Covalent organic frameworks (COFs) are excellent platforms with tailored functionalities in photocatalysis. There are still challenges in increasing the photochemical performance of COFs. Therefore, we designed and prepared a series of COFs for photocatalytic hydrogen generation. Varying different ratios of βketoenamine to imine moieties in the linkages could differ the ordered structure, visible light harvesting, and bandgap. Overall, βketoenamine-linked COFs exhibited much better photocatalytic activity than those COFs having both β-ketoenamine and imine moieties on account of a nonquenched excited state and more favorable HOMO level in the photoinduced oxidation reaction from the former. Specifically, after in situ growth of β-ketoenamine-linked COFs onto NH 2 −Ti 3 C 2 T x MXene via covalent connection, the heterohybrid showed an obvious improvement in photocatalytic H 2 evolution because of strong covalent coupling, electrical conductivity, and efficient charge transfer. This integrated linkage evolution and covalent hybridization approach advances the development of COF-based photocatalysts.
This review highlights a number of additives that can be used to make asymmetric reactions perfect. Without changing other reaction conditions, simply adding additives can lead to improved asymmetric catalysis, such as reduced reaction time, improved yield, or/and increased selectivity.
Amorpha-4,11-diene synthase (ADS) of Artemisia annua catalyzes the conversion of farnesyl diphosphate into amorpha-4,11-diene, the first committed step in the biosynthesis of the antimalarial drug artemisinin. The promoters of ADS contain two reverse-oriented TTGACC W-box cis-acting elements, which are the proposed binding sites of WRKY transcription factors. A full-length cDNA (AaWRKY1) was isolated from a cDNA library of the glandular secretory trichomes (GSTs) in which artemisinin is synthesized and sequestered. AaWRKY1 encodes a 311 amino acid protein containing a single WRKY domain. AaWRKY1 and ADS genes were highly expressed in GSTs and both were strongly induced by methyl jasmonate and chitosan. Transient expression analysis of the AaWRKY1-GFP (green fluorescent protein) reporter revealed that AaWRKY1 was targeted to nuclei. Biochemical analysis demonstrated that the AaWRKY1 protein was capable of binding to the W-box cis-acting elements of the ADS promoters, and it demonstrated transactivation activity in yeast. Co-expression of the effector construct 35S::AaWRKY1 with a reporter construct ADSpro1::GUS greatly activated expression of the GUS (beta-glucuronidase) gene in stably transformed tobacco. Furthermore, transient expression experiments in agroinfiltrated Nicotiana benthamiana and A. annua leaves showed that AaWRKY1 protein transactivated the ADSpro2 promoter activity by binding to the W-box of the promoter; disruption of the W-box abolished the activation. Transient expression of AaWRKY1 cDNA in A. annua leaves clearly activated the expression of the majority of artemisinin biosynthetic genes. These results strongly suggest the involvement of the AaWRKY1 transcription factor in the regulation of artemisinin biosynthesis, and indicate that ADS is a target gene of AaWRKY1 in A. annua.
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