Abstract Herein, we introduce catalysts that operate with chalcogen bonds. Compared to conventional hydrogen bonds, bonds are similar in strength but more directional and hydrophobic, thus ideal for precision catalysis apolar solvents. For the transfer hydrogenation of quinolines imines, rate enhancements well beyond a factor 1000 obtained Better activities deeper σ holes wider bite angles, chloride inhibition correlation computed anion binding energies consistent operational Comparable...

ConspectusThe objective of this Account is to summarize the first five years anion−π catalysis. The general idea catalysis stabilize anionic transition states on aromatic surfaces. This complementary stabilization cationic surfaces, a mode action that occurs in nature and increasingly used chemistry. Anion−π catalysis, however, rarely has been unexplored Probably because attraction anions π surfaces as such counterintuitive, interactions are much younger than cation−π remain under-recognized...

Abstract Herein, we introduce catalysts that operate with chalcogen bonds. Compared to conventional hydrogen bonds, bonds are similar in strength but more directional and hydrophobic, thus ideal for precision catalysis apolar solvents. For the transfer hydrogenation of quinolines imines, rate enhancements well beyond a factor 1000 obtained Better activities deeper σ holes wider bite angles, chloride inhibition correlation computed anion binding energies consistent operational Comparable...

HydroFlippers respond to membrane compression and hydration in the same fluorescence lifetime imaging microscopy histogram: responses do not correlate.

Anion-π interactions on fullerenes are about as poorly explored the use of in catalysis. However, strong exchange-correlation contributions and localized π holes their surface promise unique selectivities. To elaborate this promise, tertiary amines attached nearby. Dependent positioning, resulting stabilization anionic transition states is shown to accelerate disfavored enolate addition exo Diels-Alder reactions enantioselectively. The found selectivities consistent with computational...

Controlling self-organization and morphology of chemical architectures is an essential challenge in the search for higher energy-conversion efficiencies a variety optoelectronic devices. Here, we report highly ordered donor/acceptor functional material, which has been obtained using principle ionic self-assembly. Initially, electron donor π-extended tetrathiafulvalene electron-acceptor perylene-bisimide were self-organized separately obtaining n- p-nanofibers at same scale. These...

Tools to image membrane tension in response mechanical stimuli are badly needed mechanobiology. We have recently introduced mechanosensitive flipper probes report quantitatively global changes fluorescence lifetime imaging microscopy (FLIM) images of living cells. However, address specific questions on physical forces biology, the need be localized precisely interest (MOI). Herein we present a general strategy MOI by tagging our newly HaloFlippers self-labeling HaloTags fused proteins this...

Epoxide-opening ether cyclizations are shown to occur on π-acidic aromatic surfaces without the need of additional activating groups and with autocatalytic amplification. Increasing activity intrinsic π acidity benzenes, naphthalenediimides (NDIs) perylenediimides (PDIs) support that anion−π interactions account for function. Rate enhancements maximize at 270 catalysis fullerenes 5100 M–1 autocatalysis. The occurrence autocatalysis is confirmed increasing initial rates in presence product....

Cyclic oligochalcogenides (COCs) are emerging as promising systems to penetrate cells. Clearly better than and different the reported diselenolanes epidithiodiketopiperazines, we introduce benzopolysulfanes (BPS), which show efficient delivery, insensitivity inhibitors of endocytosis, compatibility with substrates large proteins. This high activity coincides reactivity, selectively toward thiols, exceeding exchange rates disulfides under tension. The result is a dynamic-covalent network...

Ellman's reagent has caused substantial confusion and concern as a probe for thiol-mediated uptake because it is the only established inhibitor available but works neither efficiently nor reliably. Here we use fluorescent cyclic oligochalcogenides that enter cells by to systematically screen more potent inhibitors, including epidithiodiketopiperazines, benzopolysulfanes, disulfide-bridged γ-turned peptides, heteroaromatic sulfones thiosulfonates, thiosulfinates disulfides. With nanomolar...

The design, synthesis and evaluation of catalytic triads composed a central C60 fullerene with an amine base on one side polarizability enhancers the other are reported. According to enolate addition benchmark reaction, fullerene-fullerene-amine display highest selectivity in anion-π catalysis observed so far, whereas NDI-fullerene-amine not much better than fullerene-amine controls (NDI=naphthalenediimide). These large differences activity conflict small intrinsic π acidity, that is, LUMO...

Abstract The design, synthesis and evaluation of catalytic triads composed a central C 60 fullerene with an amine base on one side polarizability enhancers the other are reported. According to enolate addition benchmark reaction, fullerene–fullerene–amine display highest selectivity in anion–π catalysis observed so far, whereas NDI–fullerene–amine not much better than fullerene–amine controls (NDI=naphthalenediimide). These large differences activity conflict small intrinsic π acidity, that...

In this report, cell-penetrating streptavidin (CPS) is introduced to exploit the full power of streptavidin–biotin biotechnology in cellular uptake. For purpose, transporters, here cyclic oligochalcogenides (COCs), are covalently attached lysines wild-type streptavidin. This leaves all four biotin binding sites free for at least bifunctional delivery. To maximize standards quantitative evaluation cytosolic delivery, recent chloroalkane penetration assay (CAPA) coupled with automated high...

From nano- to macroscale: The immobilization of photo- and redox-active 9,10-di(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene-based dipeptide 1 onto SWCNTs resulted in a high order self-alignment among 1/SWCNTs (see picture). assembly the is key for stabilizing long-lived charge-separated states that are formed upon photoexcitation SWCNTs.

Induced π acidity from polarizability is emerging as the most effective way to stabilize anionic transition states on aromatic surfaces, that is, anion-π catalysis. To access extreme polarizability, we propose a shift homogeneous toward heterogeneous catalysis higher carbon allotropes. According benchmark enolate addition chemistry, multi-walled nanotubes equipped with tertiary amine bases outperform single-walled nanotubes. This consistent of former not only along but also between tubes....

The cytosolic delivery of various substrates in 3D multicellular spheroids by thiol-mediated uptake is reported. This important because most orthodox systems, including polycationic cell-penetrating peptides, fail to deliver efficiently into deep tissue. grand principles supramolecular chemistry, that the pH dependence dynamic covalent disulfide exchange with known thiols on transferrin receptor, are proposed account for transcytosis tissue, while but elusive cascades along same or other...

To image membrane tension in selected membranes of interest (MOI) inside living systems, the field mechanobiology requires increasingly elaborated small-molecule chemical tools. We have recently introduced HaloFlipper, i.e., a mechanosensitive flipper probe that can localize MOI using HaloTag technology to report local changes fluorescence lifetime imaging microscopy. However, linker tethering hampers lateral diffusion all lipid domains MOI. For more global measurement any MOI, we present...

Mechanosensitive flipper probes are attracting interest as fluorescent reporters of membrane order and tension in biological systems. We introduce PhotoFlippers, which contain a photocleavable linker an ultralong tether between mechanophore various targeting motifs. Upon irradiation, the original probe is released labels most ordered that accessible by intermembrane transfer. Spatiotemporal control from flippers essential to access open, dynamic or elusive motifs without chemical physical...

Abstract Measuring forces within living cells remains a technical challenge. We developed hydrophobic mechanosensing fluorescent probes called Flippers, whose fluorescence lifetime depends on lipid packing and can report membrane tension. Here, we describe optimization of the probe imaging, diverse characterizations in various biological vitro systems. provide guideline to measure biophysical parameters cellular membranes by FLIM microscopy with Flipper probes, providing evidences that...

Abstract The development of sophisticated ordered functional materials is one the important challenges in current science. One keys to enhance properties these control organization and morphology at different scales. This work presents a novel bioinspired methodology achieve highly donor/acceptor bio‐nanohybrids using designed repeat protein as scaffold, endowed with photoactive electron donating porphyrin (P) units, efficiently wrap around accepting single wall carbon nanotubes (SWCNT). A...

An innovative approach is investigated in which a protein building block designed to organize porphyrin molecules. The strategy based on modular unit with tunable properties including stability, function and self-assembly.

Anion‐ π interactions have been recently introduced to catalysis with the idea stabilize anionic intermediates on ‐acidic surfaces. Realized examples include enolate, enamine and iminium chemistry, domino processes Diels–Alder reactions. Moving from formation of contiguous stereogenic centers surfaces, herein we report first asymmetric anion‐ cascade reactions that afford nonadjacent stereocenters. Conjugate addition‐protonation achiral disubstituted enolate donors 2‐chloroacrylonitrile...