Browse
Submit Data
Databases
API
Help

Dataset Information

17 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Transition metal catalysis in the mitochondria of living cells.

ABSTRACT: The development of transition metal catalysts capable of promoting non-natural transformations within living cells can open significant new avenues in chemical and cell biology. Unfortunately, the complexity of the cell makes it extremely difficult to translate standard organometallic chemistry to living environments. Therefore, progress in this field has been very slow, and many challenges, including the possibility of localizing active metal catalysts into specific subcellular sites or organelles, remain to be addressed. Herein, we report a designed ruthenium complex that accumulates preferentially inside the mitochondria of mammalian cells, while keeping its ability to react with exogenous substrates in a bioorthogonal way. Importantly, we show that the subcellular catalytic activity can be used for the confined release of fluorophores, and even allows selective functional alterations in the mitochondria by the localized transformation of inert precursors into uncouplers of the membrane potential.

SUBMITTER: Tomas-Gamasa M

PROVIDER: S-EPMC5023949 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts.

Project description:Bioorthogonal catalysis broadens the functional possibilities of intracellular chemistry. Effective delivery and regulation of synthetic catalytic systems in cells are challenging due to the complex intracellular environment and catalyst instability. Here, we report the fabrication of protein-sized bioorthogonal nanozymes through the encapsulation of hydrophobic transition metal catalysts into the monolayer of water-soluble gold nanoparticles. The activity of these catalysts can be reversibly controlled by binding a supramolecular cucurbit[7]uril 'gate-keeper' onto the monolayer surface, providing a biomimetic control mechanism that mimics the allosteric regulation of enzymes. The potential of this gated nanozyme for use in imaging and therapeutic applications was demonstrated through triggered cleavage of allylcarbamates for pro-fluorophore activation and propargyl groups for prodrug activation inside living cells.

| S-EPMC5697749 | biostudies-literature

Bridging the gap between transition metal- and bio-catalysis via aqueous micellar catalysis.

Project description:Previous studies have shown that aqueous solutions of designer surfactants enable a wide variety of valuable transformations in synthetic organic chemistry. Since reactions take place within the inner hydrophobic cores of these tailor-made nanoreactors, and products made therein are in dynamic exchange between micelles through the water, opportunities exist to use enzymes to effect secondary processes. Herein we report that ketone-containing products, formed via initial transition metal-catalyzed reactions based on Pd, Cu, Rh, Fe and Au, can be followed in the same pot by enzymatic reductions mediated by alcohol dehydrogenases. Most noteworthy is the finding that nanomicelles present in the water appear to function not only as a medium for both chemo- and bio-catalysis, but as a reservoir for substrates, products, and catalysts, decreasing noncompetitive enzyme inhibition.

| S-EPMC6520378 | biostudies-literature

Transition metal photoredox catalysis of radical thiol-ene reactions.

Project description:We describe the anti-Markovnikov hydrothiolation of olefins using visible-light-absorbing transition metal photocatalysts. The key thiyl radical intermediates are generated upon quenching of photoexcited Ru*(bpz)3(2) with a variety of thiols. The adducts of a wide variety of olefins and thiols are formed in excellent yield (73-99%).

| S-EPMC3573243 | biostudies-literature

Enantioselective transition-metal catalysis via an anion-binding approach.

Project description:Asymmetric transition-metal catalysis represents a powerful strategy for accessing enantiomerically enriched molecules1-3. The classical strategy for inducing enantioselectivity with transition-metal catalysts relies on direct complexation of chiral ligands to produce a sterically constrained reactive metal site that allows formation of the major product enantiomer while effectively inhibiting the pathway to the minor enantiomer through steric repulsion4. The chiral-ligand strategy has proven applicable to a wide variety of highly enantioselective transition-metal-catalysed reactions, but important scenarios exist that impose limits to its successful adaptation. Here, we report a new approach for inducing enantioselectivity in transition-metal-catalysed reactions that relies on neutral hydrogen-bond donors (HBDs)5,6 that bind anions of cationic transition-metal complexes to achieve enantiocontrol and rate enhancement through ion pairing together with other non-covalent interactions7-9. A cooperative anion-binding effect of a chiral bis-thiourea HBD is demonstrated to lead to high enantioselectivity (up to 99% enantiomeric excess) in intramolecular ruthenium-catalysed propargylic substitution reactions10. Experimental and computational mechanistic studies show the attractive interactions between electron-deficient arene components of the HBD and the metal complex that underlie enantioinduction and the acceleration effect.

| S-EPMC10388379 | biostudies-literature

Coupling Photoresponsive Transmembrane Ion Transport with Transition Metal Catalysis.

Project description:Artificial ion transporters have been explored both as tools for studying fundamental ion transport processes and as potential therapeutics for cancer and channelopathies. Here we demonstrate that synthetic transporters may also be used to regulate the transport of catalytic metal ions across lipid membranes and thus control chemical reactivity inside lipid-bound compartments. We show that acyclic lipophilic pyridyltriazoles enable Pd(II) cations to be transported from the external aqueous phase across the lipid bilayer and into the interior of large unilamellar vesicles. In situ reduction generates Pd(0) species, which catalyze the generation of a fluorescent product. Photocaging the Pd(II) transporter allows for photoactivation of the transport process and hence photocontrol over the internal catalysis process. This work demonstrates that artificial transporters enable control over catalysis inside artificial cell-like systems, which could form the basis of biocompatible nanoreactors for applications such as drug synthesis and delivery or to mediate phototargeted catalyst delivery into cells.

| S-EPMC10885138 | biostudies-literature

Understanding catalysis in a multiphasic two-dimensional transition metal dichalcogenide.

Project description:Establishing processing-structure-property relationships for monolayer materials is crucial for a range of applications spanning optics, catalysis, electronics and energy. Presently, for molybdenum disulfide, a promising catalyst for artificial photosynthesis, considerable debate surrounds the structure/property relationships of its various allotropes. Here we unambiguously solve the structure of molybdenum disulfide monolayers using high-resolution transmission electron microscopy supported by density functional theory and show lithium intercalation to direct a preferential transformation of the basal plane from 2H (trigonal prismatic) to 1T' (clustered Mo). These changes alter the energetics of molybdenum disulfide interactions with hydrogen (ΔG(H)), and, with respect to catalysis, the 1T' transformation renders the normally inert basal plane amenable towards hydrogen adsorption and hydrogen evolution. Indeed, we show basal plane activation of 1T' molybdenum disulfide and a lowering of ΔG(H) from +1.6 eV for 2H to +0.18 eV for 1T', comparable to 2H molybdenum disulfide edges on Au(111), one of the most active hydrogen evolution catalysts known.

| S-EPMC4633626 | biostudies-literature

Detection of Labile Low-Molecular-Mass Transition Metal Complexes in Mitochondria.

Project description:Liquid chromatography was used with an online inductively coupled plasma mass spectrometer to detect low-molecular-mass (LMM) transition metal complexes in mitochondria isolated from fermenting yeast cells, human Jurkat cells, and mouse brain and liver. These complexes constituted 20-40% of total mitochondrial Mn, Fe, Zn, and Cu ions. The major LMM Mn complex in yeast mitochondria, called Mn1100, had a mass of ?1100 Da and a concentration of ?2 ?M. Mammalian mitochondria contained a second Mn species with a mass of ?2000 Da at a comparable concentration. The major Fe complex in mitochondria isolated from exponentially growing yeast cells had a mass of ?580 Da; the concentration of Fe580 in mitochondria was ?100 ?M. When mitochondria were isolated from fermenting cells in postexponential phase, the mass of the dominant LMM Fe complex was ?1100 Da. Upon incubation, the intensity of Fe1100 declined and that of Fe580 increased, suggesting that the two are interrelated. Mammalian mitochondria contained Fe580 and two other Fe species (Fe2000 and Fe1100) at concentrations of ?50 ?M each. The dominant LMM Zn species in mitochondria had a mass of ?1200 Da and a concentration of ?110 ?M. Mammalian mitochondria contained a second major LMM Zn species at 1500 Da. The dominant LMM Cu species in yeast mitochondria had a mass of ?5000 Da and a concentration in yeast mitochondria of ?16 ?M; Cu5000 was not observed in mammalian mitochondria. The dominant Co species in mitochondria, Co1200, had a concentration of 20 nM and was probably a cobalamin. Mammalian but not yeast mitochondria contained a LMM Mo species, Mo730, at a concentration of ?1 ?M. Increasing Mn, Fe, Cu, and Zn concentrations 10-fold in the medium increased the concentration of the same element in the corresponding isolated mitochondria. Treatment with metal chelators confirmed that these LMM species were labile. The dominant S species at 1100 Da was not free glutathione or glutathione disulfide.

| S-EPMC4627607 | biostudies-literature

Abrupt increase in hydrogen diffusion on transition-metal surfaces during hydrogenation catalysis.

Project description:A sharp increase in the rate of hydrogen isotope scrambling was identified during the hydrogenation of olefins with H2 + D2 mixtures on Pt(111) catalysts, which spectroscopic data suggest is due to a sudden increase in atomic hydrogen surface mobility because of a decrease in the size of the islands of the adsorbed hydrocarbons.

| S-EPMC6013773 | biostudies-literature

Regioselective Simmons-Smith-type cyclopropanations of polyalkenes enabled by transition metal catalysis.

Project description:A [ i-PrPDI]CoBr2 complex (PDI = pyridine-diimine) catalyzes Simmons-Smith-type reductive cyclopropanation reactions using CH2Br2 in combination with Zn. In contrast to its non-catalytic variant, the cobalt-catalyzed cyclopropanation is capable of discriminating between alkenes of similar electronic properties based on their substitution patterns: monosubstituted > 1,1-disubstituted > (Z)-1,2-disubstituted > (E)-1,2-disubstituted > trisubstituted. This property enables synthetically useful yields to be achieved for the monocyclopropanation of polyalkene substrates, including terpene derivatives and conjugated 1,3-dienes. Mechanistic studies implicate a carbenoid species containing both Co and Zn as the catalytically relevant methylene transfer agent.

| S-EPMC5890799 | biostudies-literature

Umpolung reactivity of strained C-C σ-bonds without transition-metal catalysis.

Project description:Umpolung is an old and important concept in organic chemistry, which significantly expands the chemical space and provides unique structures. While, previous research focused on carbonyls or imine derivatives, the umpolung reactivity of polarized C-C σ-bonds still needs to explore. Herein, we report an umpolung reaction of bicyclo[1.1.0]butanes (BCBs) with electron-deficient alkenes to construct the C(sp3)-C(sp3) bond at the electrophilic position of C-C σ-bonds in BCBs without any transition-metal catalysis. Specifically, this transformation relies on the strain-release driven bridging σ-bonds in bicyclo[1.1.0]butanes (BCBs), which are emerged as ene components, providing an efficient and straightforward synthesis route of various functionalized cyclobutenes and conjugated dienes, respectively. The synthetic utilities of this protocol are performed by several transformations. Preliminary mechanistic studies including density functional theory (DFT) calculation support the concerted Alder-ene type process of C-C σ-bond cleavage with hydrogen transfer. This work extends the umpolung reaction to C-C σ-bonds and provides high-value structural motifs.

| S-EPMC10987681 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data