Chiral amines are widely used as catalysts in asymmetric synthesis to activate carbonyl groups for α-functionalization. Carbonyl catalysis reverses that strategy by using a carbonyl group to activate a primary amine. Inspired by biological carbonyl catalysis, which is exemplified by reactions of pyridoxal-dependent enzymes, we developed an N-quaternized pyridoxal catalyst for the asymmetric Mannich reaction of glycinate with aryl -diphenylphosphinyl imines. The catalyst exhibits high activity and stereoselectivity, likely enabled by enzyme-like cooperative bifunctional activation of the substrates. Our work demonstrates the catalytic utility of the pyridoxal moiety in asymmetric catalysis.
High‐performance microwave absorbers with special features are desired to meet the requirements of more complex modern service environments, especially corrosive environments. Therefore, high‐efficiency microwave absorbers with corrosion resistance should be developed urgently. Herein, a 3D NiAl‐layered double hydroxide/graphene (NiAl‐LDH/G) composite synthesized by atomic‐layer‐deposition‐assisted in situ growth is presented as an anticorrosive microwave absorber. The content of NiAl‐LDH in the composite is optimized to achieve impedance matching. Furthermore, under the cooperative effects of the interface polarization loss, conduction loss, and 3D porous sandwich‐like structure, the optimal NiAl‐LDH/G shows excellent microwave absorption performance with a minimum reflection loss of −41.5 dB and a maximum effective absorption bandwidth of 4.4 GHz at a loading of only 7 wt% in epoxy. Remarkably, the encapsulation effect of NiAl‐LDH can restrain the galvanic corrosion owing to graphene. The epoxy coating with the NiAl‐LDH/G microwave absorber on carbon steel exhibits long‐term corrosion resistance, owing to the synergetic effect of the superior impermeability of graphene and the chloridion‐capture capacity of the NiAl‐LDH. The NiAl‐LDH/G composite is a promising anticorrosive microwave absorber, and the findings of this study may motivate the development of functional microwave absorbers that meet the demands of anticorrosive performance of coatings.
Advances in flexible optoelectronic devices have led to an increasing need for developing highly efficient, low-cost, flexible transparent conducting electrodes. Copper-based electrodes have been unattainable due to the relatively low optical transmission and poor oxidation resistance of copper. Here, we report the synthesis of a completely continuous, smooth copper ultra-thin film via limited copper oxidation with a trace amount of oxygen. The weakly oxidized copper thin film sandwiched between zinc oxide films exhibits good optoelectrical performance (an average transmittance of 83% over the visible spectral range of 400–800 nm and a sheet resistance of 9 Ω sq−1) and strong oxidation resistance. These values surpass those previously reported for copper-based electrodes; further, the record power conversion efficiency of 7.5% makes it clear that the use of an oxidized copper-based transparent electrode on a polymer substrate can provide an effective solution for the fabrication of flexible organic solar cells.
The rhodium-catalyzed asymmetric hydroboration of α-arylenamides with BI-DIME as the chiral ligand and (Bpin)2 as the reagent yields for the first time a series of α-amino tertiary boronic esters in good yields and excellent enantioselectivities (up to 99% ee).
Copper has attracted significant interests as an abundant and low‐cost alternative material for flexible transparent conducting electrodes (FTCEs). However, Cu‐based FTCEs still present unsolved technical issues, such as their inferior light transmittance and oxidation durability compared to conventional indium tin oxide (ITO) and silver metal electrodes. This study reports a novel technique for fabricating highly efficient FTCEs composed of a copper ultrathin film sandwiched between zinc oxides, with enhanced transparency and antioxidation performances. A completely continuous and smooth copper ultrathin film is fabricated by a simple room‐temperature reactive sputtering process involving controlled nitrogen doping (<1%) due to a dramatic improvement in the wettability of copper on zinc oxide surfaces. The electrode based on the nitrogen‐doped copper film exhibits an optimized average transmittance of 84% over a spectral range of 380 −1000 nm and a sheet resistance lower than 20 Ω sq−1, with no electrical degradation after exposure to strong oxidation conditions for 760 h. Remarkably, a flexible organic solar cell based on the present Cu‐based FTCE achieves a power conversion efficiency of 7.1%, clearly exceeding that (6.6%) of solar cells utilizing the conventional ITO film, and this excellent performance is maintained even in almost completely bent configurations.
In this first-in-human study, we demonstrated the feasibility of using (99m)Tc-3P(4)-RGD(2) scintigraphy in differentiating SPNs. This procedure appears to be highly sensitive in detection of malignant SPNs. SPECT visual analysis seems to be sufficient for characterization of SPNs.
Improving the wetting ability of Ag on chemically heterogeneous oxides is technically important to fabricate ultrathin, continuous films that would facilitate the minimization of optical and electrical losses to develop qualified transparent Ag film electrodes in the state-of-the-art optoelectronic devices. This goal has yet to be attained, however, because conventional techniques to improve wetting of Ag based on heterogeneous metallic wetting layers are restricted by serious optical losses from wetting layers. Herein, we report on a simple and effective technique based on the partial oxidation of Ag nanoclusters in the early stages of Ag growth. This promotes the rapid evolution of the subsequently deposited pure Ag into a completely continuous layer on the ZnO substrate, as verified by experimental and numerical evidence. The improvement in the Ag wetting ability allows the development of a highly transparent, ultrathin (6 nm) Ag continuous film, exhibiting an average optical transmittance of 94% in the spectral range 400-800 nm and a sheet resistance of 12.5 Ω sq, which would be well-suited for application to an efficient front window electrode for flexible solar cell devices fabricated on polymer substrates.
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