Metal oxide redox chemistry for chemical looping processes Nat. Rev. Chem. Pub Date : 2018-10-18 Liang Zeng, Zhuo Cheng, Jonathan A. Fan, Liang-Shih Fan, Jinlong Gong
Chemical looping offers a versatile platform to convert fuels and oxidizers in a clean and efficient manner. Central to this technology are metal oxide materials that can oxidize fuels, affording a reduced material that can be reoxidized to close the loop. Recent years have seen substantial advances in the design, formulation and manufacture of these oxygen carrier materials and their incorporation into chemical looping reactors for the production of various chemicals. This Review describes the mechanisms by which oxygen carriers undergo redox reactions and how these carriers can be incorporated into robust chemical looping reactors.
Molecular-level driving forces in lignocellulosic biomass deconstruction for bioenergy Nat. Rev. Chem. Pub Date : 2018-10-18 Loukas Petridis, Jeremy C. Smith
The plant cell wall biopolymers lignin, cellulose and hemicellulose are potential renewable sources of clean biofuels and high-value chemicals. However, the complex 3D structure of lignocellulosic biomass is recalcitrant to deconstruction. Major efforts to overcome this recalcitrance have involved pretreating biomass before catalytic processing. This Perspective describes recent work aimed at elucidating the molecular-level physical phenomena that drive biomass assembly. These are at play in commonly employed aqueous-based and thermochemical pretreatments. Several key processes have been found to be driven by biomass solvation thermodynamics, an understanding of which therefore facilitates the rational improvement of methods aimed at the complete solubilization and fractionation of the major biomass components.
Methods for detection of cytosine and thymine modifications in DNA Nat. Rev. Chem. Pub Date : 2018-10-12 Mark Berney, Joanna F. McGouran
Methylation of cytosine at the 5-position is a common epigenetic modification in mammalian DNA and plays an important role in regulating gene expression. Oxidized derivatives of 5-methylcytosine were discovered recently, and some of these oxidized derivatives, in addition to being intermediates in an active demethylation pathway, might also function as epigenetic modifications. Oxidized derivatives of thymine are known to be products of DNA damage, although evidence exists that the oxidized thymine derivative 5-hydroxymethyluracil might have an epigenetic role. There is a pressing need to learn more about these modifications, as epigenetic modifications have roles in development and in diseases, including cancer. This emerging area of research requires highly accurate and sequence-specific methods for the detection of cytosine and thymine modifications in DNA. In this Review, we introduce the biochemistry of cytosine and thymine modifications and discuss established detection methods, such as bisulfite sequencing and its modifications, as well as newer methods, which have been developed to overcome the substantial obstacles associated with studying these modifications in genomic DNA.
Soft and dispersed interface-rich aqueous systems that promote and guide chemical reactions Nat. Rev. Chem. Pub Date : 2018-10-02 Sandra Serrano-Luginbühl, Kepa Ruiz-Mirazo, Ryszard Ostaszewski, Fabrice Gallou, Peter Walde
Although aqueous solutions are considered to be sustainable, environmentally friendly reaction media, their use is often limited by poor reactant solubility. This limitation can be overcome by converting aqueous solutions into soft, dispersed interface-rich systems such as polyelectrolyte solutions, micellar solutions, oil-in-water microemulsions or vesicle dispersions. All consist of homogeneously distributed dynamic structures that, in a fashion reminiscent of enzymes, provide local environments that are different from the bulk solution. The presence of soft, dispersed interface-rich structures leads to not only selective reaction accelerations but also changes in reaction pathways, whereby chemical reactions are guided towards desired products. Once again, the analogy to enzyme-catalysed transformations is enticing. In this Review, we illustrate the general concepts applied in such systems and illustrate them with selected examples, ranging from enzyme mimics, the preparation of conductive polymers and transition-metal-catalysed organic syntheses on the industrial scale to the chemistry of prebiotic systems.
Frustration leads to radical behaviour Nat. Rev. Chem. Pub Date : 2018-10-02 David Schilter
Frustration leads to radical behaviourFrustration leads to radical behaviour, Published online: 02 October 2018; doi:10.1038/s41570-018-0047-1Certain frustrated Lewis pairs can undergo single electron transfer to give frustrated radical pairs. Such radical pairs have been implicated as important species in the activation of small molecules such as dihydrogen.
Guilty and charged Nat. Rev. Chem. Pub Date : 2018-10-02 Gabriella Graziano
Guilty and chargedGuilty and charged, Published online: 02 October 2018; doi:10.1038/s41570-018-0048-0Atomically thin materials that are both electrically conductive and magnetic are highly desirable. Pedersen, Clérac and co-workers report a new layered coordination polymer — CrCl2(pyrazine)2 — that exhibits both conductive and magnetic-type properties.
Comparing quantitative prediction methods for the discovery of small-molecule chiral catalysts Nat. Rev. Chem. Pub Date : 2018-10-01 Jolene P. Reid, Matthew S. Sigman
Advances in density functional theory (DFT) mean that it is now possible to study catalytic reactions with sufficient accuracy that the results compare favourably with experiment. These high-level calculations have been applied to understand and predict variations in catalytic performance from one catalyst to another, but can require substantial computational resources. By contrast, multivariate linear regression (MLR) methods are rapidly becoming versatile, statistical tools for predicting and understanding the roles of catalysts and substrates and act as a useful complement to complex transition state calculations, with a substantially lower computational cost. Herein, we compare these approaches, DFT calculations and data analysis techniques, and discuss their ability to provide meaningful predictions of catalyst performance. Examples of applications are selected to demonstrate the advantages and limitations of both tools. Several ongoing challenges in the predictions of reaction outcomes are also highlighted.
Immersed in virtual molecules Nat. Rev. Chem. Pub Date : 2018-10-01 Simon J. Lancaster
Immersed in virtual moleculesImmersed in virtual molecules, Published online: 01 October 2018; doi:10.1038/s41570-018-0043-5A full grasp of chemistry requires students to be able to connect microscopic reality with symbolic representations. Immersive virtual reality provides a solution for those who need a tangible link between these representations.
Reversing nitrogen fixation Nat. Rev. Chem. Pub Date : 2018-09-27 Nicolai Lehnert, Hai T. Dong, Jill B. Harland, Andrew P. Hunt, Corey J. White
The nitrogen cycle is one of the most important biogeochemical cycles on Earth because nitrogen is an essential nutrient for all life forms. To supplement natural nitrogen fixation, farmers add large amounts of nitrogen-containing fertilizer to their soils such that nitrogen never becomes a limiting nutrient for plant growth. However, of the nitrogen added to fields — most of which is in the form of NH3 and NO3− — only 30–50% is taken up by plants, while the remainder is metabolized by soil microorganisms in processes with detrimental environmental impacts. The first of these processes, that is, nitrification, refers to the biological oxidation of NH3 to NO2− and NO3−, which have low retention in soil and pollute waterways, leading to downstream eutrophication and ultimately ‘dead zones’ (low oxygen zones) in coastal waters, for example, the Gulf of Mexico. In a second process, namely, denitrification, NO3− and NO2− undergo stepwise reduction to N2O and N2. Substantial amounts of the N2O produced in this process escape into the atmosphere, contributing to climate change and ozone destruction. Recent results suggest that nitrification also affords N2O. This Review describes the enzymes involved in NH3 oxidation and N2O production and degradation in the nitrogen cycle. We pay particular attention to the active site structures, the associated coordination chemistry that enables the chemical transformations and the reaction mechanisms.
Signals from single molecules Nat. Rev. Chem. Pub Date : 2018-09-27 Stephen G. Davey
Signals from single moleculesSignals from single molecules, Published online: 27 September 2018; doi:10.1038/s41570-018-0045-3Following binding kinetics over time rather than relying on differences in free-energy of binding enables detection of single molecules of mutant DNA with an estimated specificity of 99.99999%.
Synthetic materials at the forefront of gene delivery Nat. Rev. Chem. Pub Date : 2018-09-21 Irene Lostalé-Seijo, Javier Montenegro
The delivery of nucleic acids with transient activity for genetic engineering is a promising methodology with potential applications in the treatment of diseases ranging from cancer and infectious diseases to heritable disorders. Restoring the expression of a missing protein, correcting defective splicing of transcripts and silencing or modulating the expression of genes are powerful approaches that could have substantial benefits in biological research and medicine. Impressive progress in improving gene delivery has been made in the past decade, and several products have reached the market. However, translating the results of in vitro and preclinical studies into functional therapies is hindered by the suboptimal performance of gene delivery vehicles in capturing, protecting and delivering nucleic acid cargoes safely and efficaciously. Chemistry has a key role in the development of innovative synthetic materials to overcome the challenges of producing next-generation gene delivery therapies and protocols. In this Review, we discuss the latest chemical advances in the production of materials for the delivery of nucleic acids to cells and for gene therapy.
Author Correction: From a quantum-electrodynamical light–matter description to novel spectroscopies Nat. Rev. Chem. Pub Date : 2018-09-12 Michael Ruggenthaler, Nicolas Tancogne-Dejean, Johannes Flick, Heiko Appel, Angel Rubio
Author Correction: From a quantum-electrodynamical light–matter description to novel spectroscopiesAuthor Correction: From a quantum-electrodynamical light–matter description to novel spectroscopies, Published online: 12 September 2018; doi:10.1038/s41570-018-0035-5Author Correction: From a quantum-electrodynamical light–matter description to novel spectroscopies
Anything you can do… Nat. Rev. Chem. Pub Date : 2018-09-06
Anything you can do…Anything you can do…, Published online: 06 September 2018; doi:10.1038/s41570-018-0038-2Enzymes can serve as blueprints for artificial catalysts, the preparation of which may involve anything from biosynthesis of mutants to chemical synthesis of active site mimics.
From plasmon-enhanced molecular spectroscopy to plasmon-mediated chemical reactions Nat. Rev. Chem. Pub Date : 2018-08-30 Chao Zhan, Xue-Jiao Chen, Jun Yi, Jian-Feng Li, De-Yin Wu, Zhong-Qun Tian
The excitation of surface plasmons (SPs) — collective oscillation of conduction-band electrons in nanostructures — can afford photon, electron and heat energy redistribution over time and space. Making use of this ability, plasmon-enhanced molecular spectroscopy (PEMS) techniques with ultra-high sensitivity and surface selectivity have attracted much attention and have undergone considerable development over the past four decades. Recently, the development of plasmon-mediated chemical reactions (PMCRs) has shown the potential to have a large impact on the practice of chemistry. PMCRs exhibit some obvious differences from and potential advantages over traditional thermochemistry, photochemistry and photocatalysis. However, our physicochemical understanding of PMCRs is still far from complete. In this Review, we analyse the similarities and distinctive features of PEMS and PMCRs and compare PMCRs with traditional photochemical and thermochemical reactions. We then discuss how PMCRs can be improved by rationally designing and fabricating plasmonic nanostructures, selecting suitable surface and interface mediators and teaming them synergistically.
Designing electrochemically reversible H2 oxidation and production catalysts Nat. Rev. Chem. Pub Date : 2018-08-29 Arnab Dutta, Aaron M. Appel, Wendy J. Shaw
The most energy-efficient electrocatalysts mediate forward and reverse reactions at high rates with minimal overpotential requirements. Such electrocatalytic reversibility is commonly observed for redox enzymes and is an attribute that we have sought to bestow on synthetic molecules to realize highly active and robust catalysts for applications in renewable energy. The recent development of the first synthetic molecular catalysts that reversibly mediate H2 ⇌ 2 H+ + 2e− exploits an enzyme-inspired outer coordination sphere that works in concert with both first and second coordination spheres. In this Perspective, we discuss a series of molecular Ni catalysts for H2 production and oxidation that exhibit electrochemical reversibility. Study of these catalysts allows us to identify important first, second and outer coordination sphere features necessary for efficient conversions of H2 and provides direction for the rational design of electrocatalysts that operate on other small molecules.
Mimicry is not mastery Nat. Rev. Chem. Pub Date : 2018-08-29 Niki Kaiser
Mimicry is not masteryMimicry is not mastery, Published online: 29 August 2018; doi:10.1038/s41570-018-0037-3Threshold concepts are the tricky ideas that underpin so much knowledge. In teaching them, it is important to recognize that a correct answer is not necessarily evidence of understanding.
Remodelling (R)-carvone Nat. Rev. Chem. Pub Date : 2018-08-24 Stephen G. Davey
Remodelling (R)-carvone Remodelling (R)-carvone, Published online: 24 August 2018; doi:10.1038/s41570-018-0034-6 A total synthesis of xishacorene B starts from a chiral pool molecule and exploits a C–C activation reaction to form the core structure.
Patterning polarity Nat. Rev. Chem. Pub Date : 2018-08-23 Gabriella Graziano
Patterning polarityPatterning polarity, Published online: 23 August 2018; doi:10.1038/s41570-018-0036-4Water–surface interactions are strongly influenced by the polar or non-polar nature of the chemical groups on the surface. Jacob Monroe and Scott Shell used molecular dynamics simulations and genetic algorithms to show that the specific patterns of such functionalities effect water dynamics.
A N,O hope Nat. Rev. Chem. Pub Date : 2018-08-17 Andrew Bissette
A N,O hopeA N,O hope, Published online: 17 August 2018; doi:10.1038/s41570-018-0033-7Iridium chelates are attractive catalysts for asymmetric transfer hydrogenation. The mode through which a chelating ligand binds iridium turns out to have a striking effect on catalytic activity and enantioselectivity.
The plasticity of redox cofactors: from metalloenzymes to redox-active DNA Nat. Rev. Chem. Pub Date : 2018-08-17 Anja Hemschemeier, Thomas Happe
Metal cofactors considerably widen the catalytic space of naturally occurring enzymes whose specific and enantioselective catalytic activity constitutes a blueprint for economically relevant chemical syntheses. To optimize natural enzymes and uncover novel reactivity, we need a detailed understanding of cofactor–protein interactions, which can be challenging to obtain in the case of enzymes with sophisticated cofactors. As a case study, we summarize recent research on the [FeFe]-hydrogenases, which interconvert protons, electrons and dihydrogen at a unique iron-based active site. We can now chemically synthesize the complex cofactor and incorporate it into an apo-protein to afford functional enzymes. By varying both the cofactor and the polypeptide components, we have obtained detailed knowledge on what is required for a metal cluster to process H2. In parallel, the design of artificial proteins and catalytically active nucleic acids are advancing rapidly. In this Perspective, we introduce these fields and outline how chemists and biologists can use this knowledge to develop novel tailored semisynthetic catalysts.
Visualizing biologically active small molecules in cells using click chemistry Nat. Rev. Chem. Pub Date : 2018-08-16 Tatiana Cañeque, Sebastian Müller, Raphaël Rodriguez
Natural products and synthetic small molecules can be used to perturb, dissect and manipulate biological processes, thereby providing the basis for drug development. Over the past decades, the evolution of molecular biology protocols and microscopy techniques has made it possible to visually detect proteins in living systems with valuable spatiotemporal resolution, in which dynamic topological information has proved to be insightful. By contrast, although small molecules have become essential for biological studies, general methods to track them in cells remain underexplored. In this Review, we discuss how bioorthogonal chemistry, and click chemistry in particular, can be exploited to label and visualize almost any biologically active small molecule in cells and tissues. We review recent developments, highlighting cases in which visualizing small molecules has provided crucial mechanistic insights. This methodology is facile to implement, is versatile and is illuminating.
Streamlining bioactive molecular discovery through integration and automation Nat. Rev. Chem. Pub Date : 2018-07-27 Shiao Chow, Samuel Liver, Adam Nelson
The discovery of bioactive small molecules is generally driven via iterative design–make–purify–test cycles. Automation is routinely harnessed at individual stages of these cycles to increase the productivity of drug discovery. Here, we describe recent progress to automate and integrate two or more adjacent stages within discovery workflows. Examples of such technologies include microfluidics, liquid-handling robotics and affinity-selection mass spectrometry. The value of integrated technologies is illustrated in the context of specific case studies in which modulators of targets, such as protein kinases, nuclear hormone receptors and protein–protein interactions, were discovered. We note that to maximize impact on the productivity of discovery, each of the integrated stages would need to have both high and matched throughput. We also consider the longer-term goal of realizing the fully autonomous discovery of bioactive small molecules through the integration and automation of all stages of discovery.
Semiconducting quantum dots for artificial photosynthesis Nat. Rev. Chem. Pub Date : 2018-07-27 Xu-Bing Li, Chen-Ho Tung, Li-Zhu Wu
Sunlight is our most abundant, clean and inexhaustible energy source. However, its diffuse and intermittent nature makes it difficult to use directly, suggesting that we should instead store this energy. One of the most attractive avenues for this involves using solar energy to split H2O and afford H2 through artificial photosynthesis, the practical realization of which requires low-cost, robust photocatalysts. Colloidal quantum dots (QDs) of IIB–VIA semiconductors appear to be an ideal material from which to construct highly efficient photocatalysts for H2 photogeneration. In this Review, we highlight recent developments in QD-based artificial photosynthetic systems for H2 evolution using sacrificial reagents. These case studies allow us to introduce strategies — including size optimization, structural modification and surface design — to increase the H2 evolution activities of QD-based artificial photosystems. Finally, we describe photocatalytic biomass reforming and unassisted photoelectrochemical H2O splitting — two new pathways that could make QD-based solar-to-fuel conversion practically viable and cost-effective in the near future.
DNA-templated dimerization Nat. Rev. Chem. Pub Date : 2018-07-26 Stephen G. Davey
DNA-templated dimerizationDNA-templated dimerization, Published online: 26 July 2018; doi:10.1038/s41570-018-0028-4A team of French and UK researchers have used DNA to template a key photocatalysed cycloaddition reaction in the total synthesis of a marine natural product.
Pores for effect Nat. Rev. Chem. Pub Date : 2018-07-26 Zoe Budrikis
Pores for effectPores for effect, Published online: 26 July 2018; doi:10.1038/s41570-018-0027-5Isoporous block copolymer films have useful morphological features, but lack the conductivity necessary for chemiresistive sensing. Combining such films with carbon nanotubes affords new porous composites, whose conductivity is sensitive to guest molecules.
Creating molecules that modulate immune responses Nat. Rev. Chem. Pub Date : 2018-07-23 Sander I. van Kasteren, Jacques Neefjes, Huib Ovaa
During evolution, humans developed innate and adaptive immune systems to survive infection by pathogens. The immune system needs to be finely balanced, as an overactive immune system can result in autoimmunity, allergy and inflammatory disorders, whereas over-attenuation can result in infections and cancer. Here, we describe how the immune system can be modulated using chemical approaches, with a focus on the chemical modification and application of antibodies, one of the major components of the immune defence system. Progress includes the development of antibody–drug conjugates and imaging reagents based on antibody fragments and nanobodies, and their clinical and preclinical applications for the treatment of cancer and autoimmune disease are discussed.
Studying glycobiology at the single-molecule level Nat. Rev. Chem. Pub Date : 2018-07-23 Abirami Lakshminarayanan, Mylène Richard, Benjamin G. Davis
Attempts to elucidate the roles of carbohydrate-associated structures in biology have led to the distinct field of glycobiology research. The focus of this field has been in understanding the evolution, biosynthesis and interactions of glycans, both individually and as components of larger biomolecules. However, as most approaches for studying glycans (including mass spectrometry and various binding assays) use ensemble measurements, they lack the precision required to uncover the discrete roles of glycoconjugates, which are often heterogeneous, in biomolecular processes. Single-molecule techniques can examine individual events within challenging mixtures, and they are beginning to be applied to glycobiology. For example, single-molecule force spectroscopy (SMFS) by atomic force microscopy (AFM) has enabled the molecular interactions of sugars to be studied, single-molecule fluorescence microscopy and spectroscopy have led to insight into the role of sugars in biological processes and nanopores have revealed interactions between polysaccharides and their transporters. Thus, single-molecule technology is becoming a valuable tool in glycoscience.
Open shells open doors Nat. Rev. Chem. Pub Date : 2018-07-19 David Schilter
Open shells open doorsOpen shells open doors, Published online: 19 July 2018; doi:10.1038/s41570-018-0026-6Superatoms — particularly paramagnetic ones — can be difficult to isolate and study. Bulky organic ligands have been shown to stabilize a large copper-aluminium superatom with a unique open-shell electronic structure.
Comparing proteins and nucleic acids for next-generation biomolecular engineering Nat. Rev. Chem. Pub Date : 2018-07-05 Genevieve C. Pugh, Jonathan R. Burns, Stefan Howorka
Nanostructures built from biomolecules such as proteins, DNA and RNA are attracting attention in many areas of biological and materials sciences. Such nanoscale engineering was pioneered with proteins, yet the use of DNA is rapidly gaining traction. What are the advantages of the different biopolymers and which is best suited for a given molecular structure, function or application? In this Review, we evaluate the different structural properties of proteins and nucleic acids, as well as possible designs and synthetic routes for functional nanostructures. By comparing protein engineering and DNA nanotechnology, we highlight molecular architectures that are relevant in biotechnology, biomedicine and synthetic biology research, and identify emerging areas for research such as hybrid materials composed of protein and DNA/RNA.
Amino proton donors in excited-state intramolecular proton-transfer reactions Nat. Rev. Chem. Pub Date : 2018-07-03 Chi-Lin Chen, Yi-Ting Chen, Alexander P. Demchenko, Pi-Tai Chou
Proton transfer involving site-specific hydrogen-bonding interactions is one of the most fundamental and important reactions in chemistry and biology. Deliberately triggering this reaction by photoexcitation enables unique and insightful mechanistic analyses. This Review describes a particularly effective method that involves exciting a photoacid containing both an amine and a basic residue and monitoring the ensuing excited-state intramolecular proton-transfer (ESIPT) reactions. Replacing a H atom on the amine with another substituent R modulates the acidity of the amine and allows for the excited-state hydrogen-bond strength to be tuned over a very broad range. In this way, one can draw empirical correlations between N−H bond distances, acidity, hydrogen-bond strength and the ESIPT kinetics and thermodynamics. For example, stronger intramolecular N−H···N hydrogen bonding leads to faster and more exergonic ESIPT. Tuning the amine and basic residues allows one to switch the ESIPT mechanism between the kinetic and thermodynamic regimes, such that molecules can generate ratiometric emission, which is suitable for white-light generation and two-colour imaging. The identity of the amine substituent R not only affects the acidity but can be differentially sensitive towards the local chemical environment. Thus, the R group transduces environmental changes into modified ESIPT rates and/or mechanisms. Such studies open new frontiers in the fundamental aspects of proton transfer in amines, as well as their largely unexplored potential applications.
Smart access to 3D structures Nat. Rev. Chem. Pub Date : 2018-06-28 Johnny Dang, Brian Lin, Julia Yuan, Shawn T. Schwartz, Rishabh M. Shah, Neil K. Garg
Smart access to 3D structures Smart access to 3D structures, Published online: 28 June 2018; doi:10.1038/s41570-018-0021-y QR Chem is a free resource that enables teachers and researchers to link audiences directly to three-dimensional renderings of molecules.
Molecular motors in a tight spot Nat. Rev. Chem. Pub Date : 2018-06-28 Gabriella Graziano
Molecular motors in a tight spot Molecular motors in a tight spot, Published online: 28 June 2018; doi:10.1038/s41570-018-0022-x The design of machines in the nanodimesional space is advancing fast. Ben Feringa and co-workers now report on solvent-driven aggregations of molecular motors into nanodimesional bowl-shaped objects and show how molecular rotation can be controlled in such confined volumes.
Metal–ligand interactions in drug design Nat. Rev. Chem. Pub Date : 2018-06-26 Laura Riccardi, Vito Genna, Marco De Vivo
The fast-growing body of experimental data on metalloenzymes and organometallic compounds is fostering the exploitation of metal–ligand interactions for the design of new drugs. Atomistic understanding of the metal–ligand interactions will help us identify potent metalloenzyme inhibitors and metallodrugs. Static docking calculations have proved effective in identifying hit compounds that target metalloproteins. However, the flexibility, dynamics and electronic structure of metal-centred complexes pose difficult challenges for shaping metal–ligand interactions in structure-based drug design. In this respect, once-prohibitive quantum mechanics-based strategies and extensive molecular simulations are rapidly becoming practical approaches for fast-paced drug discovery. These methods account for ligand exchange and structural flexibility at metal-centred complexes and provide good estimates of the thermodynamics and kinetics of metal-aided drug binding. This Perspective examines the successes, limitations and new avenues for modelling metalloenzyme inhibitors and metallodrugs to further explore and expand the unconventional chemical space of these distinctive drugs.
Deciphering digoxin deactivation Nat. Rev. Chem. Pub Date : 2018-06-19 Stephen G. Davey
Deciphering digoxin deactivation Deciphering digoxin deactivation, Published online: 19 June 2018; doi:10.1038/s41570-018-0017-7 Digoxin is a widely used heart drug, but metabolism by bacteria in the human gut leads to variable efficacy. The enzyme responsible has now been identified and characterized.
Author Correction: The ultrafast X-ray spectroscopic revolution in chemical dynamics Nat. Rev. Chem. Pub Date : 2018-06-14 Peter M. Kraus, Michael Zürch, Scott K. Cushing, Daniel M. Neumark, Stephen R. Leone
Author Correction: The ultrafast X-ray spectroscopic revolution in chemical dynamics Author Correction: The ultrafast X-ray spectroscopic revolution in chemical dynamics, Published online: 14 June 2018; doi:10.1038/s41570-018-0016-8 Author Correction: The ultrafast X-ray spectroscopic revolution in chemical dynamics
Ions surf across salt surface Nat. Rev. Chem. Pub Date : 2018-06-04 David Schilter
Ions surf across salt surface Ions surf across salt surface, Published online: 04 June 2018; doi:10.1038/s41570-018-0014-x Aquo complexes at salt surfaces feature in important processes such as salt dissolution and water desalination. Scanning tunnelling microscopy and atomic force microscopy have afforded the first real-space data concerning the structures and dynamics of single aquo complexes.
The ultrafast X-ray spectroscopic revolution in chemical dynamics Nat. Rev. Chem. Pub Date : 2018-05-29 Peter M. Kraus, Michael Zürch, Scott K. Cushing, Daniel M. Neumark, Stephen R. Leone
The past two decades have seen rapid developments in short-pulse X-ray sources, which have enabled the study of nuclear and electronic dynamics by ultrafast X-ray spectroscopies with unprecedented time resolution ranging from nanoseconds to attoseconds. In this Perspective, we discuss some of the major achievements in the study of nuclear and electronic dynamics with X-ray pulses produced by high-harmonic, free-electron-laser and synchrotron sources. The particular dynamic processes probed by X-ray radiation highlighted in this Perspective are electronic coherences on attosecond to femtosecond timescales, chemical reactions, such as dissociations, and pericyclic ring-openings, spin-crossover dynamics, ligand-exchange dynamics and structural deformations in excited states. X-ray spectroscopic probing of chemical dynamics holds great promise for the future owing to the ongoing developments of new spectroscopies, such as four-wave mixing, and the continuous improvements in emerging laboratory-based, high-harmonic sources and large-scale, facility-based, free-electron lasers.
Go with the flow Nat. Rev. Chem. Pub Date : 2018-05-25 Gabriella Graziano
Go with the flow Go with the flow, Published online: 25 May 2018; doi:10.1038/s41570-018-0013-y Controlling shape and size of noble-metal nanocrystals in an automated fashion is highly desirable for large-scale production of nanomaterials. Younan Xia and co-workers propose the design of a device for the automated synthesis of uniform nanocrystals, featuring a droplet reactor, online separation and purification capabilities.
Modern approaches to study plant–insect interactions in chemical ecology Nat. Rev. Chem. Pub Date : 2018-05-25 Lee A. Dyer, Casey S. Philbin, Kaitlin M. Ochsenrider, Lora A. Richards, Tara J. Massad, Angela M. Smilanich, Matthew L. Forister, Thomas L. Parchman, Lanie M. Galland, Paul J. Hurtado, Anne E. Espeset, Andrea E. Glassmire, Joshua G. Harrison, Carmen Mo, Su’ad Yoon, Nicholas A. Pardikes, Nadya D. Muchoney, Joshua P. Jahner, Heather L. Slinn, Oren Shelef, Craig D. Dodson, Massuo J. Kato, Lydia F. Yamaguchi, Christopher S. Jeffrey
Phytochemical variation among plant species is one of the most fascinating and perplexing features of the natural world and has implications for both human health and the functioning of ecosystems. A key area of research on phytochemical variation has focused on insects that feed on plants and the enormous diversity of plant-derived compounds that reduce or deter damage by insects. Empirical studies on the ecology and evolution of these chemically mediated plant–insect interactions have been guided by a long history of theoretical development. However, until recently, such theory was substantially limited by inadequate data, a situation that is rapidly changing as ecologists partner with chemists utilizing the latest technological advances. In this Review, we aim to facilitate the union of ecological theory with modern chemistry by discussing important theoretical frameworks for studying chemical ecology and outlining the steps by which hypotheses on insect–phytochemical interactions can be advanced using current methodologies and statistical approaches. We highlight unique approaches to isolation, synthesis, spectroscopy, metabolomics and genomics relevant to chemical ecology and describe future areas for research that will bring an unprecedented understanding of phytochemical variation.
Heterogeneous single-atom catalysis Nat. Rev. Chem. Pub Date : 2018-05-24 Aiqin Wang, Jun Li, Tao Zhang
Single-atom catalysis has arguably become the most active new frontier in heterogeneous catalysis. Aided by recent advances in practical synthetic methodologies, characterization techniques and computational modelling, we now have a large number of single-atom catalysts (SACs) that exhibit distinctive performances for a wide variety of chemical reactions. This Perspective summarizes recent experimental and computational efforts aimed at understanding the bonding in SACs and how this relates to catalytic performance. The examples described here illustrate the utility of SACs in a broad scope of industrially important reactions and highlight the advantages these catalysts have over those presently used. SACs have well-defined active centres, such that unique opportunities exist for the rational design of new catalysts with high activities, selectivities and stabilities. Indeed, given a certain practical application, we can often design a suitable SAC; thus, the field has developed very rapidly and afforded promising catalyst leads. Moreover, the control we have over certain SAC structures paves the way for designing base metal catalysts with the activities of noble metal catalysts. It appears that we are entering a new era of heterogeneous catalysis in which we have control over well-dispersed single-atom active sites whose properties we can readily tune.
I spy in my nuclei Nat. Rev. Chem. Pub Date : 2018-05-17 Katharine H Wrighton
I spy in my nuclei I spy in my nuclei, Published online: 17 May 2018; doi:10.1038/s41570-018-0012-z This study identifies a human antibody fragment that recognizes i-motifs and shows that these DNA structures are present in the nuclei of human cells.
An old reagent becomes a new precatalyst Nat. Rev. Chem. Pub Date : 2018-05-15 David Schilter
An old reagent becomes a new precatalyst An old reagent becomes a new precatalyst, Published online: 15 May 2018; doi:10.1038/s41570-018-0011-0 The archetypal hydride donor for unsaturated organics, LiAlH4, has also been used in catalytic reductions. Indeed, LiAlH4 has now been shown to be a precatalyst for imine hydrogenation under mild conditions.
Homogeneous catalysis for the production of low-volume, high-value chemicals from biomass Nat. Rev. Chem. Pub Date : 2018-04-30 Trandon A. Bender, Jennifer A. Dabrowski, Michel R. Gagné
The transition from petroleum to biorenewable sources of carbon to meet our energy and chemical feedstock needs is difficult, in part because these sources are so different, with petroleum being under-functionalized and biomass being over-functionalized relative to commercial chemicals. However, target lists such as the US Department of Energy’s Top 10 have converged efforts to develop the technologies needed to manufacture the most important feedstocks accessible from biorenewables. Less well defined but equally important to the economic viability of an integrated biorefinery are low-volume, high-value product streams, which would help offset the capital costs of a biorefinery. In this Review, we attempt to bring together some of the advances that could fill these niche areas, with a focus on the conversion of cellulosics into chemicals using homogeneous catalysis. The products range from high-value jet fuels to monomers for high-performance polymers and materials to pharmaceutical intermediates and cover a broad range of structural complexities.
Designing catalysts for olefin polymerization and copolymerization: beyond electronic and steric tuning Nat. Rev. Chem. Pub Date : 2018-04-27 Changle Chen
More than 50 years have passed since Ziegler and Natta shared the Nobel Prize in Chemistry for their discovery of olefin polymerization catalysts. The field of metal-catalysed polymerization has since matured, in no small part owing to the development of several high-performance catalysts. Although polymerization research has in many ways been driven by catalyst development, this has often occurred as a result of trial and error discovery of a promising motif, followed by extensive tuning of the steric and electronic properties of the ligand(s) present in the lead complex. Recently, some alternative design strategies have emerged that afforded new classes of olefin polymerization catalysts. This Perspective highlights recently designed catalyst motifs and the novel reactivity patterns they enable. Special attention is given to methods specifically designed for the copolymerization of ethylene with polar-functionalized co-monomers — challenging reactions that showcase these creatively designed catalyst motifs.
Earth-abundant transition metal catalysts for alkene hydrosilylation and hydroboration Nat. Rev. Chem. Pub Date : 2018-04-27 Jennifer V. Obligacion, Paul J. Chirik
The addition of X3Si–H or X2B–H (X = H, OR or R) across a C–C multiple bond is a well-established method for incorporating silane or borane groups, respectively, into hydrocarbon feedstocks. These hydrofunctionalization reactions are often mediated by transition metal catalysts, with precious metals being the most commonly used owing to the ability to optimize reaction scope, rates and selectivities. For example, platinum catalysts effect the hydrosilylation of alkenes with anti-Markovnikov selectivity and constitute an enabling technology in the multibillion dollar silicones industry. Increased emphasis on sustainable catalytic methods and on more economic processes has shifted the focus to catalysis with more earth-abundant transition metals, such as iron, cobalt and nickel. This Review describes the use of first-row transition metal complexes in catalytic alkene hydrosilylation and hydroboration. Defining advances in the field are covered, noting the chemistry that is unique to first-row transition metals and the design features that enable them to exhibit precious-metal-like reactivity. Other important features, such as catalyst activity and stability, are covered, as are practical considerations, such as cost and safety.
A high-resolution molecular photo-shoot Nat. Rev. Chem. Pub Date : 2018-04-27 Gabriella Graziano
A high-resolution molecular photo-shoot A high-resolution molecular photo-shoot, Published online: 27 April 2018; doi:10.1038/s41570-018-0007-9 The resolution of AFM images is highly sensitive to the atomic composition and structure of the tip. Harry Mönig and co-workers show that an oxygen-terminated copper tip can enable imaging at unprecedented resolution, allowing us to study molecular interactions in exquisite detail.
The search for selectivity Nat. Rev. Chem. Pub Date : 2018-04-20 David Schilter
The search for selectivity The search for selectivity, Published online: 20 April 2018; doi:10.1038/s41570-018-0004-z It is challenging to efficiently reduce CO2, let alone do so with deliberate control of selectivity. A new study on metalloporphyrin-catalyzed CO2 electroreduction reveals why some catalysts make CO and others make HCO2H.
Water promotes dehydration Nat. Rev. Chem. Pub Date : 2018-04-18 Katherine J. Geogheghan
Water promotes dehydration Water promotes dehydration, Published online: 18 April 2018; doi:10.1038/s41570-018-0002-1 The development of a green route to allylic sulfones reveals that, counter-intuitively, water promotes a dehydration reaction.
Multiscale methods in drug design bridge chemical and biological complexity in the search for cures Nat. Rev. Chem. Pub Date : 2018-04-11 Rommie E. Amaro, Adrian J. Mulholland
Drug action is inherently multiscale: it connects molecular interactions to emergent properties at cellular and larger scales. Simulation techniques at each of these different scales are already central to drug design and development, but methods capable of connecting across these scales will extend our understanding of complex mechanisms and our ability to predict biological effects. Improved algorithms, ever-more-powerful computing architectures and the accelerating growth of rich data sets are driving advances in multiscale modelling methods capable of bridging chemical and biological complexity from the atom to the cell. Particularly exciting is the development of highly detailed, structure-based physical simulations of biochemical systems, which can now reach experimentally relevant timescales for large systems and, at the same time, achieve unprecedented accuracy. In this Perspective, we discuss how emerging data-rich, physics-based multiscale approaches are on the cusp of realizing their long-promised impact on the discovery, design and development of novel therapeutics. We highlight emerging methods and applications in this growing field and outline how different scales can be combined in practical modelling and simulation strategies.
Heterogeneous catalysis: Single atoms on a roll Nat. Rev. Chem. Pub Date : 2018-04-06 Yaoqing Zhang
Heterogeneous catalysis: Single atoms on a roll Heterogeneous catalysis: Single atoms on a roll, Published online: 06 April 2018; doi:10.1038/s41570-018-0151 The controlled deposition of single Pt atoms on a substrate affords a well-dispersed and robust CO oxidation catalyst, for which spectroscopic characterization can unravel detailed reaction pathways.
Retrosynthesis: Computer says yes Nat. Rev. Chem. Pub Date : 2018-04-06 Stephen G. Davey
Retrosynthesis: Computer says yes Retrosynthesis: Computer says yes, Published online: 06 April 2018; doi:10.1038/s41570-018-0152 Retrosyntheses of eight industrially relevant molecules have been planned by a computer and successfully executed by chemists in the laboratory.
Heterogeneous catalysis: Nanoparticle catalysts find a nice home in a foam Nat. Rev. Chem. Pub Date : 2018-03-29 Adam Weingarten
Heterogeneous catalysis: Nanoparticle catalysts find a nice home in a foam Heterogeneous catalysis: Nanoparticle catalysts find a nice home in a foam, Published online: 29 March 2018; doi:10.1038/s41570-018-0137 Heterogeneous catalysis: Nanoparticle catalysts find a nice home in a foam
Homogeneous catalysis: Synthetic models close in on enzymes Nat. Rev. Chem. Pub Date : 2018-03-29 David Schilter
Homogeneous catalysis: Synthetic models close in on enzymes Homogeneous catalysis: Synthetic models close in on enzymes, Published online: 29 March 2018; doi:10.1038/s41570-018-0147 Homogeneous catalysis: Synthetic models close in on enzymes
Homogeneous catalysis: An electrochemical and spectroscopic look at renewable energy Nat. Rev. Chem. Pub Date : 2018-03-29 Gabriella Graziono
Homogeneous catalysis: An electrochemical and spectroscopic look at renewable energy Homogeneous catalysis: An electrochemical and spectroscopic look at renewable energy, Published online: 29 March 2018; doi:10.1038/s41570-018-0130 Homogeneous catalysis: An electrochemical and spectroscopic look at renewable energy
Heterogeneous catalysis: Tuning up a hybrid catalyst Nat. Rev. Chem. Pub Date : 2018-03-29 Adam West
Heterogeneous catalysis: Tuning up a hybrid catalyst Heterogeneous catalysis: Tuning up a hybrid catalyst, Published online: 29 March 2018; doi:10.1038/s41570-018-0140 Heterogeneous catalysis: Tuning up a hybrid catalyst
Heterogeneous catalysis: Base metals break up water Nat. Rev. Chem. Pub Date : 2018-03-29 Claire Ashworth
Heterogeneous catalysis: Base metals break up water Heterogeneous catalysis: Base metals break up water, Published online: 29 March 2018; doi:10.1038/s41570-018-0133 Heterogeneous catalysis: Base metals break up water
Reorienting chemistry education through systems thinking Nat. Rev. Chem. Pub Date : 2018-03-29 Peter G. Mahaffy, Alain Krief, Henning Hopf, Goverdhan Mehta, Stephen A. Matlin
Reorienting chemistry education through systems thinking Reorienting chemistry education through systems thinking, Published online: 29 March 2018; doi:10.1038/s41570-018-0126 It is time for chemistry learning to be reoriented through systems thinking, which offers opportunities to better understand and stimulate students’ learning of chemistry, such that they can address twenty-first century challenges. Integrating systems thinking into chemistry education involves the contextualization of chemistry concepts. This will allow us to better understand how students learn, and will also equip them to tackle the many and varied challenges we face as a society.
Heterogeneous catalysis: Substrate flux dictates selectivity Nat. Rev. Chem. Pub Date : 2018-03-29 Magdalena Helmer
Heterogeneous catalysis: Substrate flux dictates selectivity Heterogeneous catalysis: Substrate flux dictates selectivity, Published online: 29 March 2018; doi:10.1038/s41570-018-0143 Heterogeneous catalysis: Substrate flux dictates selectivity
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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