Pillared Metal-Organic Framework Initiating Intermolecular Atom-Transfer Radical Addition via Visible-Light-Induced Electron Transfer Activation of Haloalkanes.

Herein, a novel metal-organic framework (MOF) with a pillared-layer structure was rationally synthesized to initiate intermolecular atom-transfer radical addition (ATRA) via photoinduced electron transfer activation of haloalkanes. The MOF synthesized via the controllable pillared-layer method is of excellent visible-light absorption and high chemical stability. Photocatalytic experiments show the atom transfer of various alkyl halides (R-X, X = Cl/Br/I) onto diverse olefins was successfully achieved to produce functional ATRA products. The mechanism and experimental investigations reveal the prepared MOF serves as an efficient photocatalyst with strong reduction potential to activate haloalkane substrates via photoinduced electron transfer, generating a highly reactive alkyl radical to trigger the ATRA reaction. Key events in the ATRA reaction, including alkyl radical photogeneration as well as halide transfer, have been further regulated to achieve preferable photocatalytic performance with higher yields, shorter reaction time, and desirable cycling capability. It is notable that the work is the first report on photoinduced electron transfer activation of halides by a MOF photocatalyst for the ATRA reaction, providing a new blueprint for MOFs to develop photoinduced radical reactions.

Photoactive Metal-Organic Frameworks for the Selective Synthesis of Thioethers: Coupled with Phosphine to Modulate Thiyl Radical Generation.

Metal-organic framework (MOF) materials are intriguing photocatalysts to trigger radical-mediated chemical transformations. We report herein the synthesis and characterization of a series of isomorphic MOFs which show a novel structure, wide visible-light absorption, high chemical stability, and specific redox potential. The prepared MOFs were explored for the photoinduced single-electron oxidation of thiol compounds, generating reactive thiyl radicals to afford thioethers via a convenient thiol-olefin reaction. Importantly, we provide a widely applicable strategy by combing a photoactive MOF with phosphine to modulate the generation of thiyl radical in the reaction, thereby producing a single product of the thioether without the formation of a disulfide byproduct due to the dimerization of thiyl radicals. The photocatalytic reaction takes advantage of this strategy, showing great generality where tens of thiols and olefins have been examined as coupling partners. In addition, the strategy has also been demonstrated to be effective for the reactions catalyzed by other MOFs. Mechanism studies reveal that the selective synthesis of C-S products relies on a synergy between the photoinduced generation of a thiyl radical over the MOF and the in situ cleavage of S-S bond into a S-H bond by phosphine. It is notable that the synthesized MOFs show advanced performance in comparison with classical MOFs. The work not only provides a series of novel MOF photocatalysts that are capable of photoinduced thiol-olefin coupling but also indicates the great potential of MOFs for photochemical transformations mediated by reactive radicals.

Expression and function analysis of Rac1 homolog in Chinese shrimp Fenneropenaeus chinensis.

Rac1 is a ubiquitous GTP-binding protein that plays a crucial role in multiple cellular processes. In the present study, a Rac1 homolog (FcRac1) was cloned from the Chinese shrimp Fenneropenaeus chinensis. The open reading frame (ORF) of FcRac1 consists of 579 bp encoding 192 aa. The predicted molecular weight (MW) of the deduced amino acid sequence of FcRac1 was 21.46 kDa, and its theoretical pI was 8.62. Homology analysis showed that the amino acid sequence of Rac1 had high conservation among those from different species. Phylogenetic analysis showed that FcRac1 closely related to Rac1 proteins from other arthropods. FcRac1 showed the highest expression level in the hemocytes. In situ hybridization detection showed that it distributed in all types of hemocytes. Recombinant protein of FcRac1 showed apparent activity of GTPase. The transcription of FcRac1 in juvenile shrimp changed after bacteria or WSSV challenge. The present data suggests that FcRac1 might play important roles in the innate immunity of shrimp.

An IκB homologue (FcCactus) in Chinese shrimp Fenneropenaeus chinensis.

This study firstly reports the characterization of a functional IκB homologue, FcCactus in Chinese shrimp Fenneropenaeus chinensis. The full length cDNA of FcCactus consists of a 1359 bp open reading frame (ORF) encoding a 453 amino acid protein with a predicted molecular weight (MW) of 48.46 kDa and theoretical pI of 5.23. Phylogenetic analysis and multiple alignments revealed that the deduced amino acid sequence of FcCactus cDNA had high similarities to Cactus or IκB reported in seven other arthropods. Genomic DNA sequence of FcCactus was also obtained with a length of more than 17698 bp and constituted of seven exons and six introns. Analysis on 5'-upstream regulatory region of its DNA sequence revealed that it contained the core promoter sequence with the TATA-box and transcription start site existing in it; furthermore, various transcription factor binding sites (HSF, Hb, BR-C Z, Dfd, CF2-II, Croc, Ttk, Dorsal, and c-Rel) were predicted. Spatial expression profiles showed that FcCactus mRNA had the highest expression level in muscle, hemocytes, heart and lymphoid organ. Gram-positive bacteria (Micrococcus lysodeikticus) and Gram-negative bacteria (Vibrio anguillarium) injection to shrimp caused the modulation of FcCactus at the transcription level. DsRNAi (double-strand RNA interference) approach was used to study the function of FcCactus and the data showed that FcCactus could regulate the expression of different antimicrobial peptides (AMPs) and antiviral factor (AV). The present data showed that FcCactus might play important roles in regulating the immune response of shrimp.

Potential relationship among three antioxidant enzymes in eliminating hydrogen peroxide in penaeid shrimp.

Antioxidant enzymes, such as glutathione peroxidase (GPx), catalase (CAT), and peroxiredoxin (Prx), are essential components in cells to eliminate excessive reactive oxygen species such as hydrogen peroxide (H(2)O(2)). GPx, CAT, and Prx genes have been reported in penaeid shrimp, and they showed different expression profiles at transcription or protein level when shrimps were challenged by microbes. In order to learn the relationship among the above three genes in their function, GPx, CAT, and Prx transcripts were analyzed, and the variation of GPx and CAT enzyme activity was detected when shrimp was injected with H(2)O(2) or one antioxidant enzyme gene was silenced in shrimp by double-strand RNA injection. The results indicated that there existed some relationships among three antioxidant enzyme genes, CAT, GPx, and Prx in shrimp at transcriptional level. The transcription of CAT and GPx could be directly induced by H(2)O(2) injection, while the transcription of Prx cannot be induced by H(2)O(2). Decreased transcription level of CAT or GPx could lead to increased transcription of the other two genes, which suggested that there existed some compensation among these three antioxidant enzyme genes. These data can help us to understand the roles of antioxidant enzymes in crustacean.