the shot, the athlete's heart rate and R-R interval (RRI) in the successful performance showed a significant decline and rise, respectively, but there was no significant change in the failure performance. (5) Approaching the firing time, the athletes' EEG and ECG have a more significant correlation in successful performance and a more synchronized trend, while the correlation was lower in failure performance. CONCLUSIONS: The psychophysiological state of young air pistol athletes was closely related to shooting performance. If the brain-cardiac system maintains a benign dual activation level during the aiming and firing period, it will be beneficial to the improvement of shooting performance, otherwise, it was easy to reduce shooting performance.

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The concurrent conversion of CH4 and CO2 into acetic acid is an ideal route to migrate the two greenhouse gases and manufacture a high-value-added C2 product with an atom economy of 100% but remains challenging due to the chemical inertness of both gases. By leveraging density functional theory (DFT) calculations, we report herein the computational design of metal-alkoxide-functionalized metal-organic framework (MOF) UiO-67 with well-defined dual sites that can activate CH4 and CO2 cooperatively to boost acetic acid synthesis. The dual sites are distributed on two adjacent functionalized organic linkers originating from the same node and feature a metal-metal distance of about 6-7 Å. Initially, a total of 13 single-site metal-alkoxide-functionalized UiO-67s (including three alkaline earth metals and 10 transition metals) are examined; then, favorable metal-alkoxides are identified and further used to design dual-site metal-alkoxide-functionalized UiO-67s for converting CH4 and CO2 into acetic acid. Detailed mechanistic investigation predicts that the dual-site UiO-67s functionalized with Mn-, Fe-, Co-, Ni-. and Zn-alkoxide are highly promising catalysts for this reaction. Compared to the single-site counterparts, the metal pair-site UiO-67s provide a subtle microenvironment for synergistic dual activation of CH4 and CO2, thus efficiently stabilizing the transition state and substantially reducing the reaction barrier for C-C coupling. The microscopic insights and design strategies in this work might advance the development of efficient MOF-based catalysts with built-in cooperative active sites toward direct acetic acid synthesis from CH4 and CO2.

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The in-depth mechanism on the simultaneous activation of O2 and surface lattice O2- on one active metallic site has not been elucidated yet. Herein, we report a strategy for the construction of abundant oxygen activation sites by rational design of Cu1 /TiO2 single atom catalysts (SACs). The charge transfer between isolated Cu and TiO2 support generates abundant CuI and 2-coordinated Olat sites in Cu1 -O-Ti hybridization structure, which facilitates the chemisorption and activation of O2 molecules. Simultaneously, the Cu1 -O-Ti induced TiO2 lattice distortion activate the adjacent surface lattice O2- , achieving the dual activation of O2 and surface lattice O2- . The Cu1 -O-Ti active site switches the CO oxidation mechanism from Eley-Rideal (80 °C) to Mars-van Krevelen route (200 °C) with the increase of reaction temperature. The dual activation of O2 and surface lattice O2- can by modulating the electron properties of SACs can boost the heterogeneous catalytic oxidation activity.

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Inflammation usually results in high-level reactive oxygen species (ROS) and reactive nitrogen species (RNS) not only in acidic tissue but also in alkaline tissue. However, noninvasively in vivo monitoring reactive species specifically within alkaline tissue remains a huge challenge. Here we introduce a dual activatable fluorescent probe PN910 located in the second near-infrared window (NIR-II, 900-1700 nm), which shows high selectivity toward H2 O2 and OONO- at pH beyond 7.4. Then we verified that PN910 could be used for the real-time, specific and accurate monitoring of cystitis and colitis for living animals. This report presents a unique approach to the development of dual activatable probe for in vivo biosensing.

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In this work, a detailed characterization was carried out of the ring-closure mechanism of EPB (1-ethynyl-2-(phenylethynyl)benzene) toward the 5-exo-dig and 6-endo-dig cyclization reactions, catalyzed by two Au-N-heterocyclic carbene (NHC) moieties. It was found that the 5-exo-dig cyclization takes place with a slightly lower activation barrier and larger exothermicity compared to that of the 6-endo-dig cyclization, in agreement with the available experimental data. A phenomenological partition (structural and electronic) for rate constants computed using transition-state theory and the reaction force analysis was used to shed light into the nature of the activation rate constant. It was found that rate constants are influenced by a strong structural component, which is larger for the 5-exo-dig cyclization due to the strain to form the five-membered ring. On the other hand, the gold activation mechanism is evidenced by a σ- and π-coordination of the Au-NHC moieties to the EPB substrate. It was found that differences in the σ-coordination arise on the reaction path for the 5-exo-dig and 6-endo-dig cyclizations. Thus, in the 6-endo-dig cyclization the σ gold-EPB interaction is weakened as a consequence of the formation of the cationic aryl intermediate, while for the 5-exo-dig cyclization this interaction was found to be favored. Furthermore, although minor changes in the Au-EPB coordination occur on the reaction path, these bonds are formally established in the TS vicinity. Results support the concerted nature of the dual gold activation mechanism.

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Al-F bonds are among the most stable σ bonds known, exhibiting an even higher bond energy than Si-F bonds. Despite a stability advantage and a potentially high Lewis acidity of Al-F complexes, they have not been described as structurally defined catalysts for enantioselective reactions. We show that Al-F salen complexes with appended ammonium moieties give exceptional catalytic activity in asymmetric carboxycyanations. In addition to aromatic aldehydes, enal and aliphatic substrates are well accepted. Turnover numbers up to around 104 were achieved, whereas with previous catalysts 101 -102 turnovers were typically attained. In contrast to Al-Me and Al-Cl salen complexes, the analogous Al-F species are remarkably stable towards air, water, and heat, and can be recovered unchanged after catalysis. They possess a considerably increased Lewis acidity as shown by DFT calculations.

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Incorporation of CO2 into heterocyclic compounds (i.e., 2-oxazolidinones) under mild conditions, especially at atmospheric pressure still remains challenging. The mononuclear ZnII complex ZnCl2 (TBD)2 , where TBD=1,5,7-triazabicyclo[4.4.0]dec-5-ene, in this study was demonstrated as a robust catalyst for the carboxylative cyclization of propargylic amines with CO2 to exclusively afford various 2-oxazolidinones in excellent yields. Notably, the ZnII catalytic species is readily generated in situ from ZnCl2 and TBD without pre-preparation and further isolation. Such a CO2 fixation protocol could proceed smoothly under atmospheric pressure at mild temperature in an atom economic and environmentally benign manner. 13 C NMR and control experiments were performed to explore the possible interaction between ZnII and the carbon-carbon triple bond of propargylic amine. The dual catalytic role of the Zn catalyst to enhance O-nucleophilicity of the carbamate anion intermediate and activate the carbon-carbon triple bond is proposed based on mechanistic investigations.

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In this work, we reported the synthesis of bifunctional carbocatalyst with acid-base dual-activation mechanism by introducing organoamines on the basal planes of graphene oxide (GO). Interestingly, GO-supported primary amine (AP-GO) exclusively promoted one-pot Henry-Michael reactions with excellent activity to give synthetically valuable multifunctionalized nitroalkanes. Notably, it also exhibited significantly higher activity than those using propylamine, activated carbon-supported primary amine, and mesoporous silica-supported primary amine as the catalysts. This superior catalytic performance originated from the unique properties of AP-GO, which provided the acid-base cooperative effect by the appropriate positioning of primary amines on their basal planes and carboxyl acids along their edges and the decreased diffusion resistance of the reactants and the intermediates during the multistep catalytic cycles because of its open two-dimensional sheet-like structure. Moreover, it could be readily recycled by simple filtration and subsequently reused without significant loss of its catalytic activity in a six times run test.

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Various haloalkynes are converted in the presence of a dual activation gold catalyst. Via a dual activation process a completely atom economic head-to-tail coupling delivers gem-dihalogenated conjugated enynes as valuable building blocks for organic synthesis.

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The competition between π- and dual σ,π-gold-activation modes is revealed in the gold(I)-catalyzed heterocyclization of 1-(o-ethynylaryl)urea. A noticeable effect of various ligands in gold complexes on the choice of these activation modes is described. The cationic [Au(IPr)](+) (IPr=2,6-bis(diisopropylphenyl)imidazol-2-ylidene) complex cleanly promotes the π activation of terminal alkynes, whereas [Au(PtBu3 )](+) favors intermediate σ,π species. In this experimental and mechanistic study, which includes kinetic and cross-over experiments, several σ-gold, σ,π-gold, and other gold polynuclear reaction intermediates have been isolated and identified by NMR spectroscopy, X-ray diffraction, or MALDI spectrometry. The ligand control in the simultaneous or alternative π- and σ,π-activation modes is also supported by deuterium-labeling experiments.