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151.
152.
    
Methods to synthesize crystalline covalent triazine frameworks (CTFs) are limited and little attention has been paid to development of hydrophilic CTFs and photocatalytic overall water splitting. A route to synthesize crystalline and hydrophilic CTF-HUST-A1 with a benzylamine-functionalized monomer is presented. The base reagent used plays an important role in the enhancement of crystallinity and hydrophilicity. CTF-HUST-A1 exhibits good crystallinity, excellent hydrophilicity, and excellent photocatalytic activity in sacrificial photocatalytic hydrogen evolution (hydrogen evolution rate up to 9200 μmol g−1 h−1). Photocatalytic overall water splitting is achieved by depositing dual co-catalysts in CTF-HUST-A1, with H2 evolution and O2 evolution rates of 25.4 μmol g−1 h−1 and 12.9 μmol g−1 h−1 in pure water without using sacrificial agent.  相似文献   
153.
    
Squaraines (SQs) with tunable emission in the solid state is of great importance for various demands; however a remaining challenge is emission quenching upon aggregation. Herein, a unique SQ, named as CIEE-SQ, is designed to exhibit strong emission in crystal, undergoing crystallization-induced reverse from dark 1(n+σ,π*) to bright 1(π,π*) excited states. Such an excited state of CIEE-SQ can be subtly tuned by molecular conformation changes during the unexpected temperature-triggered single-crystal to single-crystal (SCSC) reversible transformation. Furthermore, co-crystallization between CIEE-SQ and chloroform largely stabilize the 1(π,π*) state, enhancing the transition dipole moment and decreasing the reorganization energy to boost the fluorescence, which is promising in data encryption and decryption.  相似文献   
154.
By transplanting identity elements into E. coli tRNAfMet, we have engineered an orthogonal initiator tRNA (itRNATy2) that is a substrate for Methanocaldococcus jannaschii TyrRS. We demonstrate that itRNATy2 can initiate translation in vivo with aromatic non-canonical amino acids (ncAAs) bearing diverse sidechains. Although the initial system suffered from low yields, deleting redundant copies of tRNAfMet from the genome afforded an E. coli strain in which the efficiency of non-canonical initiation equals elongation. With this improved system we produced a protein containing two distinct ncAAs at the first and second positions, an initial step towards producing completely unnatural polypeptides in vivo. This work provides a valuable tool to synthetic biology and demonstrates remarkable versatility of the E. coli translational machinery for initiation with ncAAs in vivo.  相似文献   
155.
    
Boron-containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron-containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B2(OH)xO(3−x/2) (x=0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM-22 isomorphously substituted with boron (B-MWW). Using 11B solid-state NMR spectroscopy, we show that the majority of boron species in B-MWW exist as isolated BO3 units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B-MWW for ODH of propane falsifies the hypothesis that site-isolated BO3 units are the active site in boron-based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium-based catalysts and provides an important piece of the mechanistic puzzle.  相似文献   
156.
Metal–organic frameworks (MOFs) with long-term stability and reversible high water uptake properties can be ideal candidates for water harvesting and indoor humidity control. Now, a mesoporous and highly stable MOF, BIT-66 is presented that has indoor humidity control capability and a photocatalytic bacteriostatic effect. BIT-66 (V3(O)3(H2O)(BTB)2), possesses prominent moisture tunability in the range of 45–60 % RH and a water uptake and working capacity of 71 and 55 wt %, respectively, showing good recyclability and excellent performance in water adsorption–desorption cycles. Importantly, this MOF demonstrates a unique photocatalytic bacteriostatic behavior under visible light, which can effectively ameliorate the bacteria and/or mold breeding problem in water adsorbing materials.  相似文献   
157.
Enantiospecific intramolecular Suzuki–Miyaura-type coupling with α-(2-halobenzoylamino)benzylboronic esters to give 3-substituted isoindolinones is achieved by using copper catalysts with 2,2′-bipyridine-based achiral ligands. Enantioenriched α-aminobenzylboron reactants bearing a hydrogen atom at the boron-bound stereogenic carbons undergo stereoinvertive coupling in the presence of a 6-phenyl-2,2′-bipyridine ligand with high enantiospecificity. α-Aminobenzylboronates bearing fully substituted boron-bound stereogenic centers also gave the 3,3-disubstituted isoindolinones with stereospecific stereochemical inversion in the presence of simple 2,2′-bipyridine as a ligand.  相似文献   
158.
    
Herein, we report a theoretical and experimental study of the water-gas shift (WGS) reaction on Ir1/FeOx single-atom catalysts. Water dissociates to OH* on the Ir1 single atom and H* on the first-neighbour O atom bonded with a Fe site. The adsorbed CO on Ir1 reacts with another adjacent O atom to produce CO2, yielding an oxygen vacancy (Ovac). Then, the formation of H2 becomes feasible due to migration of H from adsorbed OH* toward Ir1 and its subsequent reaction with another H*. The interaction of Ir1 and the second-neighbouring Fe species demonstrates a new WGS pathway featured by electron transfer at the active site from Fe3+−O⋅⋅⋅Ir2+−Ovac to Fe2+−Ovac⋅⋅⋅Ir3+−O with the involvement of Ovac. The redox mechanism for WGS reaction through a dual metal active site (DMAS) is different from the conventional associative mechanism with the formation of formate or carboxyl intermediates. The proposed new reaction mechanism is corroborated by the experimental results with Ir1/FeOx for sequential production of CO2 and H2.  相似文献   
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