The preparation of the thermally stable, well-defined NHC-ligated difluoromethylated silver complexes 1a,b is described. were fully characterized, and structural assignments ambiguously further confirmed by single-crystal X-ray diffraction. Reactions [(SIPr)Ag(CF2H)] with a variety activated electrophiles such as diaryliodonium salts, vinyl(aryl)iodonium aryldiazonium acid chlorides in presence or absence CuI occurred smoothly at room temperature to generate compounds good excellent yields.

Abstract Pd‐catalyzed difluoromethylation of di‐, tri‐ or tetra‐substituted vinyl bromides, triflates, tosylates and nonaflates under mild conditions is described. The reaction tolerates a wide range functional groups, such as bromide, chloride, fluoride, ester, amine, nitrile, protected carbonyl, thus providing general route for the preparation difluoromethylated alkenes.

Nucleic acid-templated reactions have attracted significant attention for nucleic acid sensing and imaging. The level of signal amplification obtained from templated is a function the template turnover, wherein acts as catalyst. Herein, we report application pyridinium linker that immolates upon photocatalytic reduction with ruthenium complex to yield fastest reaction reported date. We show turnover limited by duplex dissociation kinetics beyond probes longer than 6-mer proceeded 5-mer PNA...

Novel photocaged lipids have been developed to release sphingosine at specific locations revealing a metabolic bias in ceramide synthesis based on subcellular location.

DNA-based circuitry empowers logic gated operations and amplifications but is restricted to nucleic acid output. Templated reactions enable the translation of cues into diverse small-molecule outputs are more limited in their amplification. Herein, we demonstrate coupling a DNA circuit templated order achieve high levels amplification output small molecules, response input. We that allows for detection fM concentration analyte can respond with release cytotoxic drug.

Enzyme-assisted posttranslational modifications (PTMs) constitute a major means of signaling across different cellular compartments. However, how nonenzymatic PTMs-despite their direct relevance to covalent drug development-impinge on cross-compartment remains inaccessible as current target-identification (target-ID) technologies offer limited spatiotemporal resolution, and proximity mapping tools are also not guided by specific, biologically-relevant, ligand chemotypes. Here we establish...

On a (pyr)role: A mild and highly efficient catalytic system has been developed for the asymmetric Friedel–Crafts alkylation of pyrroles with nitroalkenes (see scheme). High yields, excellent enantioselectivities regioselectivities were obtained broad range substrates. The synthetic utility this methodology mechanistic studies involving novel, negative, nonlinear effect are also presented. Detailed facts importance to specialist readers published as "Supporting Information". Such documents...

RNA , originally perceived as a simple information transfer biopolymer, is emerging an important regulator in cellular processes. A number of non‐coding s are double‐stranded and there need for technologies to reliably detect image such biological biomedical research. Herein we report ‐specific templated reaction resulting from PNA ‐reagent conjugates that brought within reactive distance through the formation sequence‐specific triplexes onto . The makes use ruthenium‐based photocatalyst...

Detection of specific oligonucleotide sequences is central to numerous applications, and technologies amenable point-of-care diagnostics or end users are needed. Here, we report a technology making use bioluminescent readout smartphone quantification. The sensor semisynthetic luciferase (H-Luc-PNA conjugate) that turned on by strand-displacement reaction. We demonstrated sensing three different microRNAs (miRs), as representative cancer biomarkers, demonstrate the possibility integrate an...

Abstract The ability to control the activity of kinases spatially and temporally is essential elucidate role signalling pathways in development physiology. Progress this direction has been hampered by lack tools manipulate kinase a highly controlled manner vivo. Here we report strategy modify BI2536, well characterized inhibitor conserved mitotic Polo-like 1 (Plk1). We introduce same coumarin photolabile protecting group (PPG) at two positions inhibitor. At one position, prevents interaction...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTElectrochemical studies of a novel ruthenium(II, III) dimer, trifluoroacetamidatoruthenium chloride (Ru2(HNOCCF3)4Cl)T. Malinski, D. Chang, F. N. Feldmann, J. L. Bear, and K. M. KadishCite this: Inorg. Chem. 1983, 22, 3225–3233Publication Date (Print):October 1, 1983Publication History Published online1 May 2002Published inissue 1 October 1983https://pubs.acs.org/doi/10.1021/ic00164a012https://doi.org/10.1021/ic00164a012research-articleACS...

Nucleic acid templated reactions have attracted attention as an important technology to sense oligonucleotides and translate nucleic acid-based instructions into diverse outputs. Great progress has been made in accelerating the reaction order improve signal amplification, reaching rates where substrate turnover rather than chemical is rate limiting. Herein we explore utility of architectures inspired by three-way junction that yield a cleavage strand thus turnover. We demonstrate such design...

Abstract Bioluminescence resonance energy transfer (BRET) has been widely used for studying dynamic processes in biological systems such as protein–protein interactions and other signaling events. Aside from acting a reporter, BRET can also turn on functions living systems. Herein, we report the application of to performing biorthogonal reaction cells; namely, releasing functional molecules through coumarin molecule, process termed bioluminolysis. An efficient Nanoluc‐Halotag chimera protein...

Protein trafficking and protein–protein interactions (PPIs) are central to regulatory processes in cells. Induced dimerization systems have been developed control PPIs regulate protein (localization) or interactions. Chemically induced (CID) has proven be a robust approach localization. The most recent embodiment of this technology relies on CID conjugates that react with self-labeling one side photocaged ligand the other provide spatiotemporal interaction interest. Advancing further is...

Abstract Proteome synthesis is profoundly influenced by subcellular stress. However, both the nature of spatiotemporally-restricted cues and underpinning local responders mediating these remain elusive. Unlocking mechanisms requires an ability to functionally map in living cells locale-specific stress simultaneously interrogate how a localized cue on specific players contextually impacts proteome trans . Here we resolve this prime problem integrating precision electrophile delivery...

Abstract A general route towards difluoromethylated alkenes is presented.

Abstract A new chiral catalyst system based on a central Cu 2 O four‐membered ring is used for asymmetric Friedel—Crafts alkylations of pyrroles with nitroalkenes.