Oleksandr

Nature Chemistry. doi:10.1038/nchem.2817

Authors: Claudia Bonfio, Luca Valer, Simone Scintilla, Sachin Shah, David J. Evans, Lin Jin, Jack W. Szostak, Dimitar D. Sasselov, John D. Sutherland & Sheref S. Mansy

Current mineral-based theories do not fully address how enzymes emerged from prebiotic catalysts. Now, iron–sulfur clusters can be synthesized by UV-light-mediated photolysis of organic thiols and photooxidation of ferrous ions. Iron–sulfur peptides may have formed easily on early Earth, facilitating the emergence of iron–sulfur-cluster-dependent metabolism.

Nuclear magnetic resonance (NMR) spectroscopy is a key analytical technique in chemistry, biology, and medicine. However, conventional NMR spectroscopy requires an at least nanoliter-sized sample volume to achieve sufficient signal. We combined the use of a quantum memory and high magnetic fields with a dedicated quantum sensor based on nitrogen vacancy centers in diamond to achieve chemical shift resolution in ¹H and ¹⁹F NMR spectroscopy of 20-zeptoliter sample volumes. We demonstrate the application of NMR pulse sequences to achieve homonuclear decoupling and spin diffusion measurements. The best measured NMR linewidth of a liquid sample was ~1 part per million, mainly limited by molecular diffusion. To mitigate the influence of diffusion, we performed high-resolution solid-state NMR by applying homonuclear decoupling and achieved a 20-fold narrowing of the NMR linewidth.

The development of new methodologies to affect non–ortho-functionalization of arenes has emerged as a globally important arena for research, which is key to both fundamental studies and applied technologies. A range of simple arene feedstocks (namely, biphenyl, meta-terphenyl, para-terphenyl, 1,3,5-triphenylbenzene, and biphenylene) is transformed to hitherto unobtainable multi-iodoarenes via an s-block metal sodium magnesiate templated deprotonative approach. These iodoarenes have the potential to be used in a whole host of high-impact transformations, as precursors to key materials in the pharmaceutical, molecular electronic, and nanomaterials industries. To prove the concept, we transformed biphenyl to 3,5-bis(N-carbazolyl)-1,1'-biphenyl, a novel isomer of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CPB), a compound which is currently widely used as a host material for organic light-emitting diodes.

Polyaromatic molecular peanuts

Nature Communications, Published online: 28 June 2017; doi:10.1038/ncomms15914

The complex, multicomponent structures often found in nature are difficult to mimic synthetically. Here, the authors assemble a molecular analogue of a peanut through coordinative and π-stacking interactions, in which a polyaromatic double capsule ‘pod’ held together by metal ions encapsulates fullerene ‘beans’.

Abstract

Nature Chemistry. doi:10.1038/nchem.2795

Authors: Douglas P. Solowey, Manoj V. Mane, Takashi Kurogi, Patrick J. Carroll, Brian C. Manor, Mu-Hyun Baik & Daniel J. Mindiola

The direct, selective conversion of linear alkanes to α-olefins — without isomerization — is an important reaction in the field of catalysis from both a fundamental and industrial perspective. Now, a detailed pathway has been described for how a base metal can promote such a reaction with several turnovers, in a non-oxidative set of C–H activation reactions, thus preventing olefin isomerization.

Nature Chemistry. doi:10.1038/nchem.2812

Authors: Kotagiri Venkata Rao, Daigo Miyajima, Atsuko Nihonyanagi & Takuzo Aida

An attractive feature of supramolecular polymers is their reversibility — they typically depolymerize upon heating. Now, in the presence of a scavenger molecule, a metalloporphyrin derivative bearing eight amide-containing side chains has been shown to undergo supramolecular polymerization on heating as well as cooling through π-stacking and multivalent hydrogen-bonding interactions.

Abstract

Abstract

Adaptive self-assembly and induced-fit transformations of anion-binding metal-organic macrocycles

Nature Communications, Published online: 16 June 2017; doi:10.1038/ncomms15898

Container-molecules capable of recognizing charged species possess great potential as sensors, but are typically limited by their rigid frameworks. Here, Sun and co-workers design a family of adaptive metal-organic macrocycles that exhibit shape and size induced-fit transformations upon anion-binding.

Biological molecular motors translate their local directional motion into ordered movement of other parts of the system to empower controlled mechanical functions. The design of analogous geared systems that couple motion in a directional manner, which is pivotal for molecular machinery operating at the nanoscale, remains highly challenging. Here, we report a molecular rotary motor that translates light-driven unidirectional rotary motion to controlled movement of a connected biaryl rotor. Achieving coupled motion of the distinct parts of this multicomponent mechanical system required precise control of multiple kinetic barriers for isomerization and synchronous motion, resulting in sliding and rotation during a full rotary cycle, with the motor always facing the same face of the rotor.

Alicia Altemose, María Antonieta Sánchez-Farrán, Dr. Wentao Duan, Steve Schulz, Prof. Dr. Ali Borhan, Prof. Dr. Vincent H. Crespi and Prof. Dr. Ayusman Sen

Tunable colloidal oscillations: An autonomous oscillatory system involves Ag₃PO₄ colloidal particles under UV illumination in the presence of hydrogen peroxide. The particles oscillate between clustered and dispersed states, exhibiting signal propagation and synchronization. The behavior follows an electrolytic self-diffusiophoretic mechanism based on the redox chemistry of silver.

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