Chemical Science

List of Papers (Total 4,436)

Total synthesis of griseusins and elucidation of the griseusin mechanism of action.

A divergent modular strategy for the enantioselective total synthesis of 12 naturally-occurring griseusin type pyranonaphthoquinones and 8 structurally-similar analogues is described. Key synthetic highlights include Cu-catalyzed enantioselective boration–hydroxylation ...

Insights from 125Te and 57Fe nuclear resonance vibrational spectroscopy: a [4Fe-4Te] cluster from two points of view.

Iron–sulfur clusters are common building blocks for electron transport and active sites of metalloproteins. Their comprehensive investigation is crucial for understanding these enzymes, which play important roles in modern biomimetic catalysis ...

Electrochemical C-H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source.

High-valent iron-oxo complexes are key intermediates in C–H functionalization reactions. Herein, we report the generation of a (TAML)Fe-oxo species (TAML = tetraamido macrocyclic ligand) via electrochemical proton-coupled oxidation of the corresponding ...

A natural solution to photoprotection and isolation of the potent polyene antibiotic, marinomycin A.

The photoprotection and isolation of marinomycin A using sporopollenin exine capsules (SpECs) derived from the spores of the plant Lycopodium clavatum is described. The marinomycins have a particularly short half-life in natural light, which severely ...

Fatty acid based transient nanostructures for temporal regulation of artificial peroxidase activity.

Natural systems access transient high energy self-assembled structures for temporal regulation of different biological functions through dissipative processes. Compartmentalization within self-assembled structures is used by living systems to organize ...

Enantioselective palladium/copper-catalyzed C-C σ-bond activation synergized with Sonogashira-type C(sp3)-C(sp) cross-coupling alkynylation.

The Sonogashira-type cross-coupling reaction is one of the most significant alkynylation transformations in organic chemistry. However, highly enantioselective alkynylation via the Sonogashira-type cross-coupling reaction is rather limited, mainly due ...

Targeting trimeric transmembrane domain 5 of oncogenic latent membrane protein 1 using a computationally designed peptide.

Protein–protein interactions are involved in diverse biological processes. These interactions are therefore vital targets for drug development. However, the design of peptide modulators targeting membrane-based protein–protein interactions ...

Rational synthesis of three-dimensional core-double shell upconversion nanodendrites with ultrabright luminescence for bioimaging application.

Herein, we rationally fabricated three-dimensional upconversion core–double shell nanodendrites as efficient and safe luminescent probes for in vitro and in vivo bioimaging.Engineering the morphology of rare-earth doped NaYF[4] -based upconversion ...

Structural and defect engineering of cobaltosic oxide nanoarchitectures as an ultrahigh energy density and super durable cathode for Zn-based batteries.

The key challenges of aqueous Zn-based batteries (ZBBs) are their unsatisfactory energy density and poor lifespan, mainly arising from the low capacity and irreversibility of the cathode materials. Herein, a three-dimensional (3D) ordered mesoporous nanoarchitecture ...

Designer artificial membrane binding proteins to direct stem cells to the myocardium.

We present a new cell membrane modification methodology where the inherent heart tissue homing properties of the infectious bacteria Streptococcus gordonii are transferred to human stem cells. This is achieved via the rational design of a chimeric protein–polymer ...

Heterogeneous Rh and Rh/Ag bimetallic nanoparticle catalysts immobilized on chiral polymers.

The development of heterogeneous chiral catalysts has lagged far behind that of homogeneous chiral catalysts in spite of their advantages, such as environmental friendliness for a sustainable society. We describe herein novel heterogeneous chiral Rh and ...

A K+-promoted Diels-Alder reaction by using a self-assembled macrocyclic boronic ester containing two crown ether moieties.

A K[+] -promoted Diels–Alder reaction of 1,4,9,10-anthradiquinone with various dienes is achieved in the presence of a self-assembled macrocyclic boronic ester [2+2][crown] containing two crown ether moieties. The reaction rate is remarkably ...

Two dimensional diffusion-controlled triplet-triplet annihilation kinetics.

We show with time-resolved second harmonic generation and molecular mechanics simulations that the kinetics of a two-dimensional triplet–triplet annihilation reaction at the liquid–liquid interface is affected by molecular crowding.Diffusion ...

Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts.

The free energy landscape of catalytic intermediates in the two-electron reduction of proton donors and/or CO[2] to H[2] , CO and HCO[2] [–] is mapped with density functional theory to screen catalyst candidates from a library of different transition ...

Two-photon-excited ultralong organic room temperature phosphorescence by dual-channel triplet harvesting.

Due to inefficient molecular design strategies, two-photon-excited ultralong organic room temperature phosphorescence (TPUOP) has not yet been reported in single-component materials. Herein, we present an innovative design method by dual-channel triplet ...

Stereoselective total synthesis of parthenolides indicates target selectivity for tubulin carboxypeptidase activity.

The discovery of novel allylboration reagents enabled to the stereoselective synthesis of parthenolides. Biological screening for microtubule detyrosination and nerve growth promotion revealed protein target selectivity.The 2-(silyloxymethyl)allylboration ...

Molecular mechanism for thermal denaturation of thermophilic rhodopsin.

Studies of microbial rhodopsins revealed that hydrolysis of the retinal protonated Schiff base is the rate-determining step of the thermal denaturation process.Understanding the factors affecting the stability and function of proteins at the molecular ...

Mild synthesis of diboryldiborenes by diboration of B-B triple bonds.

A set of diboryldiborenes are prepared by the mild, catalyst-free, room-temperature diboration of the B–B triple bonds of doubly base-stabilized diborynes. Two of the product diboryldiborenes are found to be air- and water-stable in the solid ...

Bis(catecholato)silanes: assessing, rationalizing and increasing silicon's Lewis superacidity.

Although bis(catecholato)silanes have been known for several decades, their substantial Lewis acidity is not yet well described in the literature. Herewith, the synthesis and characterization of multiple substituted bis(catecholato)silanes and their triethylphosphine ...

Effector responsive hydroformylation catalysis.

A bidentate ligand with an integrated anion receptor forms dimeric rhodium complexes that become monomeric upon binding acetate guest, which is the basis for effector responsive hydroformylation catalysis.Herein, we report a supramolecular rhodium complex ...

Formamide catalyzed activation of carboxylic acids - versatile and cost-efficient amidation and esterification.

A novel, broadly applicable method for amide C–N and ester C–O bond formation is presented based on formylpyrrolidine (FPyr) as a Lewis base catalyst. Herein, trichlorotriazine (TCT), which is the most cost-efficient reagent for OH-group ...

Thymine DNA glycosylase recognizes the geometry alteration of minor grooves induced by 5-formylcytosine and 5-carboxylcytosine.

The dynamic DNA methylation–demethylation process plays critical roles in gene expression control and cell development. The oxidation derivatives of 5-methylcytosine (5mC) generated by Tet dioxygenases in the demethylation pathway, namely 5-hydroxymethylcytosine ...

Selective switching of multiple azobenzenes.

Multi-state photoswitchable compounds are highly attractive for application in data storage or multi-responsive materials. In this work, a trisazobenzene macrocycle capable of three-state isomerization is presented. The compound can be switched into each ...

Rhodium catalyzed template-assisted distal para-C-H olefination.

Rhodium catalysis has been extensively used for ortho-C–H functionalization reactions, and successfully extended to meta-C–H functionalization. Its application to para-C–H activation remains an unmet challenge. Herein we disclose ...

Storing redox equivalent in the phenalenyl backbone towards catalytic multi-electron reduction.

Storing and transferring electrons for multi-electron reduction processes are considered to be the key steps in various important chemical and biological transformations. In this work, we accomplished multi-electron reduction of a carboxylic acid via ...