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Recent years have witnessed a surge of interest in targeted covalent inhibition of disease-associated proteins. Among the electrophiles used to interact with nucleophilic residues in protein structures, boron is unique for its chameleonic ability to display a range of coordination modes upon interaction with protein targets.
Biological drugs can offer high potency and selectivity; however, this class of therapeutics often shows poor stability upon oral administration and during subsequent circulation. This Review highlights the materials and methods used to deliver biological drugs, and discusses how these approaches can improve their pharmacokinetics.
Numerous dynamic molecular crystals whose physical properties can be switched by external stimuli have recently been developed. This Review discusses how the precise control of the electron, proton and molecular movement within the crystals through the application of external stimuli can lead to considerable changes in their properties.
Natural products are a prime source of innovative molecular fragments and privileged scaffolds for drug discovery and chemical biology. Advanced machine-learning approaches can help analyse and design synthetically accessible, natural-product-derived, compound libraries and provide insight into the high selectivity of such compounds.
Chemical protein synthesis can enable the preparation of proteins containing post-translational modifications or unnatural variations such as D-amino acids. Such modified proteins are not easily fabricated by other methods. This Review provides an overview of the current approaches for the chemical synthesis of proteins.
In enzyme-catalysed metabolic pathways, substrate channelling often directs the movement of intermediates from one active site to the next. Intramolecular tunnels, electrostatic interactions and chemical swing arms pass intermediates from one enzyme to the next, enhancing pathway catalysis. Introducing mechanisms of bounded diffusion in chemical cascades can increase selectivity, transient rates and overall yield.
In a remote functionalization, reaction occurs at a site distant from the site of initial activation. This Review discusses attempts to achieve this challenging goal with a particular focus on reactions that exploit alkene isomerizations to effect transit of the catalyst from a reactive alkene to a distant sp3 centre.
Vinyl polymers are appealing materials owing to their ease of synthesis and broad diversity. Their carbon–carbon backbones resist degradation, however, which limits the applications for which they can be used. This Review Article considers the most promising approaches to the design of degradable vinyl polymers and discusses the potential of these materials for biomedical applications.
Ferroelectric materials hold much promise for the development of devices such as nonvolatile memories, sensors and nonlinear optic materials. This Review describes the molecular features required to devise organic molecular ferroelectrics, and presents the supramolecular chemistry strategies available for controlling molecular organization and dynamics across different length scales.
Bringing porphyrins in contact with well-defined interfaces generates a rich playground of chemical behaviour and properties for exploration and exploitation. This Review examines our current understanding of surface-confined tetrapyrroles and their embedding in nanoarchitectures - discussing both the structural and functional attributes, and methods by which to manipulate their intramolecular and organizational features.
A critical overview and analysis of contemporary screening approaches toward the discovery of new reactivity is provided. A breakdown of each approach in terms of strategy, practicality and utility from the perspective of a synthetic chemist is also given, as well as considerations on the future of high-throughput screening in reaction discovery.
This Review draws an analogy between acid–base catalysis and redox catalysis. The 'electron is a catalyst' paradigm unifies mechanistically an assortment of synthetic transformations that otherwise have little or no apparent relationship. Various radical cascades catalysed by the electron are discussed.
Ion mobility-mass spectrometry (IM-MS) is enhancing many areas of (bio)chemical analysis because it can separate ions both by their mass-to-charge ratio and differences in their cross-sectional area. IM-MS can be used for structural characterization, enhanced analysis of complex mixtures or to gain insights into conformational dynamics.
The successes and failures of past research in the development of microfluidic reactors for chemical synthesis are highlighted. Current roadblocks are assessed and a series of challenges for the future of this area are identified.
The application of catalytic methods to main group substrates has recently allowed access to a wide range of catenated structures based on elements across the p-block. These breakthroughs have already impacted areas such as hydrogen storage and transfer, functional inorganic polymers, and ceramic thin films.
Two-dimensional polymers, which exhibit periodic bonding in two orthogonal directions, offer mechanical, electronic and structural properties distinct from their linear or irregularly crosslinked polymer counterparts. Their potential is largely unexplored because versatile and controlled synthetic strategies are only now emerging. This Review describes recent developments in two-dimensional polymerization methods.
Two-dimensional materials have recently garnered much interest in the scientific and technology communities. This Review describes how ultrathin transition metal dichalcogenides combine tunable structure and electronic properties, achieved through altering their composition, with versatile chemistry. This makes them attractive in various fields, for example as lithium-ion battery electrodes and electrocatalysts for the hydrogen evolution reaction.
α-Helix-mediated protein–protein interactions (PPIs) play a key role in the development of numerous infection and disease states. Modulating such interactions offers considerable therapeutic potential, however, identifying suitable inhibitors has proved challenging. This Review highlights recent and generic approaches for designing inhibitors of helix-mediated PPIs.
The complexity of living systems makes attempts to gain a molecular-level understanding of them a unique and inspiring challenge. This Review summarizes progress in the development of bioorthogonal reaction-based fluorescent probes used to follow the spatial and temporal dynamics of biologically important analytes within living systems.
