Selina Hollstein

ChemRxiv has grown into the premier preprint server for the chemical sciences, with a global audience and a wide array of scholarly content. On the service's fifth anniversary, we would like to reflect on the past five years and take a look at what is next for ChemRxiv.

Abstract

ChemRxiv was launched on August 15, 2017 to provide researchers in chemistry and related fields a home for the immediate sharing of their latest research. In the past five years, ChemRxiv has grown into the premier preprint server for the chemical sciences, with a global audience and a wide array of scholarly content that helps advance science more rapidly. On the service's fifth anniversary, we would like to reflect on the past five years and take a look at what is next for ChemRxiv.

Nature Chemistry, Published online: 01 December 2022; doi:10.1038/s41557-022-01094-w

Interlocked shape-persistent organic cages are rare structures and the majority are formed using π-stacking as the driving force. Now it is shown that weak dispersion interactions—which are modulated by changing the 1,4-substituents of the constituent dialdehyde linkers—can be used to form interlocked dimeric and trimeric catenated cages.

Communications Chemistry, Published online: 22 August 2022; doi:10.1038/s42004-022-00720-5

[n]cycloparaphenylenes feature extensive para-conjugation that leads to useful electronic and optoelectronic properties, but their strained topology prevents their conversion into planar macrocycles. Now, on-surface coupling of cleverly designed precursors affords planar π-extended [12]cycloparaphenylene.

Every electrochemical synthesis is paired with conversion at the counter electrode. In electro-organic synthesis, often only the desired half reaction is described well, although good control over the counter reaction is essential. In this Review, the impact of the counter electrode reaction in electro-organic synthesis is highlighted through a collection of common and unusual counter reactions.

Abstract

Over the past two decades, electro-organic synthesis has gained significant interest, both in technical and academic research as well as in terms of applications. The omission of stoichiometric oxidizers or reducing agents enables a more sustainable route for redox reactions in organic chemistry. Even if it is well-known that every electrochemical oxidation is only viable with an associated reduction reaction and vice versa, the relevance of the counter reaction is often less addressed. In this Review, the importance of the corresponding counter reaction in electro-organic synthesis is highlighted and how it can affect the performance and selectivity of the electrolytic conversion. A selection of common strategies and unique concepts to tackle this issue are surveyed to provide a guide to select appropriate counter reactions for electro-organic synthesis.

Nature Chemistry, Published online: 06 June 2022; doi:10.1038/s41557-022-00957-6

The emerging field of dissipative DNA nanotechnology aims at developing synthetic devices and nanomaterials with life-like properties such as directional motion, transport, communication or adaptation. This Review surveys how dissipative DNA systems combine the programmability of nucleic-acid reactions with the consumption of energy stored in chemical fuel molecules to perform work and cyclical tasks.

Droplet-based microfluidics were used to encapsulate a fuel-driven cycle that drives phase separation into coacervate-based droplets. This approach enables the analysis of every coacervate-based droplet in the reaction container throughout its lifetime. The nucleation, growth, and dissolution of active coacervate-based droplets were investigated with this setup.

Abstract

Active droplets are a great model for membraneless organelles. However, the analysis of these systems remains challenging and is often limited due to the short timescales of their kinetics. We used droplet-based microfluidics to encapsulate a fuel-driven cycle that drives phase separation into coacervate-based droplets to overcome this challenge. This approach enables the analysis of every coacervate-based droplet in the reaction container throughout its lifetime. We discovered that the fuel concentration dictates the formation of the coacervate-based droplets and their properties. We observed that coacervate-based droplets grow through fusion, decay simultaneously independent of their volume, and shrinkage rate scales with their initial volume. This method helps to further understand the regulation of membraneless organelles, and we believe the analysis of individual coacervate-based droplets enables future selection- or evolution-based studies.

Color is central to scientific communication, but its use comes with the responsibility to ensure universally accessible and accurate data presentation. This short Viewpoint Article aims to sensitize the chemical community to the importance of mindful color choices in scientific illustrations.

Abstract

Color is a central element to scientific communication, but its use comes with the responsibility to ensure universally accessible and accurate data presentation. This short Viewpoint Article aims to sensitize the chemical community to the importance of mindful color choices in scientific illustrations.

The chemical versatility of sulfur allows the formation of several dynamic sulfur-based bonds (DSBs). This Review summarizes the advances achieved with each DSB, together with some applications. In addition, dynamic multilevel systems in which two or more DSBs are combined in the same system are discussed.

Abstract

Sulfur has been important in dynamic covalent chemistry (DCC) since the beginning of the field. Mainly as part of disulfides and thioesters, dynamic sulfur-based bonds (DSBs) have a leading role in several remarkable reactions. Part of this success is due to the almost ideal properties of DSBs for the preparation of dynamic covalent systems, including high reactivity and good reversibility under mild aqueous conditions, the possibility of exploiting supramolecular interactions, access to isolable structures, and easy experimental control to turn the reaction on/off. DCC is currently witnessing an increase in the importance of DSBs. The chemical flexibility offered by DSBs opens the door to multiple applications. This Review presents an overview of all the DSBs used in DCC, their applications, and remarks on the interesting properties that they confer on dynamic chemical systems, especially those containing several DSBs.

Volume 33, Issue 8, August 2021, Page 442-449
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Nature Chemistry, Published online: 27 January 2022; doi:10.1038/s41557-021-00850-8

Decoupling the processes of light harvesting and catalytic hydrogen evolution could be a potentially important step in storing solar energy. This has now been achieved with a single molecular unit: a light-harvesting ruthenium complex–polyoxometalate dyad that absorbs light, separates and stores charge and then generates hydrogen on demand following the addition of a proton donor.

Nature Communications, Published online: 13 December 2021; doi:10.1038/s41467-021-27493-0

RNA therapeutics have benefited significantly from decades of research on lipid nanoparticles, specifically its key component—the ionizable lipid. This comment discusses the major ionizable lipid types, and provides perspectives for future development.

Nature Chemistry, Published online: 22 November 2021; doi:10.1038/s41557-021-00849-1

Early-career researchers have been particularly impacted by the COVID-19 pandemic. To re-assemble the supramolecular research community, the inaugural Women in Supramolecular Chemistry workshop promoted a community-led approach to skills development, as Ruhee Dawood and Alyssa-Jennifer Avestro recount.

Volume 33, Issue 4, April 2021, Page 143-149
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A chiral, anionic tetrahedral cage was self-assembled in water by condensing an anionic trisbenzaldehyde and a trisamine in a [4+4] manner, enantioselectively, with the help of templating by a chiral guest. The tetrahedron is remarkably stable and can accommodate a variety of guest molecules when in water.

Abstract

Self-assembly of host molecules in aqueous media via metal–ligand coordination is well developed. However, the preparation of purely covalent counterparts in water has remained a formidable task. An anionic tetrahedron cage was successfully self-assembled in a [4+4] manner by condensing a trisamine and a trisformyl in water. Even although each individual imine bond is rather labile and apt to hydrolyze in water, the tetrahedron is remarkably stable or inert due to multivalence. The tetrahedral cages, as well as its neutral counterparts dissolved in organic solvent, have homochirality, namely that their four propeller-shaped trisformyl residues adopt the same rotational conformation. The cage is able to take advantage of hydrophobic effect to accommodate a variety of guest molecules in water. When a chiral guest was recognized, the formation of one enantiomer of the cage became more favored relative to the other. As a consequence, the cage could be produced in an enantioselective manner. The tetrahedron is able to maintain its chirality after removal of the chiral guest—probably on account of the cooperative occurrence of intramolecular forces that restrict the intramolecular flipping of phenyl units in the cage framework.

Communications Chemistry, Published online: 14 June 2021; doi:10.1038/s42004-021-00528-9

Deep neural networks are potent tools for computational chemistry, but experimental feed data can limit their reach. Here the authors develop deep neural network data augmentation models to predict octanol–water partition coefficients (log P) of a variety of tautomers.