Marnix van der Kolk

Nature, Published online: 04 October 2023; doi:10.1038/d41586-023-03138-8

A machine-learning algorithm suggests that volcanic activity, rather than an asteroid, killed the dinosaurs. Plus, quantum dots win the chemistry Nobel Prize and a second malaria vaccine to win global approval.

Nature, Published online: 06 October 2023; doi:10.1038/d41586-023-03185-1

Same-sex sexual behaviour seems to have evolved as a way to smooth out social relationships when mammals started living in groups. Plus, a dispatch from a Ukrainian scientist in the trenches and how embracing the command line opens up the world of computational biology.

Nature, Published online: 09 October 2023; doi:10.1038/d41586-023-02482-z

As deadly heatwaves become more common, researchers are studying what people can tolerate.

Nature Reviews Chemistry, Published online: 09 October 2023; doi:10.1038/s41570-023-00540-8

Heterogeneous single-cluster catalysts comprising atomically precise metal clusters stabilized on supports offer exciting prospects for delivering novel reactivity patterns in chemical transformations. This Review examines the progress in controlling cluster environments and understanding the performance of single-cluster catalysts.

In this review, we present a concise overview of recent breakthroughs in photochemical C−H methylation. These advancements encompass a variety of methodologies, including transition metal-based photocatalysis, organophotocatalysis, and various metal-free approaches, such as electron donor-acceptor -enabled processes.

Abstract

Direct C−H methylation is a highly valuable approach for introducing methyl groups into organic molecules, particularly in pharmaceutical chemistry. Among the various methodologies available, photo-induced methylation stands out as an exceptional choice due to its mild reaction conditions, energy efficiency, and compatibility with functional groups. This article offers a comprehensive review of photochemical strategies employed for the direct and selective methylation of C(sp³)−H, C(sp²)−H, and C(sp)−H bonds in various organic molecules. The discussed methodologies encompass transition-metal-based photocatalysis, organophotocatalysis, as well as other metal-free approaches, including electron donor-acceptor (EDA)-enabled transformations. Importantly, a wide range of easily accessible agents such as tert-butyl peroxide, methanol, DMSO, methyl tert-butyl ether, TsOMe, N-(acetoxy)phthalimide, acetic acid, methyl halides, and even methane can serve as effective methylating reagents for modifying diverse targets. These advancements in photochemical C−H methylation are anticipated to drive further progress in the fields of organic synthesis, photocatalysis, and pharmaceutical development, opening up exciting avenues for creating novel organic molecules and discovering new drug compounds.

The electrocatalytic oxygen reduction reaction (ORR) plays a crucial role in numerous energy and sustainability systems, such as fuel cells, metal-air batteries, and water electrolysers. It holds significant potential for renewable energy generation, transportation, and storage, heralding a cleaner and more sustainable future. Recent trends have shown increased use of single-atom catalysts (SACs), particularly metal-N4 moieties grown on graphene-based 2D materials, for enhancing ORR efficiency. However, the rational design of SAC for high-performance ORR faces challenges due to unclear structure-property relationships and the limits of conventional experimental trial-and-error approaches. In this study, we harnessed the power of the density functional theory (DFT) calculations, combined with cutting-edge machine learning (ML) techniques, to explore 144 SACs featuring dual interacting M1-N4 and M2-N4 moieties (M1, M2 = Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag Ir, Pt, Au), denoted as M1-M2, grown on graphene. Of all the catalysts we examined, Fe-Pd emerged as the top performer, achieving an impressive overpotential of 0.211 V vs. RHE in alkaline conditions — outperforming most previously reported SACs. Even more striking, 25 of the evaluated SACs surpassed the renowned Fe-N4 SAC in catalytic efficiency, including more economically viable alternatives like Fe-Ag. Venturing further, we developed three ML models that accurately predict the overpotentials of various M1-M2 SACs, showing their strong ability to capture the relationship between single-atom metal site properties and overpotential. These models provide useful navigation toolkits for the rational design of effective electrocatalysts. Our study sheds light on the path toward achieving efficient SAC-catalyzed ORR, contributing to a more sustainable and energy-efficient future.

Nature Synthesis, Published online: 05 October 2023; doi:10.1038/s44160-023-00411-6

The selective synthesis of non-symmetrical diamides and amido-esters is a challenge. Now a Pd-catalysed dicarbonylation method is reported that generates non-symmetrical diamides and amido-esters through diamino- and amino-alkoxy carbonylations of propargylic acetates using two different nucleophiles. Mechanistic studies reveal that the process occurs through a sequential carbonylation process.

Nature, Published online: 03 October 2023; doi:10.1038/d41586-023-03126-y

First study of hammerhead shark embryos shows how their heads develop their iconic shape. Plus, attoseconds physics wins Nobel Prize and a huge new satellite outshines nearly every star in the sky.

Science, Volume 381, Issue 6662, Page 1079-1085, September 2023.

Nature, Published online: 02 October 2023; doi:10.1038/d41586-023-03046-x

Katalin Karikó and Drew Weissman laid the groundwork for immunizations that were rolled out during the pandemic at record-breaking speed.

The local structures of Ni single-atom catalysts were regulated by adjusting carbonization temperature of their precursors. The oxidation state, total coordination number, and bond length of the metal center decrease with the increase of the carbonization temperature. The relationship between structure and performance was explored. The structure after regulation could promote the adsorption of CO₂ and improve electrocatalytic CO₂ reduction activity.

Abstract

Single-atom catalysts (SACs) have the unique coordination environment and electronic structure due to the quantum size effect, which plays an essential role in facilitating catalytic reactions. However, due to the limited understanding of the formation mechanism of single atoms, achieving the modulation of the local atomic structure of SACs is still difficult and challenging. Herein, we have prepared a series of Ni SACs loaded on nitrogen-doped carbon substrates with different parameters using a dissolution-and-carbonization method to systematically investigate the effect of temperature on the structure of the SACs. The results of characterization and electrochemical measurements are analyzed to reveal the uniform law between temperature and the metal loading, bond length, coordination number, valence state and CO₂ reduction performance, showing the feasibility of controlling the structure of SACs through temperature to regulate the catalytic performance. This is important for the understanding of catalytic reaction mechanisms and the design of efficient catalysts.

We report here a new method to make polyketones from the coupling of diketones and diols using a manganese pincer complex. The methodology allows us to access a new type of polyketone (polyarylalkylketone) containing aryl, alkyl, and ether functionalities bridging the gap between the two classes of commercially available polyketones – aliphatic polyketones and polyaryletherketones. Based on previous reports and our studies, we suggest that the polymerization occurs via a hydrogen-borrowing mechanism that involves the dehydrogenation of diols to dialdehyde followed by aldol condensation of dialdehyde with diketones to form chalcone derivatives and their subsequent hydrogenation to form polyarylalkylketones.