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 potatoPhotoluminescence: Nanocrystals play hot potato, Published online: 10 January 2018; doi:10.1038/s41570-017-0107Semiconductor 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 acrylonitrileSustainability: Sweet new route to acrylonitrile, Published online: 10 January 2018; doi:10.1038/s41570-017-0110A 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
Polynuclear complexes: Buckyball's silver cousin Nat. Rev. Chem. Pub Date : 2017-11-29 Ariane Vartanian
Polynuclear complexes: Buckyball's silver cousin Polynuclear complexes: Buckyball's silver cousin, Published online: 29 November 2017; doi:10.1038/s41570-017-0102 Polynuclear complexes: Buckyball's silver cousin
Metal halide perovskite tandem and multiple-junction photovoltaics Nat. Rev. Chem. Pub Date : 2017-11-29 Giles E. Eperon, Maximilian T. Hörantner, Henry J. Snaith
Metal halide perovskite-based solar cells have attracted considerable attention in recent years owing to their inexpensive and easy fabrication and rapidly increasing efficiencies, which already match those of the industrially dominant multi-crystalline silicon. The incorporation of perovskite absorber materials into multiple (multi-)junction cells could potentially allow us to go well beyond silicon-based technology and reach even higher power conversion efficiencies. Layering multiple solar-absorber junctions on top of each other enables the absorption of different regions of the solar spectrum, so that more energy can be extracted from sunlight. The possibility of tuning the bandgap of perovskite materials over a wide range, along with the ability to generate high open-circuit voltages from wide-bandgap absorbers, make perovskites ideal candidates. Perovskites can be used in combination with or as a substitute for silicon in photovoltaic technologies already in use and can be assembled in hybrid tandem architectures or layered in all-perovskite multi-junction cells. In this Review, we discuss opportunities for perovskite multi-junction cells, explore the progress made so far, describe the theoretical possibilities and discuss perspectives and challenges for the future of this emergent technology.
Dynamic control of function by light-driven molecular motors Nat. Rev. Chem. Pub Date : 2017-11-29 Thomas van Leeuwen, Anouk S. Lubbe, Peter Štacko, Sander J. Wezenberg, Ben L. Feringa
The field of dynamic functional molecular systems has progressed enormously over the past few decades. By coupling the mechanical properties of molecular switches and motors to chemical and biological processes, exceptional control of function has been attained. Overcrowded alkene-based light-driven molecular motors are very attractive in this respect owing to their unique multistate photochemically and thermally induced switching processes and their helical chirality inversion in each switching step. However, extending our control over properties from the molecular scale to larger length scales is still a fundamental challenge. In this Perspective, we discuss recent developments that address this challenge, ranging from the application of these motors in catalysis and synthetic materials to the control of biological properties. We may now be positioned at the dawn of a new era in which artificial molecular motors are able to perform programmed tasks and dynamic functions akin to the biological machines that are found in daily life.
Hexafluoroisopropanol as a highly versatile solvent Nat. Rev. Chem. Pub Date : 2017-11-08 Ignacio Colomer, Anna E. R. Chamberlain, Maxwell B. Haughey, Timothy J. Donohoe
1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) has recently become a very popular solvent or additive with applications across the spectrum of chemistry. Analysis shows that it possesses a wide range of interesting and unique properties. In this Perspective, we detail the main uses of HFIP in the natural sciences and disclose the underlying principles that give it such wide appeal. Accordingly, we show the broad usage and beneficial effects in many areas of chemistry.
New avenues for the large-scale harvesting of blue energy Nat. Rev. Chem. Pub Date : 2017-11-08 Alessandro Siria, Marie-Laure Bocquet, Lydéric Bocquet
Salinity gradients have been identified as promising clean, renewable and non-intermittent sources of energy — so-called blue energy. However, the low efficiency of current harvesting technologies is a major limitation for large-scale viability and is mostly due to the low performances of the membrane processes currently in use. Advances in materials fabrication with dedicated chemical properties can resolve this bottleneck and lead to a new class of membranes for blue-energy conversion. In this Perspective, we briefly present current technologies for the conversion of blue energy, describe their performances and note their limitations. We then discuss new avenues for the development of a new class of membranes, combining considerations in nanoscale fluid dynamics and surface chemistry. Finally, we discuss how new functionalities originating from the exotic behaviour of fluids in the nanoscale regime can further boost energy conversion, making osmotic energy a tangible, clean alternative.
By invitation only? Nat. Rev. Chem. Pub Date : 2017-11-08
By invitation only? By invitation only?, Published online: 08 November 2017; doi:10.1038/s41570-017-0094 NatureArticleSnippet(type=short-summary, markup= Nature Reviews Chemistry welcomes your proposals for review articles. In this editorial, we provide some details on what makes a good proposal. , isJats=true)
Steering chemical reactions with force Nat. Rev. Chem. Pub Date : 2017-11-02 Sergi Garcia-Manyes, Amy E. M. Beedle
Chemical reactivity underlies our fundamental understanding of many physical and biological phenomena. Chemical reactions are typically initiated by heat, electric current or light. Albeit far less studied, mechanical force is yet another way to orthogonally catalyse chemical reactions. An applied force can substantially reduce the reaction energy barrier, thus enabling reaction pathways that are too slow (or even forbidden) according to the laws of thermodynamics. Single-molecule nanomechanical techniques, including optical and magnetic tweezers and atomic force microscopy, offer the possibility to apply a directional force on an individual chemical bond. In non-covalent (or soft) mechanochemistry, low, sub-nN forces trigger bond rotation or hydrogen-bond rupture. By contrast, in covalent mechanochemistry, higher forces typically result in the breaking and re-forming of individual bonds. This Review focuses on the advances in our mechanistic understanding of single-bond mechanochemistry resulting from single-molecule measurements, as well as on the exciting new perspectives that we envision for this burgeoning field in the near future.
Towards an intelligent design of molecular electrocatalysts Nat. Rev. Chem. Pub Date : 2017-10-25 Cyrille Costentin, Jean-Michel Savéant
There is a need for the quantitative assessment of molecular electrocatalysts, particularly those designed to address modern energy challenges. This calls for systematic benchmarking to help rationalize the wealth of available data and to apply the lessons learnt to the innovative design of more efficient catalysts. For these purposes, it is tempting to examine the relationship between the reaction kinetics and the stabilization of a single primary intermediate by constructing a volcano plot. The attractiveness and inherent flaw in this oversimplified approach stem from accounting for complicated multi-electron, multistep processes with a single descriptor. In this Perspective, we instead advocate correlating the turnover frequency with the overpotential through a catalytic Tafel plot, which provides a much less restrictive and more reliable evaluation of intrinsic catalyst performance. Within this framework, one way to optimize molecular catalysts involves altering ligand substituents to tune the electronic structure of the catalyst. These inductive through-structure effects are subject to an ‘iron law’, which dictates that gains in the form of smaller overpotentials come at the price of reduced turnover frequencies (and vice versa). This law can be circumvented by instead engineering through-space effects that stabilize the primary catalytic intermediate. These considerations should be based on the patient gathering of reliable experimental data obtained upon variation of the maximal number of operational parameters.
Rethinking practical classes Nat. Rev. Chem. Pub Date : 2017-10-25 Andrea Sella
Rethinking practical classes Nature Reviews Chemistry, Published online: 25 October 2017; doi:10.1038/s41570-017-0090 Undergraduate practical classes that include more real science are to the benefit of students, teachers and society more broadly.
Erratum: Mapping and elucidating the function of modified bases in DNA Nat. Rev. Chem. Pub Date : 2017-10-11 Eun-Ang Raiber, Robyn Hardisty, Pieter van Delft, Shankar Balasubramanian
Erratum: Mapping and elucidating the function of modified bases in DNA Nature Reviews Chemistry, Published online: 11 October 2017; doi:10.1038/s41570-017-0085
The chemistry of Cas9 and its CRISPR colleagues Nat. Rev. Chem. Pub Date : 2017-10-04 Janice S. Chen, Jennifer A. Doudna
RNA-guided binding and cleavage of nucleic acids by CRISPR–Cas systems is a defining feature of bacterial and archaeal adaptive immunity against viruses and plasmids. As a result of their programmable ability to cut specific DNA and RNA sequences, Cas9 and related single-subunit effector proteins from CRISPR–Cas systems have been widely adopted for research and therapeutic genome engineering applications. In this Review, we discuss the chemistry of macromolecules involved in the multistep interference pathway used by CRISPR–Cas systems that mediate accurate nucleic acid target recognition and cutting. Although this Review mainly focuses on DNA interference by Cas9, we briefly explore nucleic acid targeting by the single-effector proteins Cas12 and Cas13 to emphasize the conserved themes of precision DNA and RNA cleavage within class 2 CRISPR–Cas systems. We further highlight the unique mechanisms of surveillance complex formation, substrate recognition and target cleavage in molecular detail across diverse single-subunit CRISPR–Cas interference proteins.
Multi-phase systems: Hydrogel-driven compartmentalization Nat. Rev. Chem. Pub Date : 2017-10-04 Prabhjot Saini
Multi-phase systems: Hydrogel-driven compartmentalization Nature Reviews Chemistry, Published online: 4 October 2017; doi:10.1038/s41570-017-0084
Radical cascade reactions triggered by single electron transfer Nat. Rev. Chem. Pub Date : 2017-10-04 Mateusz P. Plesniak, Huan-Ming Huang, David J. Procter
The rapid generation of molecular complexity from simple starting materials is of paramount importance in synthetic chemistry. The unique combination of high reactivity and high selectivity often associated with open-shell intermediates makes radical chemistry ideal for cascade reactions, in which simple substrates undergo a series of processes involving bond formation (and bond cleavage) to give complex, high-value products. Crucially, radical cascade reactions can greatly diminish the time, cost and amount of waste associated with complex target synthesis. Recent exciting advances in the field of radical chemistry initiated by single electron transfer (SET) have led to a considerable upward shift in our ability to design powerful new cascade reactions. This Review highlights recent advances in the development of radical cascades, triggered by SET processes, that deliver molecular constructs of importance in medicine and biology.
Analysis of aptamer discovery and technology Nat. Rev. Chem. Pub Date : 2017-10-04 Matthew R. Dunn, Randi M. Jimenez, John C. Chaput
Aptamers are nucleic acid molecules that mimic antibodies by folding into complex 3D shapes that bind to specific targets. Although some aptamers exist naturally as the ligand-binding elements of riboswitches, most are generated in vitro and can be tailored for a specific target. Relative to antibodies, aptamers benefit from their ease of generation, low production cost, low batch-to-batch variability, reversible folding properties and low immunogenicity. However, the true value of aptamers lies in the simplicity by which these molecules can be engineered into sensors, actuators and other devices that are often central to emerging technologies. This Review examines changing trends in aptamer technology by analysing the first quarter century of aptamer data that is available in the scientific literature (1990–2015). We highlight specific examples that showcase the use of aptamers in key applications, discuss challenges that have impeded the success of aptamers in practical applications, provide suggestions for choosing chemical modifications that can lead to enhanced activity or stability, and propose standards for the characterization of aptamers in the scientific literature.
Chemistry challenges to enable a sustainable bioeconomy Nat. Rev. Chem. Pub Date : 2017-09-20 Nichole D. Fitzgerald
Chemistry challenges to enable a sustainable bioeconomy Nature Reviews Chemistry, Published online: 20 September 2017; doi:10.1038/s41570-017-0080 A bioeconomy — that is, an economy in which fuels, chemicals and other products are sourced from biomass — can contribute to a sustainable and prosperous future. Realizing a bioeconomy will necessitate new methods for processing the complex structure of biomass to produce commodity chemicals. Many exciting opportunities are availing themselves to chemists brave enough to tackle this challenging problem.
Read, copy, edit and repeat Nat. Rev. Chem. Pub Date : 2017-09-06
Read, copy, edit and repeat Nature Reviews Chemistry, Published online: 6 September 2017; doi:10.1038/s41570-017-0075 A detailed picture of how DNA is copied and modified comes from a molecular-level understanding of DNA and the enzymes that process it. Why is DNA not always copied correctly, and what happens when its bases are modified?
How DNA polymerases catalyse replication and repair with contrasting fidelity Nat. Rev. Chem. Pub Date : 2017-09-06 Wen-Jin Wu, Wei Yang, Ming-Daw Tsai
DNA polymerases were named for their function of catalysing DNA replication, a process that is necessary for growth and propagation of life. DNA involving Watson–Crick base-pairing can be synthesized with high fidelity, the structural and mechanistic origins of which have been investigated for many decades. Despite this, new chemical insights continue to be uncovered, including recent findings that may explain newly discovered functions for many DNA polymerases in DNA repair and mutation. Some of these reactions involve non-Watson–Crick base-pairing. In addition, certain DNA polymerases have been engineered for a wide variety of applications in biotechnology and biomedicine. This Review describes the molecular basis for the diverse and contrasting functions of different DNA polymerases, providing an up-to-date understanding of how these tasks are accomplished and the means by which we can benefit from them.
Relating DNA base-pairing in aqueous media to DNA polymerase fidelity Nat. Rev. Chem. Pub Date : 2017-09-06 John Petruska, Myron F. Goodman
Relating DNA base-pairing in aqueous media to DNA polymerase fidelity Nature Reviews Chemistry, Published online: 6 September 2017; doi:10.1038/s41570-017-0074 Controversy surrounds the perceived absence of a relationship between DNA polymerase fidelity (kinetic discrimination) and free energy changes determined from DNA melting studies (thermodynamic discrimination). Thermodynamic discrimination together with aqueous solvent effects can account for kinetic fidelities on the order of those observed experimentally.
The medicinal chemistry of ferrocene and its derivatives Nat. Rev. Chem. Pub Date : 2017-09-06 Malay Patra, Gilles Gasser
Ferrocene derivatives have attracted significant interest as anticancer, antibacterial, antifungal and antiparasitic drug candidates. Discovered in the 1990s, the two most prominent derivatives, ferroquine and ferrocifen, have since been studied extensively for the treatment of malaria and cancer, respectively. The ferrocenyl moiety in these two compounds participates in important metal-specific modes of action that contribute to the overall therapeutic efficacy of the molecules. Although ferroquine is currently in phase II clinical trials and ferrocifen is in preclinical evaluation, no other ferrocene derivative — in fact, no other non-radioactive organometallic compound of any kind — has advanced into clinical trials. This Perspective delineates strategies for the systematic incorporation of ferrocenyl groups into known drugs or drug candidates, with a view to finding new drug leads. In addition, we provide a critical evaluation of the difficulties associated with obtaining the clinical approval that would enable ferrocene-containing molecules to transition from being synthetic curiosities to effective drugs.
Mapping and elucidating the function of modified bases in DNA Nat. Rev. Chem. Pub Date : 2017-09-06 Eun-Ang Raiber, Robyn Hardisty, Pieter van Delft, Shankar Balasubramanian
Chemically modified bases exist naturally in genomic DNA. Research into these bases has been invigorated by the discovery of several modified bases in the mammalian genome, in particular 5-methylcytosine and its oxidized derivatives, such as 5-(hydroxymethyl)cytosine and 5-formylcytosine, as well as the enzymes that form and process them, such as the DNA methyltransferases and the ten-eleven translocation enzymes. In this Review, we provide an overview of natural modified bases that have been reported in DNA, our current knowledge of their roles, and the techniques that have enabled us to probe their functions. Analytical methods have been invaluable in helping to advance this field. For example, chemical and enzymatic methods have provided the means to detect and decode modified bases, giving rise to an expanding array of sequencing approaches. Advanced liquid chromatography and tandem mass spectrometry have provided the means to detect and quantify modified bases with very high sensitivity, increasing the prospect of discovering unknown modifications. It is already evident that natural modified DNA bases and their associated enzymology are of fundamental importance to normal biology and to disease. The next decade promises to yield more insights, discoveries and applications from this burgeoning field of research.
Stereospecific and stereoconvergent cross-couplings between alkyl electrophiles Nat. Rev. Chem. Pub Date : 2017-08-23 Erika L. Lucas, Elizabeth R. Jarvo
The development of metal-catalysed cross-coupling reactions between one electrophilic and one organometallic nucleophilic partner has revolutionized the practice of chemical synthesis, with coupling reactions between sp2 centres now commonplace in both academic and industrial research. Methods to allow coupling of sp3 centres are rapidly being developed, with many recent advances even enabling control of the absolute configuration of newly formed stereogenic centres. The related cross-electrophile couplings have not been developed as thoroughly owing to the challenge of obtaining cross-selectivity between two substrates with similar reactivity. However, the discovery of improved methods to address this challenge has led to significant recent progress. The development of enantioselective cross-electrophile coupling reactions is an emerging area of research. Both stereoconvergent and stereospecific variants have been reported for the synthesis of a range of products containing tertiary stereogenic centres. Many of these transformations build on lessons learnt from traditional (electrophile–nucleophile) cross-couplings of alkyl electrophiles. For example, all enantioselective transformations described to date use a nickel catalyst. Continued progression is likely to provide strategic disconnections for asymmetric synthesis of natural products and medicinal agents.
Total synthesis: Polyketides as easy as ABC (and D) Nat. Rev. Chem. Pub Date : 2017-08-23 David Schilter
Total synthesis: Polyketides as easy as ABC (and D) Nature Reviews Chemistry, Published online: 23 August 2017; doi:10.1038/s41570-017-0073
Biogeochemistry: A subglacial microbial methane sink Nat. Rev. Chem. Pub Date : 2017-08-16 Sinéad Lyster
Biogeochemistry: A subglacial microbial methane sink Nature Reviews Chemistry, Published online: 16 August 2017; doi:10.1038/s41570-017-0070 Microbial communities beneath Antarctic subglacial lakes play an important role in biogeochemical cycling, and might mitigate enhanced global warming during ice sheet retreat.
The active template approach to interlocked molecules Nat. Rev. Chem. Pub Date : 2017-08-09 Mathieu Denis, Stephen M. Goldup
The active template approach to interlocked molecules takes advantage of the ability of metal ions to both organize precursor fragments for mechanical bond formation and to mediate the final covalent bond-forming reaction that captures the interlocked structure. Since its inception just a decade ago, this new methodology has expanded rapidly from a single reaction for rotaxane synthesis to a range of metal-mediated bond formations for the synthesis of complex interlocked molecules. In this Review, we introduce the active template concept, its key advantages for the synthesis of interlocked molecules and outline recent advances that have been made using this technology. We will conclude with comments about future directions and challenges.
Surface-enhanced Raman spectroscopy for in vivo biosensing Nat. Rev. Chem. Pub Date : 2017-08-09 Stacey Laing, Lauren E. Jamieson, Karen Faulds, Duncan Graham
Surface-enhanced Raman scattering (SERS) is of interest for biomedical analysis and imaging because of its sensitivity, specificity and multiplexing capabilities. The successful application of SERS for in vivo biosensing requires probes to be biocompatible and procedures to be minimally invasive, challenges that have respectively been met by developing new nanoprobes and instrumentation. This Review presents recent developments in these areas, describing case studies in which sensors have been implemented, as well as outlining shortcomings that must be addressed before SERS sees clinical use.
Evolution of macromolecular complexity in drug delivery systems Nat. Rev. Chem. Pub Date : 2017-08-09 Ashok Kakkar, Giovanni Traverso, Omid C. Farokhzad, Ralph Weissleder, Robert Langer
Designing therapeutics is a process with many challenges. Even if the first hurdle — designing a drug that modulates the action of a particular biological target in vitro — is overcome, selective delivery to that target in vivo presents a major barrier. Side-effects can, in many cases, result from the need to use higher doses without targeted delivery. However, the established use of macromolecules to encapsulate or conjugate drugs can provide improved delivery, and stands to enable better therapeutic outcomes. In this Review, we discuss how drug delivery approaches have evolved alongside our ability to prepare increasingly complex macromolecular architectures. We examine how this increased complexity has overcome the challenges of drug delivery and discuss its potential for fulfilling unmet needs in nanomedicine.
Total synthesis: Closing the box on (+)-dendrowardol C Nat. Rev. Chem. Pub Date : 2017-08-02 Mina Razzak
Total synthesis: Closing the box on (+)-dendrowardol C Nature Reviews Chemistry, Published online: 2 August 2017; doi:10.1038/s41570-017-0067
Reaction mechanisms: Computing reactions in a qubit Nat. Rev. Chem. Pub Date : 2017-07-26 Gabriella Graziano
Reaction mechanisms: Computing reactions in a qubit Nature Reviews Chemistry, Published online: 26 July 2017; doi:10.1038/s41570-017-0064
Electrocatalysis: Reduced ring makes catalyst sing Nat. Rev. Chem. Pub Date : 2017-07-19 Christopher Windle
Electrocatalysis: Reduced ring makes catalyst sing Nature Reviews Chemistry, Published online: 19 July 2017; doi:10.1038/s41570-017-0062
Dimeric magnesium(I) β-diketiminates: a new class of quasi-universal reducing agent Nat. Rev. Chem. Pub Date : 2017-07-19 Cameron Jones
Since the first report of their isolation in 2007, magnesium(I) dimers have transitioned from being chemical curiosities to versatile reducing agents that are used by an ever-increasing number of synthetic chemists. Magnesium(I) dimers have a unique combination of advantageous properties that sees them used in the syntheses of new, and often applicable, compound types that are impossible or difficult to access using conventional reductants. This Perspective describes the synthesis and properties of these dimers, and provides notable examples of their application in organic and inorganic synthesis. Magnesium(I) dimers, especially complexes of β-diketiminates, may now be viewed as widely applicable, quasi-universal reducing agents with a promising future in synthetic chemistry. It is hoped that the reader will develop a familiarity with these reagents, such that the complexes can be successfully used in many synthetic programmes.
Alkane dehydrogenation: Alkanes ylide-vised to go near titanium Nat. Rev. Chem. Pub Date : 2017-07-05 David Schilter
Alkane dehydrogenation: Alkanes ylide-vised to go near titanium Nature Reviews Chemistry, Published online: 5 July 2017; doi:10.1038/s41570-017-0058
Global chemical analysis of biology by mass spectrometry Nat. Rev. Chem. Pub Date : 2017-07-05 Alexander A. Aksenov, Ricardo da Silva, Rob Knight, Norberto P. Lopes, Pieter C. Dorrestein
Mass spectrometry instruments measure the mass to charge ratio of ions, from which we infer the molecular structures. They are key tools for investigating the incredibly diverse chemistry that is associated with biological systems. Typically, when one thinks about the chemistry of biology, one thinks of biochemical pathways, structural lipids or carbohydrates. However, numerous additional chemistries are part of various biological systems. These include molecules that originate from diet, water treatment, personal care, medications, pollutants and environmental exposures including plastics, clothes and furniture. These principles apply not only to people but to all of biology, from the worms at the bottom of the ocean, to the bacteria in our belly buttons and to the birds that fly over Mount Everest. In the past decade, our capacity to inventory the chemistry of biological systems using mass spectrometry at a global level has been revolutionized. In this Review, we discuss the informatics and hardware tools that are available for small-molecule analysis and provide an overview of the tools that could transform how we study the chemistry of biological systems; perhaps in the future this will be as easy as taking a photograph with a smartphone.
Carbon dioxide utilization: A carbon-neutral energy cycle Nat. Rev. Chem. Pub Date : 2017-07-05 Yaoqing Zhang
Carbon dioxide utilization: A carbon-neutral energy cycle Nature Reviews Chemistry, Published online: 5 July 2017; doi:10.1038/s41570-017-0057
Tessellated multiporous two-dimensional covalent organic frameworks Nat. Rev. Chem. Pub Date : 2017-07-05 Yinghua Jin, Yiming Hu, Wei Zhang
In the past decade, covalent organic frameworks (COFs) have emerged as a new class of highly ordered crystalline organic porous polymers. They have attracted tremendous research interest because of their unique structures and potential applications in gas storage and separation, energy storage, catalysis and optoelectronic materials development. Although the skeletons and pore structures of COFs are customizable through judicious selection of chemical building blocks, COF materials have been mainly limited to uniform pore structures with homogeneous pore environments. Two-dimensional COFs with complex multipore structures are largely unexplored, perhaps owing to the challenges that are inherent in designing selective syntheses. Simple tessellation has been remarkably successful in the preparation of regular 2D COFs, but building multiporous systems requires the aid of mathematical design. In this Perspective, we discuss four different approaches to tessellated 2D COFS with a focus on the mathematical rules for their application. A comparison of these strategies should provide guidance to those designing new applications of COF materials.
The merger of transition metal and photocatalysis Nat. Rev. Chem. Pub Date : 2017-07-05 Jack Twilton, Chi (Chip) Le, Patricia Zhang, Megan H. Shaw, Ryan W. Evans, David W. C. MacMillan
The merger of transition metal catalysis and photocatalysis, termed metallaphotocatalysis, has recently emerged as a versatile platform for the development of new, highly enabling synthetic methodologies. Photoredox catalysis provides access to reactive radical species under mild conditions from abundant, native functional groups, and, when combined with transition metal catalysis, this feature allows direct coupling of non-traditional nucleophile partners. In addition, photocatalysis can aid fundamental organometallic steps through modulation of the oxidation state of transition metal complexes or through energy-transfer-mediated excitation of intermediate catalytic species. Metallaphotocatalysis provides access to distinct activation modes, which are complementary to those traditionally used in the field of transition metal catalysis, thereby enabling reaction development through entirely new mechanistic paradigms. This Review discusses key advances in the field of metallaphotocatalysis over the past decade and demonstrates how the unique mechanistic features permit challenging, or previously elusive, transformations to be accomplished.
New space for chemical discoveries Nat. Rev. Chem. Pub Date : 2017-06-28 Richard Jones, Ferenc Darvas, Csaba Janáky
New space for chemical discoveries Nature Reviews Chemistry, Published online: 28 June 2017; doi:10.1038/s41570-017-0055 For long-duration space exploration to be successful, it is essential that chemistry research in space — which has been neglected to date — is intensified. The results of this research is also likely to be of benefit to those at home on Earth.
Computation of enzyme cold adaptation Nat. Rev. Chem. Pub Date : 2017-06-21 Johan Åqvist, Geir Villy Isaksen, Bjørn Olav Brandsdal
Earth has several environments that are potentially hostile to life. The survival of organisms has required the expression of proteins that are adapted to function under extreme temperature, pH, pressure or ionic strength. However, the origin of such adaptations remains, in most cases, an open question. This Review presents a detailed analysis of the specialized enzymes that are able to maintain high catalytic rates at low temperatures and highlights the important role that computational studies have in uncovering the evolutionary principles behind the cold adaptation of enzymes. Although often highly homologous to their mesophilic counterparts, these cold-adapted enzymes have characteristic and universal properties that reflect their evolutionary optimization. In addition to exhibiting maximum reaction rates at lower temperatures, cold-adapted enzymes are more heat-labile and their catalytic mechanisms have distinct signatures in terms of the thermodynamic activation parameters. The structural origins of these properties have been elusive but are hypothesized to be related to protein flexibility.
Evaluating ever-changing curricula Nat. Rev. Chem. Pub Date : 2017-05-17 Kristy Turner
Evaluating ever-changing curricula Nature Reviews Chemistry, Published online: 17 May 2017; doi:10.1038/s41570-017-0044 Experienced practitioners often feel that studying chemistry was harder during their time at school, but is this really true?
The added value of small-molecule chirality in technological applications Nat. Rev. Chem. Pub Date : 2017-06-07 Jochen R. Brandt, Francesco Salerno, Matthew J. Fuchter
Chirality is a fundamental symmetry property; chiral objects, such as chiral small molecules, exist as a pair of non-superimposable mirror images. Although small-molecule chirality is routinely considered in biologically focused application areas (such as drug discovery and chemical biology), other areas of scientific development have not considered small-molecule chirality to be central to their approach. In this Review, we highlight recent research in which chirality has enabled advancement in technological applications. We showcase examples in which the presence of small-molecule chirality is exploited in ways beyond the simple interaction of two different chiral molecules; this can enable the detection and emission of chiral light, help to control molecular motion, or provide a means to control electron spin and bulk charge transport. Thus, we demonstrate that small-molecule chirality is a highly promising avenue for a wide range of technologically oriented scientific endeavours.
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