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We discuss the implication of the advances in the context of optoelectronic applications. This journal is © The Royal Society of Chemistry 2020.Atomically precise engineering on the nanocluster surface remains highly desirable for the fundamental understanding of how surface structures of a nanocluster contribute to its overall properties. In this paper, the concept of "graft-onto" has been exploited to facilitate nanocluster growth on surface structures. Specifically, the Ag2(DPPM)Cl2 complex is used for re-constructing the surface structure of Pt1Ag28 (SR)18(PPh3)4 (Pt1Ag28 , SR = 1-adamantanethiolate) and producing a size-growth nanocluster - Pt1Ag31 (SR)16(DPPM)3Cl3 (Pt1Ag31 ). The grafting effect of Ag2(DPPM)Cl2 induces both direct changes on the surface structure (e.g., size growth, structural transformation, and surface rotation) and indirect changes on the kernel structure (from a fcc configuration to an icosahedral configuration). Remarkable differences have been observed by comparing optical properties between Pt1Ag28 and Pt1Ag31 . Significantly, Pt1Ag31 exhibits high photo-luminescent intensity with a quantum yield of 29.3%, which is six times that of the Pt1Ag28 . Overall, this work presents a new approach (i.e., graft-onto) for the precise dictation of nanocluster surface structures at the atomic level. This journal is © The Royal Society of Chemistry 2020.The high-valent nickel(iii) complex Ni(pyalk)2 + (2) was prepared by oxidation of a nickel(ii) complex, Ni(pyalk)2 (1) (pyalk = 2-pyridyl-2-propanoate). 2 and derivatives were fully characterized by mass spectrometry and X-ray crystallography. Electron paramagnetic resonance spectroscopy and X-ray photoelectron spectroscopy confirm that the oxidation is metal-centered. 2 was found to react with a variety of phenolic and hydrocarbon substrates. A linear correlation between the measured rate constant and the substrate bond dissociation enthalpy (BDE) was found for both phenolic and hydrocarbon substrates. Large H/D kinetic isotope effects were also observed for both sets of substrates. These results suggest that 2 reacts through concerted proton-electron transfer (CPET). Analysis of measured thermodynamic parameters allows us to calculate a bond dissociation free energy (BDFE) of ∼91 kcal mol-1 for the O-H bond of the bound pyalk ligand. These findings may shed light onto CPET steps in oxidative catalysis and have implications for ligand design in catalytic systems. This journal is © The Royal Society of Chemistry 2020.A new selenophosphoramide-catalyzed diamination of terminal- and trans-1,2-disubstituted olefins is presented. Key to the success of this transformation was the introduction of a fluoride scavenger, trimethylsilyl trifluoromethanesulfonate (TMSOTf), to prevent a competitive syn-elimination pathway, as was the use of a phosphoramide ligand on selenium to promote the desired substitution reaction. A screen of catalysts revealed that more electron-rich phosphine ligands resulted in higher yields of the desired product, with selenophosphoramides giving the optimal results. A broad range of substrates and functional groups were tolerated and yields were generally good to excellent. For (E)-1,2-disubstituted olefins, diastereoselectivities were always high, giving exclusively anti products. The conditions were also applied to substrates bearing internal nucleophiles such as esters and carbonates, giving rise to 1,2-aminoesters and cyclic carbonates, respectively. This journal is © The Royal Society of Chemistry 2020.A divergent cyclopropanation reaction has been accomplished via the dearomative addition of sulfur ylides to activated N-heteroarenes. A series of biologically significant molecular skeletons was obtained by the direct cyclopropanation of quinolinium zwitterions. Furthermore, a straightforward synthetic route to optically enriched cyclopropane-fused heterocycles was developed using sulfur ylides as chiral nucleophiles in the 1,4-dearomative reaction. This journal is © The Royal Society of Chemistry 2020.Given the powerful regulation roles of chemical modification networks in protein structures and functions, it is of vital importance to acquire the spatiotemporal chemical modification pattern information in a protein-specific fashion, which is by far a highly challenging task. Herein, we design a localized DNA automaton, equipped with an anticoding-coding sequential propagation algorithm, for in situ visualization of a given protein subtype with two chemical modifications of interest on the cell surface. The automaton is composed of three probes respectively for the protein and two types of modifications. Selleck NXY-059 Once anchored on the cell surface and triggered, the automaton performs sequential protein-localized, DNA hybridization-based computations on the proximity status of each modification type with the protein and contracts the set of close proximity information into a single fluorescence signal turn-on using the designed algorithm. The modular and scalable features of the automaton enable its operation in scaled-down versions for protein-specific identification of one given modification. Thus, this work opens up the possibility of using automata for revealing complex regulation mechanisms of protein posttranslational modifications. This journal is © The Royal Society of Chemistry 2020.Precise genetic manipulation is vital to studying bacterial physiology, but is difficult to achieve in some bacterial species due to the weak intrinsic homologous recombination (HR) capacity and lack of a compatible exogenous HR system. Here we report the establishment of a rapid and efficient method for directly converting adenine to guanine in bacterial genomes using the fusion of an adenine deaminase and a Cas9 nickase. The method achieves the conversion of adenine to guanine via an enzymatic deamination reaction and a subsequent DNA replication process rather than HR, which is utilized in conventional bacterial genetic manipulation methods, thereby substantially simplifying the genome editing process. A systematic screening targeting the possibly editable adenine sites of cntBC, the importer of the staphylopine/metal complex in Staphylococcus aureus, pinpoints key residues for metal importation, demonstrating that application of the system would greatly facilitate the genomic engineering of bacteria. This journal is © The Royal Society of Chemistry 2020.
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