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Genome editing relies on engineered nucleases to change an organism’s DNA, but has not yet been achieved using abiotic materials. Now, chiral cysteine-capped CdTe nanoparticles are found to specifically recognize and, following photoirradiation, cut between bases T and A at the GATATC restriction site in DNA with over 90 base pairs.
That K+ channels conduct K+ ions at near-diffusion limited rates, but block the passage of smaller Na+ ions, creates an apparent contradiction. Now, atomistic simulations and free-energy calculations are used to show that both K+ permeation and ion selectivity are governed by the direct knock-on of completely desolvated ions in the channels’ selectivity filter.
Properly designed polyyne substrates are shown to undergo efficient cascades of thermal cycloaddition reactions initiated by (rate-limiting) benzyne formation. Proceeding through naphthyne, anthracyne or tetracyne intermediates, rapid access to highly fused, polycyclic aromatic compounds can be achieved.
On copper catalysts, Cuδ+ sites play a key role in the electrochemical reduction of CO2 to C2 hydrocarbons, however, they are prone to being reduced (to Cu0) themselves. Now, a Cuδ+-based catalyst is reported that is stable for in excess of ~40 hours while electrochemically reducing CO2 to multi-carbon hydrocarbons and that exhibits a Faradaic efficiency for C2 of ~80%.
A series of tungsten hydride complexes have been synthesized to mimic a proton-coupled electron transfer (PCET) step undergone by metal–hydride intermediates during solar fuel catalysis. It is shown that, by incorporating proton-accepting bases into the second coordination sphere, their PCET oxidation mechanism changes and its rate increases by several orders of magnitude.
Nucleophilic aromatic substitution reactions have long been thought to occur primarily via stepwise mechanisms. New and sensitive methodology for measuring carbon kinetic isotope effects now shows that most such substitutions actually occur through concerted mechanisms.
Molecular dynamics simulations for seven members of the Src kinase family have now revealed a conserved step-wise deactivation process, potentially druggable intermediate states, and quantitatively similar thermodynamics and kinetics across the entire family.
Chiral tertiary aldols are encountered in a variety of biologically relevant molecules. Making these valuable compounds directly from unbiased ketones has proven to be extremely challenging. Now it has been shown that sub-ppm levels of in situ generated silylium-based organic Lewis acid catalysts can give quantitative product formation in very high enantiopurity through a Mukaiyama aldol reaction.
Atomic manipulation was used to control the reductive rearrangement of 1,1-dibromo alkenes to acetylenes on a NaCl surface at 5 K, and the stages of the reaction were visualized with atomic resolution using AFM. Polyynes ranging from triyne to octayne were prepared in this way, and STM was used to map their frontier orbitals and determine their transport gaps.
An enzyme in which a reactive unnatural amino acid functions as a catalytic residue has now been designed. Embedding an aniline side chain into the promiscuous binding pocket of a multidrug resistance regulator endowed the protein scaffold with new-to-nature activities for hydrazone and oxime formation.
As of yet, no clear structure–performance descriptors have been developed to tune the catalytic activity of zeolitic methanol-to-olefin catalysts. Now it has been shown that introducing Lewis acidity into Brønsted acidic zeolites boosts their performance. Although Brønsted acidity is found to define propylene selectivity, Lewis acidity is responsible for prolonging lifetime.
Electrophilic aromatic substitution (EAS) favours arene functionalization at positions meta to electron-withdrawing groups and para to electron-donating groups. Now, with a class of bridgehead-modified norbonene derivatives that can overcome the ortho constraint typical in palladium/norbornene catalysis, arene functionalization with site-selectivity complementary to EAS approaches can be achieved.
As a consequence of high chemical resistance and low solubility in conventional solvents, deconstructing biomass into fuels and other useful chemical building blocks remains a challenge. Now, through enzyme modification and ionic liquid solvents, it is possible to homogeneously biocatalytically convert cellulose to sugars at a rate 30 times greater than is achievable in water.
Sodium chloride phases with unconventional non-1:1 stoichiometries are known to exist under high-pressure conditions. Now, Na2Cl and Na3Cl two-dimensional crystals have been obtained under ambient conditions, on graphene surfaces, from dilute solutions.
Encoded chemical libraries can be used to screen a vast array of compounds against a protein target to identify potent binders. A collection of articles in this issue discuss different methods to increase the chemical space sampled by encoded macrocycle libraries and the advantages that such libraries offer for discovering new drug leads.