Review Articles

The design of synthetic systems that mimic the ability of biological systems to control chemical reactions using intricate molecular machines is a long-held dream of nanotechnology. This Review discusses how developments in controlled molecular switching and movement are being exploited in the design of catalysts that are just beginning to emulate the complexity of living systems.

Iterative approaches to synthesis have revolutionized the preparation and study of peptides, nucleic acids and sugars. This Review discusses whether and how such iterative syntheses can be applied more broadly towards an ultimate goal of developing a building block approach to the synthesis of most small organic molecules.

The metals in polyoxometalates need not be in their highest oxidation states. Indeed, polyoxometalates can exist in reduced forms, and several different metals can be incorporated into various structural archetypes. This Review describes the synthesis and characterization of these complexes, along with their topical catalytic, electronic and biological properties.

Building on the theoretical prediction and experimental realization of planar tetracoordinate carbons, there has been great progress in the theoretical prediction of species containing planar pentacoordinate carbon (ppC) centres. From simple clusters such as CAl₅⁺ to complicated ppCs in 2D materials, this Review summarizes the ppC-containing species predicted to date and the design principles behind them.

The electrochemical oxidation and reduction of water and carbon dioxide are associated with the release or storage of energy. This Review reports the latest developments in the design and use of low-dimensional materials and their van der Waals heterostructures for electrocatalytic and photocatalytic hydrogen evolution and CO₂ conversion.

Some plant-derived ligands for the cannabinoid receptors — phytocannabinoids — are promising pharmaceuticals. This Review covers the chemical synthesis of phytocannabinoids and metabolites to enable the study of compounds otherwise inaccessible on a practical scale. Availability of drug candidates is also hindered by policy issues, which we discuss with regard to possession, use and control.

Electrocatalysts for the oxygen reduction reaction are important components of energy technologies such as fuel cells. The study of molecular catalysts affords mechanistic insights that further the development of robust, active and energy-efficient systems. This Review describes state-of-the-art metal complexes that operate either in solution or immobilized on an electrode.

The tunable bandgap of perovskites and their combination in multi-junction solar cells can afford highly efficient photovoltaic technologies. This Review reports the latest developments in tandem multi-junction perovskite solar cells and discusses prospects for this technology to achieve energy conversion efficiencies well beyond those attained by silicon-based cells.

Mechanical forces can be used as an alternative source of energy to increase chemical reactivity. This Review reports on the latest single-molecule measurements and how they have improved the current understanding of single-bond mechanochemistry.

This Review considers cascade reactions initiated by single electron transfer. Open-shell intermediates are highly reactive but undergo reactions with high selectivity. They are thus ideal intermediates in cascade reactions that generate complex, high-value products from simple starting materials

Aptamers are nucleic acid molecules that can be evolved to bind to specific molecular targets and have found applications in technologies such as sensors and actuators. This Review provides a critical analysis of the first 25 years of aptamer research.

Owing to their programmable ability to cut specific nucleic acid sequences, CRISPR–Cas systems have been used for precise genome engineering. In this Review, the authors discuss the chemistry and molecular mechanisms of interference by single-effector CRISPR–Cas proteins.

Research into naturally occurring chemically modified DNA bases has been invigorated by new chemical and enzymatic methods that, when coupled with sequencing approaches, enable us to detect and decode them. These techniques will support a better understanding of the role of chemically modified DNA bases in normal physiology and disease.

DNA polymerases are responsible for DNA replication, repair and mutation. Although these processes occur through conserved mechanisms, this Review highlights how large differences in the fidelity of DNA replication arise from subtle structural differences between individual DNA polymerases. These differences enable polymerases to perform diverse functions that are important to nature as well as technology.

Polymeric nanomaterials have a rich history of applications in the selective delivery of small-molecule drugs to their biological targets. This Review discusses the evolution of drug delivery using such polymers and explores how these approaches have evolved in parallel with the ability to prepare ever more architecturally complex macromolecular structures.

Surface-enhanced Raman scattering (SERS) is a physical phenomenon first discovered in 1974. SERS has since been exploited for bioanalysis because of its high sensitivity and multiplexing capabilities. This Review describes the progress made and problems faced with respect to using in vivo SERS in humans.

The active template approach to interlocked molecules uses metal ions to both pre-organize reaction components and catalyse the final covalent bond formation that captures the interlocked structure. This Review looks at the history of the method, its application in the synthesis of ever more complex interlocked molecules and future directions.

Transition metal catalysis is well established as an enabling tool in synthetic organic chemistry. Photoredox catalysis has recently emerged as a method to effect reactions that occur through single-electron-transfer pathways. Here we review the combination of the two to show how this provides access to highly reactive oxidation states of transition metals and distinct activation modes that further enable the synthetic chemist.

An untargeted mass spectrometry analysis of a biological sample will detect both biological molecules and compounds that are derived from, for example, diet and the environment. This Review examines the design of such experiments, how to process and interpret the vast amount of data that are produced, and how far we are from being able to use mass spectrometry to inventory the world around us.

Enzymes that are optimized for low temperatures have characteristics that are distinct from those that operate under milder conditions. This Review examines cold-adapted enzymes and describes how computational studies have highlighted structural and energetic consequences that arise from adaptation to cold environments.