Chemical Science

List of Papers (Total 4,436)

Cobalt-catalyzed acylation-reactions of (hetero)arylzinc pivalates with thiopyridyl ester derivatives.

A cobalt-catalyzed acylation reaction of (hetero)arylzinc pivalates using primary, secondary and tertiary alkyl, benzyl and (hetero)aryl S-pyridyl thioesters has been developed.A cobalt-catalyzed acylation reaction of various primary, secondary and tertiary ...

A cruciform phthalocyanine pentad-based NIR-II photothermal agent for highly efficient tumor ablation.

Photothermal therapy in the second near-infrared window (NIR-II, 1000–1700 nm) exhibits a significant advantage over the first near-infrared window (NIR-I, 650–950 nm) in terms of both maximum permissible exposure (MPE) and penetration ...

A quantitative uncertainty metric controls error in neural network-driven chemical discovery.

Machine learning (ML) models, such as artificial neural networks, have emerged as a complement to high-throughput screening, enabling characterization of new compounds in seconds instead of hours. The promise of ML models to enable large-scale chemical ...

Fluoro-electrochemical microscopy reveals group specific differential susceptibility of phytoplankton towards oxidative damage.

In the vicinity of an electrode creating a highly oxidising environment the fluorescence – arising from the presence of chlorophyll-a – of single cellular phytoplankton becomes inhibited. Even for phytoplankton that are very comparable ...

Before Förster. Initial excitation in photosynthetic light harvesting.

Fluorescence detected double quantum coherence 2D spectroscopy reveals strong correlation between weakly coupled pigment pools directly after absorption of light before the Förster transfer regime sets in.Electronic 2D spectroscopy allows nontrivial ...

Nanoscale electrostatic gating of molecular transport through nuclear pore complexes as probed by scanning electrochemical microscopy.

The nuclear pore complex (NPC) is a large protein nanopore that solely mediates molecular transport between the nucleus and cytoplasm of a eukaryotic cell. There is a long-standing consensus that selective transport barriers of the NPC are exclusively ...

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates.

Supporting two metal binding sites by a tailored polydentate trop-based (trop = 5H-dibenzo[a,d]cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium() complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an ...

Electrochemical oxidation induced selective tyrosine bioconjugation for the modification of biomolecules.

Directly introducing a beneficial functional group into biomolecules under mild, clean and easy-to-handle conditions is of great importance in the field of chemical biology and pharmacology. Herein, we described an electrochemical strategy to perform ...

Pore-size dominated electrochemical properties of covalent triazine frameworks as anode materials for K-ion batteries.

Two homologous covalent triazine frameworks (CTFs) have been developed for the first time as anode materials for high performance K-ion batteries (KIBs). The two-dimensional sheet-like structure as well as the regular channels in CTFs enable the process ...

Anthracene-based mechanophores for compression-activated fluorescence in polymeric networks.

The recent attention given to functionalities that respond to mechanical force has led to a deeper understanding of force transduction and mechanical wear in polymeric materials.The recent attention given to functionalities that respond to mechanical ...

Relayed hyperpolarization from para-hydrogen improves the NMR detectability of alcohols.

The detection of alcohols by magnetic resonance techniques is important for their characterization and the monitoring of chemical change. Hyperpolarization processes can make previously inpractical measurements, such as the determination of low concentration ...

Tumour suppression by targeted intravenous non-viral CRISPRa using dendritic polymers.

Aberrant gene expression is a hallmark of cancer. Although transcription is traditionally considered ‘undruggable’, the development of CRISPR-associated protein 9 (Cas9) systems offers enormous potential to rectify cancer-associated transcriptional ...

Unraveling the structural and chemical features of biological short hydrogen bonds.

The three-dimensional architecture of biomolecules often creates specialized structural elements, notably short hydrogen bonds that have donor–acceptor separations below 2.7 Å. In this work, we statistically analyze 1663 high-resolution ...

A sterically encumbered photoredox catalyst enables the unified synthesis of the classical lignan family of natural products.

Herein, we detail a unified synthetic approach to the classical lignan family of natural products that hinges on divergence from a common intermediate that was strategically identified from nature's biosynthetic blueprints. Efforts toward accessing the ...

Uncovering two kinetic factors in the controlled growth of topologically distinct core-shell metal-organic frameworks.

Constructing core–shell metal–organic frameworks (MOFs) based on two topologically distinct MOFs is a great way to increase MOF material complexity and explore their new functions. However, such a nucleation process is energetically less ...

Spectroscopic, thermodynamic and computational evidence of the locations of the FADs in the nitrogen fixation-associated electron transfer flavoprotein.

Experiments and computation establish the locations of the two flavins whose contrasting reactivities produce electron bifurcation in ETFs. They confirm the accepted model and support homologies & distinctions between bifurcating and canonical ...

Ultralong room-temperature phosphorescence of a solid-state supramolecule between phenylmethylpyridinium and cucurbit[6]uril.

We report an ultralong room-temperature phosphorescence (2.62 s) based on cucurbit[6]uril host and phenyl-methyl-pyridinium guest for data encryption. Encapsulation of CB[6] boosts intersystem crossing and suppresses nonradiative relaxation of guest.Long-lived ...

Structure and effective charge characterization of proteins by a mobility capillary electrophoresis based method.

Measuring the conformations and effective charges of proteins in solution is critical for investigating protein bioactivity, but their rapid analysis remains a challenging problem. Here we report a mobility capillary electrophoresis (MCE) based method ...

Bio-inspired synthesis of xishacorenes A, B, and C, and a new congener from fuscol.

The xishacorene natural products are structurally unique apolar diterpenoids that feature a bicyclo[3.3.1] framework. These secondary metabolites likely arise from the well-studied, structurally related diterpenoid fuscol. In this manuscript, we describe ...

A reactive oxygen species-generating, cancer stem cell-potent manganese(ii) complex and its encapsulation into polymeric nanoparticles.

Intracellular redox modulation offers a viable approach to effectively remove cancer stem cells (CSCs), a subpopulation of tumour cells thought to be responsible for cancer recurrence and metastasis. Here we report the breast CSC potency of reactive oxygen ...

The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis.

The popularity of NHCs in transition metal catalysis has prompted the development of chiral versions as electron-rich neutral stereodirecting ancillary ligands for enantioselective transformations. Herein we demonstrate that cyclic (alkyl)(amino)carbene ...

Nucleophile-intercepted Beckmann fragmentation reactions.

We describe the first examples of nucleophile-intercepted Beckmann fragmentations of indoline oximes. This reaction uses MsCl as a promoter to give cyano chlorides and is believed to proceed through an aziridinium intermediate via a double stereoinvertive ...

Near-infrared fluorescein dyes containing a tricoordinate boron atom.

Tricoordinate boron imparts near-infrared absorption/emission and unusual multi-stage changes in the photophysical properties to fluorescein dyes.Bora-fluoresceins (BFs), fluorescein analogues containing a tricoordinate boron atom instead of an oxygen ...

α-Silicon effect assisted Curtin-Hammett allylation using allylcopper reagents derived from 1,3-dienylsilanes.

Cu-catalyzed stereoselective synthesis of (E)-δ-silyl-anti-homoallylic alcohols from 1,3-dienylsilane was developed. Mechanistic studies revealed that the borocupration of dienylsilane proceeded through a 1,2-addition pathway to give an allylcopper ...

Using sulfur bridge oxidation to control electronic coupling and photochemistry in covalent anthracene dimers.

Covalently tethered bichromophores provide an ideal proving ground to develop strategies for controlling excited state behavior in chromophore assemblies. In this work, optical spectroscopy and electronic structure theory are combined to demonstrate that ...