Articles in 2021

Fidaxomicin is a narrow spectrum antibiotic, and broadening its activity through structural modification could provide new antibiotics. Here semi-synthetic derivatives are prepared through site-selective esterification and allylic substitution to efficiently modify or substitute key carbohydrate moieties.

In theoretical models, used to process experimental data on biopolymer conformations, the description of water-polymer interactions is challenging. Here the authors present a model that extracts the values of H-bonding energies and determines the conditions for cold denaturation from the energetic balance.

Metallo-supramolecular polymers have demonstrated promise for applications in displays, sensors, and storage devices, but control over their synthesis remains a challenge. Here, the authors report on the stepwise introduction of three different transition metals into a metallo-supramolecular polymer and highlight its potential as an electrochromic display material.

Aggregation-induced emission (AIE) is exploited for several optoelectronic applications, but synthesizing molecules that respond to multiple stimuli is challenging. Here, the authors report a hydroquinone bearing an AIE-active core that responds to both redox and pH changes.

Dearomative hydrogenation of benzoic acid and its derivatives is challenging to achieve selectively. Here, a highly active Pt/TiO₂ catalyst which works in the presence of common catalyst poisons, including bi- and tri-benzoic acids, is described.

Flow reactors have applications in reaction screening and optimisation, but typically operate in linear or radial configurations. Here a bench-top parallel flow synthesiser which distributes reagents between sixteen microreactors allows for rapid optimisation of chemical libraries, with uniform flow distribution even when clogging occurs.

Superabsorbent materials can absorb many times their weight in water, but are commonly derived from petroleum. Here, acylation of coagulated potato protein concentrate or soluble potato protein fruit juice yields an effective, mould-resistant, and biodegradable superabsorbent polymer.

Mechanistic insight into enantioselective reactions at intrinsically chiral surfaces can be challenging to obtain. Here the catalytic activity of Pd₁- and Pd₃-terminated PdGa{111} surfaces is shown to differ substantially, with Pd₁-terminated surfaces promoting on-surface azide– alkyne cycloadditions enantioand regioselectively.

Ionizing radiation damage to DNA plays a fundamental role in cancer therapy, whereby water radiolysis effects are important to take into account. Here, near-ambient-pressure X-ray photoelectron-spectroscopy is used to directly measure DNA damage during irradiation in water and compared to that in a dry atmosphere.

Halide salts exhibit complex radiation-induced reactions that are relevant in atmospheric chemistry, but detailed characterizations in high-level radiation fields are challenging to obtain. Here, the authors use a custom atomic force microscope to study alkali halide surface transformations in situ under 18 kGy/hr irradiation.

Porphyrins have been incorporated into metal–organic frameworks in a periodic fashion in order to exploit their unique photophysical and electrochemical properties. This article reviews progress in the field, focusing on the fundamental physical properties that arise in porphyrin-based MOFs.

Interpreting ultrafast non-adiabatic vibronic processes of complex systems such as the excited benzene cation remains highly challenging. Here, a computational model is reported, where non-adiabatic events are seen far from a conical intersection and are controlled by electron dynamics involving a superposition of non-adjacent adiabatic states.

Robust and selective C–H functionalisation of alkanes remains a challenge. Here, iodine(III) mediates the radical coupling of N-hydroxyphthalimide and unactivated C(sp³)–H bonds in a range of cyclic and acyclic alkanes.

Chemical warfare agents and simulants are commonly detected with fluorescent sensing materials containing nitrogen-based groups, however these groups’ basicity can cause false positives in the presence of acids. Here, the authors disentangle the response of pyridyl-containing sensing materials to acid-containing and acid-free Sarin and simulants.

Electrocatalytic reactions depend on ion transport phenomena within the electric double layer, but the electrochemical response of single gas bubbles that form on catalyst surfaces remains unclear. Here, the authors use alternating current electrochemical impedance spectroscopy to detect a gateway through which ions can exchange between gas bubble surfaces and solid-state catalyst surfaces.

Criegee intermediates are reactive intermediates formed in Earth’s atmosphere through ozonolysis of alkenes. Here the authors outline the fundamental chemistry that influences their highly conformer- and substituent-dependent unimolecular and bimolecular reactivity, and discuss open questions of fundamental and atmospheric interest.

Existing routes to dibenzofurans have intrinsic regioselectivity, limiting the substitution patterns available in the products. Here a double 1,4-conjugate addition-annulation cascade between propargylamines and imidazolium methylides provides direct access to dibenzofurans with a complementary substitution pattern.

Nidovirus RNA synthesis machineries catalyze nucleotide transfer, but characterization of this activity is limited using existing methods. Here the nucleotidyl transferase activity of SARSCoV-2 replicase proteins is characterized by mass spectrometry of GMP and UMP protein adducts, allowing identification of nucleotidylation sites in vitro.

Thioesters are often suggested to be key intermediates in primordial metabolism, but prebiotic CO₂ fixation routes to thioesters remain elusive. Here, the authors show nickel sulfide, partially reduced to Ni(0) with realistic geoelectric potentials, facilitates thioester (S-methyl thioacetate) formation via CO₂-to-CO electroreduction, followed by a CO-methanethiol reaction.

The formation of solid solutions can result in changes of relative stabilities of crystal polymorphs. Here, the elusive form III of benzamide is stabilized through solid solution formation with nicotinamide. It is shown, experimentally and computationally, how such thermodynamic switching allows for consistent and facile crystallization of the otherwise elusive benzamide form III.