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
C–H functionalization: Access to arylomycin antibiotics Nat. Rev. Chem. Pub Date : 2018-03-21 Stephen G. Davey
C–H functionalization: Access to arylomycin antibiotics C–H functionalization: Access to arylomycin antibiotics, Published online: 21 March 2018; doi:10.1038/s41570-018-0150 C–H functionalization: Access to arylomycin antibiotics
Electrocatalysis for the generation and consumption of fuels Nat. Rev. Chem. Pub Date : 2018-03-14
Electrocatalysis for the generation and consumption of fuels Electrocatalysis for the generation and consumption of fuels, Published online: 14 March 2018; doi:10.1038/s41570-018-0125 Efficient redox catalysis offers an important avenue in using renewable energy to process fuels. To this end, efforts in homogeneous, heterogeneous and microbial catalysis may each advance our fundamental understanding and technological capabilities.
The increasing dynamic, functional complexity of bio-interface materials Nat. Rev. Chem. Pub Date : 2018-03-07 Bárbara Santos Gomes, Bárbara Simões, Paula M. Mendes
The increasing dynamic, functional complexity of bio-interface materials The increasing dynamic, functional complexity of bio-interface materials, Published online: 07 March 2018; doi:10.1038/s41570-018-0120 Bio-interface materials inspired by natural systems that respond efficiently to various external stimuli can dynamically regulate molecular interactions between biological entities and material surfaces. In this Review, Gomes and colleagues describe advances in bio-interface materials that may provide insights into cell behaviour, biofouling and the production of on-demand devices with medical applications, among others.
From a quantum-electrodynamical light–matter description to novel spectroscopies Nat. Rev. Chem. Pub Date : 2018-03-07 Michael Ruggenthaler, Nicolas Tancogne-Dejean, Johannes Flick, Heiko Appel, Angel Rubio
From a quantum-electrodynamical light–matter description to novel spectroscopies From a quantum-electrodynamical light–matter description to novel spectroscopies, Published online: 07 March 2018; doi:10.1038/s41570-018-0118 Quantum electrodynamics (QED) is the most complete theoretical framework to date to complement experimental spectroscopies in chemistry. Owing to its complexity, several approximations are needed in order to be able to apply QED in practice. This Review highlights how the breakdown of some of these approximations challenges our understanding of light–matter interactions and discusses how new theoretical developments can help to overcome these approximations.
Erratum: Towards the generalized iterative synthesis of small molecules Nat. Rev. Chem. Pub Date : 2018-03-07 Jonathan W. Lehmann, Daniel J. Blair, Martin D. Burke
Erratum: Towards the generalized iterative synthesis of small molecules Erratum: Towards the generalized iterative synthesis of small molecules, Published online: 07 March 2018; doi:10.1038/s41570-018-0128 Erratum: Towards the generalized iterative synthesis of small molecules
C–H functionalization: Access to arylomycin antibiotics Nat. Rev. Chem. Pub Date : 2018-03-07 Stephen G. Davey
C–H functionalization: Access to arylomycin antibiotics C–H functionalization: Access to arylomycin antibiotics, Published online: 07 March 2018; doi:10.1038/s41570-018-0124 C–H functionalization logic has enabled rapid synthetic access to arylomycin antibiotics which could lead to the identification of new broad-spectrum antibiotics.
Molecular collisions: A crash course in energy transfer Nat. Rev. Chem. Pub Date : 2018-03-07 Gabriella Graziano
Molecular collisions: A crash course in energy transfer Molecular collisions: A crash course in energy transfer, Published online: 07 March 2018; doi:10.1038/s41570-018-0127 High-resolution experimental and theoretical velocity map imaging data explain the intricate and conterintuitive mechanism of bimolecular collisions.
Learn to embrace the enabling power of tech Nat. Rev. Chem. Pub Date : 2018-02-28 Katherine Haxton
Learn to embrace the enabling power of tech Learn to embrace the enabling power of tech, Published online: 28 February 2018; doi:10.1038/s41570-018-0123 Lecture capture is just one way in which new technology is changing teaching, but we should embrace its opportunities rather than fear its shortcomings, argues Katherine Haxton.
Nuclear quantum effects enter the mainstream Nat. Rev. Chem. Pub Date : 2018-02-28 Thomas E. Markland, Michele Ceriotti
Atomistic simulations of chemical, biological and materials systems have become increasingly precise and predictive owing to the development of accurate and efficient techniques that describe the quantum mechanical behaviour of electrons. Nevertheless, the overwhelming majority of such simulations still assumes that the nuclei behave as classical particles. Historically, this approximation could sometimes be justified owing to the complexity and computational overhead. However, neglecting nuclear quantum effects has become one of the largest sources of error, especially when systems containing light atoms are treated using current state-of-the-art descriptions of chemical interactions. Over the past decade, this realization has spurred a series of methodological advances that have dramatically reduced the cost of including these important physical effects in the structure and dynamics of chemical systems. Here, we discuss how these developments are now allowing nuclear quantum effects to become a mainstream feature of molecular simulations. These advances have led to new insights into phenomena that are relevant to different areas of science — from biochemistry to condensed matter — and open the door to many exciting future opportunities.
Molecular machines for catalysis Nat. Rev. Chem. Pub Date : 2018-02-28 Lucy van Dijk, Michael J. Tilby, Robert Szpera, Owen A. Smith, Holly A. P. Bunce, Stephen P. Fletcher
The past few decades have seen tremendous progress in the synthesis and operation of molecular systems capable of controlled mechanical movement. Here, we review the use of molecular machines as catalysts for controlling chemical reactions. We highlight the various catalyst designs with a focus on how mechanical motion is used to control catalysis with varying degrees of success. This Review discusses the current challenges of designing effective catalysts, the scope and limitations of various systems and the future potential and aims for the field. Although it is difficult to predict which concepts will become most important, as much of the work is at the proof-of-concept level, it seems clear that molecular machines have the potential to substantially impact the field of catalysis.
Synthetic methodology: Labelling of bioactive azaarenes Nat. Rev. Chem. Pub Date : 2018-02-21 Andrew Bissette
Synthetic methodology: Labelling of bioactive azaarenes Synthetic methodology: Labelling of bioactive azaarenes, Published online: 21 February 2018; doi:10.1038/s41570-018-0119 Phosphonium adducts of pyridines are labile in basic solution, an undesirable property with regard to organic synthesis. Yet, this very lability proves valuable for the labelling of pyridine and diazines with heavier isotopes of hydrogen.
Electrocatalysis: Volcano spews out hot new catalyst Nat. Rev. Chem. Pub Date : 2018-02-07 David Schilter
Electrocatalysis: Volcano spews out hot new catalyst Electrocatalysis: Volcano spews out hot new catalyst, Published online: 07 February 2018; doi:10.1038/s41570-018-0116 Electrocatalytic O2 reduction on metal surfaces is well understood in acidic solution, but the mechanism in basic solution has been a point of contention. On studying the O2 reduction activities of a series of Pt(111)–Cu surface alloys, it becomes clear that the surface-bound oxygenic intermediates are the same regardless of the pH.
Synthesis, structures and applications of electron-rich polyoxometalates Nat. Rev. Chem. Pub Date : 2018-02-07 Nadiia I. Gumerova, Annette Rompel
Ever since the discovery and development of polyoxometalates (POMs), it has been known that they can exist in electron-rich reduced forms of different archetypes, structural flexibilities and functionalities. There are now reliable synthetic strategies for electron-rich POMs — materials that have unique and potentially useful catalytic, electronic and magnetic properties. This Review covers the synthesis and applications of these reduced species, and also highlights their differences and advantages relative to fully oxidized POMs. More than 200 reduced POM structures are described in this Review, with emphasis placed on how reduction influences POM structure, function and properties.
Towards the generalized iterative synthesis of small molecules Nat. Rev. Chem. Pub Date : 2018-02-07 Jonathan W. Lehmann, Daniel J. Blair, Martin D. Burke
Small molecules have extensive untapped potential to benefit society, but access to this potential is too often restricted by limitations inherent to the highly customized approach that is currently used to synthesize this class of chemical matter. An alternative ‘building block approach’ — that is, generalized iterative assembly of interchangeable parts — has now proved to be a highly efficient and flexible method of constructing things ranging from skyscrapers and macromolecules to artificial intelligence algorithms. The structural redundancy found in many small molecules suggests that they possess a similar capacity for generalized building block-based construction. It is also encouraging that many customized iterative synthesis methods have been developed that already improve access to specific classes of small molecules. There has also been substantial recent progress towards the iterative assembly of many different types of small molecules, including complex natural products, pharmaceuticals, biological probes and materials, using common building blocks and coupling chemistry. Collectively, these advances suggest that a generalized building block approach for small-molecule synthesis may be within reach.
Planar pentacoordinate carbons Nat. Rev. Chem. Pub Date : 2018-02-07 Valentin Vassilev-Galindo, Sudip Pan, Kelling J. Donald, Gabriel Merino
Carbon centres in typical organic molecules have a coordination number that can reach a maximum of four, in which case the bonded atoms are situated at the vertices of a tetrahedron. Exceptions to those two structural rules have been posited and examined for decades, and planar tetracoordinate carbon (ptC) species are notable molecules that violate the second rule. There is continued interest in experimental and theoretical studies of ptCs, as well as emerging molecules that contain planar pentacoordinate carbon (ppC) and planar hexacoordinate carbon (phC) atoms, species that violate both structural rules. This Review describes recent progress in the theoretical prediction of viable entities that contain ppC centres. The first such molecule reported, the D5h-symmetric ppC species CAl5+, was followed by a series of predicted ppC species that could be obtained by substituting the Al centres for other heteroatoms. More complicated ppC systems have also been suggested, including metallocene-stabilized ppCs and quasi-ppCs embedded within cage structures or 2D materials. To date, computational studies have identified at least 65 local and 39 global minimum energy structures that contain ppCs or quasi-ppCs. The general design principles for ptC-centred candidate structures include delocalization of the central C 2pz lone electron pair, ensuring an 18 valence electron count and allowing for strong electron delocalization. These principles have been extended to ppC systems with some success. It is hard to predict the extent to which the coordination number of planar C can be increased because it depends not only on the valence and size of C but also on the size of the atoms bonded to it and the mode of bonding. Although a few energetically low-lying planar hexacoordinate and heptacoordinate C species have been identified computationally, none have been observed experimentally.
Spectroscopy: Aromatic astrochemistry Nat. Rev. Chem. Pub Date : 2018-01-31 Gabriella Graziano
Spectroscopy: Aromatic astrochemistry Spectroscopy: Aromatic astrochemistry, Published online: 31 January 2018; doi:10.1038/s41570-018-0113 The first detection of rotational features of benzonitrile offers the opportunity to undesrtand the origin of PAHs in space.
Atom-transfer radical polymerization: New method breathes life into ATRP Nat. Rev. Chem. Pub Date : 2018-01-31 Johannes Kreutzer
Atom-transfer radical polymerization: New method breathes life into ATRP Atom-transfer radical polymerization: New method breathes life into ATRP, Published online: 31 January 2018; doi:10.1038/s41570-018-0111 The practicality of radical polymerizations is limited by their sensitivity to O2. This inhibitor can be enzymatically degraded into H2O2, which is scavenged by pyruvate as part of a new atom transfer radical polymerization (ATRP) methodology.
Low-dimensional catalysts for hydrogen evolution and CO2 reduction Nat. Rev. Chem. Pub Date : 2018-01-10 Damien Voiry, Hyeon Suk Shin, Kian Ping Loh, Manish Chhowalla
Low-dimensional materials and their hybrids have emerged as promising candidates for electrocatalytic and photocatalytic hydrogen evolution and CO2 conversion into useful molecules. Progress in synthetic methods for the production of catalysts coupled with a better understanding of the fundamental catalytic mechanisms has enabled the rational design of catalytic nanomaterials with improved performance and selectivity. In this Review, we analyse the state of the art in the implementation of low-dimensional nanomaterials and their van der Waals heterostructures for hydrogen evolution and CO2 reduction by electrocatalysis and photocatalysis. We explore the mechanisms involved in both reactions and the different strategies to further optimize the activity, efficiency and selectivity of low-dimensional catalysts.
Photoluminescence: Nanocrystals play hot potato Nat. Rev. Chem. Pub Date : 2018-01-10 David Schilter
Photoluminescence: Nanocrystals play hot potato Photoluminescence: Nanocrystals play hot potato, Published online: 10 January 2018; doi:10.1038/s41570-017-0107 Semiconductor nanocrystals absorb light and are involved in energy transfer to and from surface chromophores. Tuning the nanocrystal- and chromophore-centred exciton energies affords exquisite control over an excited-state equilibrium.
Sustainability: Sweet new route to acrylonitrile Nat. Rev. Chem. Pub Date : 2018-01-10 Stephen G. Davey
Sustainability: Sweet new route to acrylonitrile Sustainability: Sweet new route to acrylonitrile, Published online: 10 January 2018; doi:10.1038/s41570-017-0110 A new route to acrylonitrile from a bio-based feedstock offers an improved yield, lower emissions and a safer process.
Biomimetic power sources: Eelectric hydrogels Nat. Rev. Chem. Pub Date : 2017-12-20 Gabriella Graziano
Biomimetic power sources: Eelectric hydrogels Biomimetic power sources: Eelectric hydrogels, Published online: 20 December 2017; doi:10.1038/s41570-017-0106 Biomimetic power sources: Eelectric hydrogels
The evolving science of phytocannabinoids Nat. Rev. Chem. Pub Date : 2017-12-20 Tristan A. Reekie, Michael P. Scott, Michael Kassiou
The cannabis plant has had a tumultuous past. Once revered for its medicinal properties, it then became a banned narcotic and now the perceived medical benefits of cannabis see it receiving renewed attention. The active ingredients in cannabis plant extracts — phytocannabinoids — are now being investigated, both as formulations and in isolation, for pharmaceutical applications. The most abundant phytocannabinoid is (−)-trans-Δ9-tetrahydrocannabinol, a compound readily extracted from Cannabis sativa. There are over 100 known phytocannabinoids, some of which are present in such low concentrations that chemical syntheses are necessary to advance their medicinal potential. In this Review, we examine phytocannabinoids in terms of their mode of action, biosynthesis, and various total syntheses and derivatizations. Finally, we describe the policy issues surrounding the possession, use and control of phytocannabinoids.
Precision synthesis versus bulk-scale fabrication of graphenes Nat. Rev. Chem. Pub Date : 2017-12-20 Xiao-Ye Wang, Akimitsu Narita, Klaus Müllen
Graphene is a fascinating material with unique properties, such as extreme mechanical strength, ultrahigh electrical and thermal conductivities and remarkable transparency. Further reduction in the dimensionality of graphene in the form of graphene quantum dots and graphene nanoribbons has compensated for the lack of a bandgap in the extended 2D material. These nanoscale graphenes exhibit finite bandgaps because of quantum confinement, making them attractive as next-generation semiconductors. Numerous fabrication methods for various types of graphenes have been developed, which can generally be categorized into ‘top-down’ and ‘bottom-up’ procedures. These methods afford, on different production scales, a wide range of graphene structures of different sizes, shapes and quality (defect density, edge roughness and so on). Atomically precise syntheses are indispensable for fundamental research and future technological development, but the projection of the existing methods to cost-effective bulk-scale fabrication techniques is required for upcoming industrial applications of graphenes.
Natural inspirations for metal–ligand cooperative catalysis Nat. Rev. Chem. Pub Date : 2017-12-13 Matthew D. Wodrich, Xile Hu
In conventional homogeneous catalysis, supporting ligands act as spectators that do not interact directly with substrates. However, in metal–ligand cooperative catalysis, ligands are involved in facilitating reaction pathways that would be less favourable were they to occur solely at the metal centre. This catalysis paradigm has been known for some time, in part because it is at play in enzyme catalysis. For example, studies of hydrogenative and dehydrogenative enzymes have revealed striking details of metal–ligand cooperative catalysis that involve functional groups proximal to metal active sites. In addition to the more well-known [FeFe]-hydrogenase and [NiFe]-hydrogenase enzymes, [Fe]-hydrogenase, lactate racemase and alcohol dehydrogenase each makes use of cooperative catalysis. This Perspective highlights these enzymatic examples of metal–ligand cooperative catalysis and describes functional bioinspired molecular catalysts that also make use of these motifs. Although progress has been made in developing molecular catalysts, considerable challenges will need to be addressed before we have synthetic catalysts of practical value.
Molecular electrocatalysts for the oxygen reduction reaction Nat. Rev. Chem. Pub Date : 2017-12-06 Subal Dey, Biswajit Mondal, Sudipta Chatterjee, Atanu Rana, Sk Amanullah, Abhishek Dey
The past decade has seen considerable growth in the development of materials for fuel cell electrodes, and there is a desire for active electrocatalysts derived from base metals instead of noble metals. Fuels cells that consume H2 and O2 require catalysts to cleave these reactants, with the oxygen reduction reaction (ORR) — either 4H+/4e− reduction to 2H2O or 2H+/2e− reduction to H2O2 — being particularly challenging. The ORR is efficiently performed by certain metalloenzymes, and understanding the links between their structure and function aids the design of molecular ORR electrocatalysts. These bio-inspired catalysts exhibit good activity relative to previous synthetic systems and, furthermore, have provided mechanistic insights relevant to synthetic and enzymatic catalysts. This Review covers recent developments in homogeneous and heterogeneous molecular ORR catalysis, placing emphasis on reaction mechanisms and the factors governing rates and selectivities.
C–H functionalization: Functionalization of cyclic amines Nat. Rev. Chem. Pub Date : 2017-12-06 Giovanni Bottari
C–H functionalization: Functionalization of cyclic amines C–H functionalization: Functionalization of cyclic amines, Published online: 06 December 2017; doi:10.1038/s41570-017-0104 C–H functionalization: Functionalization of cyclic amines
Don't get lost in translation Nat. Rev. Chem. Pub Date : 2017-12-06 Stephen Caddick
Don't get lost in translation Don't get lost in translation, Published online: 06 December 2017; doi:10.1038/s41570-017-0103 Stephen Caddick discusses the role of technology transfer offices and their future in translating research
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