Background Despite successful recanalization, up to half of patients with acute ischemic stroke caused by large‐vessel occlusion treated with endovascular treatment (EVT) do not recover to functional independence. We aim to evaluate the role of cerebral circulation time (CCT) as outcome predictor after EVT. Methods and Results We retrospectively enrolled consecutive patients with acute ischemic stroke–large‐vessel occlusion undergoing EVT. Three categories of CCT based on digital subtraction angiography were studied: CCT of the stroke side, CCT of the healthy side), and change of CCT of the stroke side versus CCT of the healthy side. Dramatic clinical recovery was defined as a 24‐hour National Institutes of Health Stroke Scale score ≤2 or ≥8 points drop. A modified Rankin Scale score ≤2 at 3 months was considered a favorable outcome. Logistic regression analysis was performed to evaluate the prediction of CCT on prognosis. One hundred patients were enrolled, of which 38 (38.0%) experienced a dramatic clinical recovery and 43 (43.0%) achieved a favorable outcome. Logistic regression analysis found that shorter change of CCT of the stroke side versus CCT of the healthy side and CCT of the stroke side were independent positive prognostic factors for dramatic clinical recovery (odds ratio [OR], 0.189; P =0.033; OR, 0.581; P =0.035) and favorable outcomes (OR, 0.142; P =0.020; OR, 0.581; P =0.046) after adjustment for potential confounders. A model including the change of CCT of the stroke side versus CCT of the healthy side also had significantly higher area under the curve values compared with the baseline model in patients with dramatic clinical recovery (0.780 versus 0.742) or favorable outcome (0.759 versus 0.713). Conclusions To our knowledge, this is the first report that CCT based on digital subtraction angiography data exhibits an independent predictive performance for clinical outcome in patients with acute ischemic stroke–large‐vessel occlusion after EVT. Given that this readily available CCT can provide alternative perfusion information during EVT, a prospective, multicenter trial is warranted.

homogeneous and heterogeneous catalysts for N 2 reduction. [8][9][10][11][12][13][14][15] Artificial catalysts show a great potential because of high activity and tunability, as well as the flexibility to be incorporated into sophisticated electrode assemblies. [16][17][18] Various model catalyst complexes for N 2 reduction were synthesized, which contain low-oxidationstate central metal (such as Mo, Fe, Co, etc.) [19][20][21][22][23] and the supporting ligand that is invariably highly electron donating, such as amides, [10] phosphines, [24][25][26] sulfido, and/or cyclic alkyl(amino)carbenes. [8,27,28] This indicates that the large charge buffer capacity of the central metal is crucial to the catalytic N 2 -to-NH 3 conversion. [14,29,30] To gain further insight into the redoxflexible character of active site in N 2 reduction, studies have been focused on the role of the interaction between central metal and its linked main-group atom in binding, activating, and functionalizing N 2 . [31][32][33] The landmark work on welldefined Fe-based complex with tris(phosphino)alkyl (XP iPr 3 ) (X = C, [28] Si, [34,35] B [20,36] ) ligand featuring axial C/Si/B donor has established a modestly effective catalyst for N 2 -to-NH 3 conversion by addition of protons and electrons at low temperatures. Among the isostructural BP iPr 3 , CP iPr 3 , and SiP iPr 3 series, the system with the most flexible axial linkage, (BP iPr 3 )Fe, gives the greatest catalytic yield under a common set of reaction conditions. [8,20,28,[35][36][37][38][39][40][41][42][43][44] A recent theoretical study elucidated that the reverse-dative Fe→B bonding is of critical importance for the stabilization of different nitrogen intermediates and oxidation states of the Fe center in the catalytic N 2 -to-NH 3 conversion. [45] The dominant contributions to the dative bond originate from the valence d-shell of the active metal center and corresponding ligand-centered bonding orbitals. [46] In addition to main group donors, the Lewis acidic ancillary metals in bimetallic cobaltdinitrogen complexes were also suggested to enhance the reverse-dative bond flexibility and electronic tuning of the active metal, priming a positive effect on reactivity. [47][48][49][50] Considering the importance of reverse-dative bonding between active metal and Lewis-acidic anchor in the catalytic N 2 fixation, a natural question is what happens with the substitution of the apical B atom of Lewis-acidic character with the Lewis-basic N atom in (XP iPr 3 )Fe complex (X denotes the anchor atom). In general, the presence of strong donor groups, such as amides, phosphines, and nitrogen-heterocyclic (NHC) carbenes, Due to the enigmatic existence of the carbon atom in the MoFeS cluster of iron-molybdenum cofactor (FeMoco), the design of biomimetic model catalysts featuring a dative bond between a transition metal and a main group atom is an important topic for efficient reduction of N 2 to NH 3 at ambient conditions. Different anchor atoms (X) for the trigonal bipyramidal (XP iPr 3 )Fe (X =...

A Au55 nanocluster with the composition of [Au55(p‐MBT)24(Ph3P)6](SbF6)3 (p‐MBT=4‐methylbenzenethiolate) is synthesized via direct reduction of gold‐phosphine and gold‐thiolate precursors. Single‐crystal X‐ray diffraction reveals that this Au55 nanocluster features a face‐centered cubic (fcc) Au55 kernel, different from the well‐known two‐shell cuboctahedral arrangement in Au55(Ph3P)12Cl6. The Au55 cluster shows a wide optical absorption band with optical energy gap (Eg=1.28 eV). It is found that the exclusion of chloride is crucial for the formation of the title cluster, otherwise rod‐like [Au25(SR)5(PPh3)10Cl2]2+ is obtained. The strategy to run synthetic reaction in the absence of halide leads to new members of phosphine/thiolate co‐protected metal nanoclusters. The Au55 nanocluster exhibits high catalytic activity and selectivity for electrochemical reduction of CO2 to CO; the Faradaic efficiency (FE) reaches 94.1 % at −0.6 V vs. reversible hydrogen electrode (RHE).

Highly Diastereoselective Synthesis of Cyclopentenones via a One-Pot Gold Catalysis, Nazarov Cyclization and Alkylation Cascade. -Propargylic carboxylates are converted to cyclopentenones by alkyl halogenides or nitrostyrene in a gold-catalyzed three-step one-pot synthesis. -(LIU, M.-Q.; ZHOU, A.-H.; JIANG, S.; WANG, J.-Q.; YE*, L.-W.; Synthesis 46 (2014) 16, 2161-2167, http://dx.

Developing highly efficient and low‐cost photocatalysts for overall water splitting has long been a pursuit for converting solar power into clean hydrogen energy. Herein, we demonstrate that a nonstoichiometric nickel–cobalt double hydroxide can achieve overall water splitting by itself upon solar light irradiation, avoiding the consumption of noble‐metal co‐catalysts. We employed an intensive laser to ablate a NiCo alloy target immersed in alkaline solution, and produced so‐called L‐NiCo nanosheets with a nonstoichiometric composition and O2−/Co3+ ions exposed on the surface. The nonstoichiometric composition broadens the band gap, while O2− and Co3+ ions boost hydrogen and oxygen evolution, respectively. As such, the photocatalyst achieves a H2 evolution rate of 1.7 μmol h−1 under AM 1.5G sunlight irradiation and an apparent quantum yield (AQE) of 1.38 % at 380 nm.