Nature Chemistry Contents February 2018 Volume 10 Number 2 pp 111 - 244

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Advertisement Nature Collection: 2017 Nobel Prize in Chemistry  Nature Research present this Collection of articles celebrating the 2017 Nobel Prize in Chemistry to Jacques Dubochet, Joachim Frank and Richard Henderson, recognised "for developing cryo-electron microscopy for the high-resolution structure determination of biomolecules in solution".  Access here >>  Produced with support from  Thermo Fisher Scientific  TABLE OF CONTENTS February 2018 Volume 10, Issue 2 Thesis News and Views Articles Corrigendum Erratum In Your Element   Advertisement   Do you have a career question? The Naturejobs podcast features one-on-one Q&As, panel discussions and other exclusive content to help scientists with their careers. Hosted on the Naturejobs blog, the podcast is also available on iTunes and Soundcloud. Listen today!   Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Nature Catalysis is now live! Explore the first issue which is free to access online for a limited time.  READ NOW >>    Advertisement npj Microgravity is a new open access journal specifically dedicated to publishing research which enables space exploration and research that is enabled by spaceflight and ground-based spaceflight analogues. npj Microgravity is published in cooperation the Biodesign Institute at Arizona State University, and is part of the Nature Partner Journals series.   Find out more >>>   Thesis Top Introducing organic   pp111 - 112 Bruce Gibb doi:10.1038/nchem.2933 As another semester of organic chemistry comes to a close, Bruce Gibb looks back on what he has learned about learning.   News and Views Top Solution-phase reaction dynamics: Gaining control   pp113 - 114 Amanda S. Case doi:10.1038/nchem.2937 Using infrared light to control the outcome of a chemical reaction is problematic in solution because of numerous interactions and non-specific sample heating. Now, condensed-phase results showing the vibrational enhancement of an otherwise thermally driven reaction may reinvigorate discussion of the practical applications of vibrational control. See also: Article by Stensitzki et al. Mass spectrometry: Raw protein from the top down   pp114 - 116 Kathrin Breuker doi:10.1038/nchem.2936 Mass spectrometry is a powerful technique for analysing proteins, yet linking higher-order protein structure to amino acid sequence and post-translational modifications is far from simple. Now, a native top-down method has been developed that can provide information on higher-order protein structure and different proteoforms at the same time. See also: Article by Li et al. C–H carbonylation: In situ acyl triflates ace it   pp116 - 117 Yong Ho Lee and Bill Morandi doi:10.1038/nchem.2934 A simple palladium catalyst has mediated the facile formation of aroyl triflates — an extremely reactive class of electrophiles. These intermediates, generated in situ, enable the Friedel-Crafts acylation of traditionally unreactive arenes, addressing a significant gap in C–H carbonylation methodology. See also: Article by Garrison Kinney et al. Chemistry JOBS of the week Junior Group Leader Positions Insitut Curie Chemical Biology / Medicinal Chemistry � Tenure track Position University of Nebraska Medical Center Assistant Professor of Nutritional Chemistry Cornell University The 4th Silk Road International Spring Symposium for Distinguished Young Scholars Xi'an Jiaotong University (XJTU) PhD student in Chemical Reaction Dynamics Department of Chemistry and Molecular Biology - University of Gothenburg More Science jobs from Chemistry EVENT 3rd Green and Sustainable Chemistry Conference 13.05.18 Berlin, Germany More science events from Articles Top Biocatalytic site- and enantioselective oxidative dearomatization of phenols   pp119 - 125 Summer A. Baker Dockrey, April L. Lukowski, Marc R. Becker and Alison R. H. Narayan doi:10.1038/nchem.2879 Within natural product biosynthetic pathways, nature has evolved highly selective catalysts capable of complexity-generating reactions. Leveraging these tools, a suite of catalysts with complementary site- and stereoselectivity have been applied to the oxidative dearomatization of phenolic compounds, enabling one-pot transformations of phenols into various natural products. Chemical compounds Acceleration of a ground-state reaction by selective femtosecond-infrared-laser-pulse excitation   pp126 - 131 Till Stensitzki, Yang Yang, Valeri Kozich, Ashour A. Ahmed, Florian Kössl et al. doi:10.1038/nchem.2909 A practical realization of selective IR-driven reaction-rate control has been hampered by competing processes leading to sample heating. Now, the acceleration of a bimolecular ground-state reaction in solution using the IR excitation of a vibration connected to the reaction coordinate is demonstrated. The behaviour is monitored and understood using a combination of femtosecond IR-pump IR-probe spectroscopy and theoretical calculations. See also: News and Views by Case Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors   pp132 - 138 Jiawen Chen, Franco King-Chi Leung, Marc C. A. Stuart, Takashi Kajitani, Takanori Fukushima et al. doi:10.1038/nchem.2887 A centimetre-long string formed by the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor — composed of 95 wt% of water — undergoes muscle-like contraction. Under irradiation, rotary motion at the molecular level is amplified through non-covalent interactions to sustain a fast macroscopic mechanical motion of large amplitude. Chemical compounds An integrated native mass spectrometry and top-down proteomics method that connects sequence to structure and function of macromolecular complexes   pp139 - 148 Huilin Li, Hong Hanh Nguyen, Rachel R. Ogorzalek Loo, Iain D. G. Campuzano and Joseph A. Loo doi:10.1038/nchem.2908 An integrated native mass spectrometry and top-down proteomics method using Fourier transform ion cyclotron resonance has been developed for the characterization of macromolecular protein complexes. This approach directly yields primary to quaternary structural information in a single native top-down experiment. See also: News and Views by Breuker Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption   pp149 - 154 Xueli Zheng, Bo Zhang, Phil De Luna, Yufeng Liang, Riccardo Comin et al. doi:10.1038/nchem.2886 Water oxidation is key to the production of chemical fuels from electricity. Now, guided by theory, NiCoFeP oxyhydroxide catalysts have been developed that require an overpotential lower than that required by IrO2. In situ soft X-ray absorption studies of neutral-pH NiCoFeP catalysts indicate formation of Ni4+, which is favourable for water oxidation.   Programmable autonomous synthesis of single-stranded DNA   pp155 - 164 Jocelyn Y. Kishi, Thomas E. Schaus, Nikhil Gopalkrishnan, Feng Xuan and Peng Yin doi:10.1038/nchem.2872 Primer exchange reaction (PER) cascades have now been used to grow nascent single-stranded DNA with user-specified sequences following prescribed reaction pathways. PER synthesis occurs in a programmable, autonomous, in situ and environmentally responsive fashion, providing a platform for engineering molecular circuits and devices with a wide range of sensing, monitoring, recording, signal processing and actuation capabilities.   Direct α-C–H bond functionalization of unprotected cyclic amines   pp165 - 169 Weijie Chen, Longle Ma, Anirudra Paul and Daniel Seidel doi:10.1038/nchem.2871 Cyclic amines bearing α-substituents are valuable building blocks for drug discovery and natural product synthesis. Introduction of α-substituents via site-selective replacement of C–H bonds is highly attractive but typically limited to protected amine substrates. Now, an operationally simple hydride-transfer-based approach enables the introduction of α-substituents on unprotected amines. Chemical compounds Structure-based inhibitors of tau aggregation   pp170 - 176 P. M. Seidler, D. R. Boyer, J. A. Rodriguez, M. R. Sawaya, D. Cascio et al. doi:10.1038/nchem.2889 Tau aggregation is associated with Alzheimer's disease and dozens of related dementias. Now atomic structures of the aggregation-prone segment VQIINK in repeat 2 of tau have been reported. Inhibitors designed using these structures block seeding by full-length tau better than inhibitors that target the VQIVYK aggregation segment in repeat 3.   Coherent wavepackets in the Fenna–Matthews–Olson complex are robust to excitonic-structure perturbations caused by mutagenesis   pp177 - 183 Margherita Maiuri, Evgeny E. Ostroumov, Rafael G. Saer, Robert E. Blankenship and Gregory D. Scholes doi:10.1038/nchem.2910 Spectroscopists and theorists are closing in on an understanding of the origin of oscillatory features in the spectral response of light-harvesting complexes to femtosecond pulsed excitation. Now, the photosynthetic Fenna–Matthews–Olson complex is probed by femtosecond pump–probe spectroscopy and compared with a series of genetically modified mutants with distinct excitonic interactions, allowing electronic and vibrational contributions to coherence to be distinguished.   DNA-imprinted polymer nanoparticles with monodispersity and prescribed DNA-strand patterns   pp184 - 192 Tuan Trinh, Chenyi Liao, Violeta Toader, Maciej Barlóg, Hassan S. Bazzi et al. doi:10.1038/nchem.2893 DNA–polymer conjugates are attractive materials that combine the programmability of nucleic acid assembly with polymer functionality. Now, through a DNA cube template, monodisperse polymer particles have been imprinted with several DNA strands in pre-designed orientations — each independently set and addressable. The resulting hybrid particles can further assemble into well-defined, non-centrosymmetric structures.   A general approach to intermolecular carbonylation of arene C–H bonds to ketones through catalytic aroyl triflate formation   pp193 - 199 R. Garrison Kinney, Jevgenijs Tjutrins, Gerardo M. Torres, Nina Jiabao Liu, Omkar Kulkarni et al. doi:10.1038/nchem.2903 Catalytic transformations that incorporate carbonyl functional groups in arene C–H bonds have remained limited, despite being attractive synthetic steps. Now, the intermolecular carbonylative coupling of a broad range of simple arenes into ketones has been developed. The reaction occurs through the palladium-catalysed generation of high-energy aroyl triflate electrophiles. Chemical compounds See also: News and Views by Lee & Morandi Oxidase catalysis via aerobically generated hypervalent iodine intermediates   pp200 - 204 Asim Maity, Sung-Min Hyun and David C. Powers doi:10.1038/nchem.2873 Oxidation chemistry is critical to introducing molecular complexity during chemical synthesis. Development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Access to hypervalent iodine compounds — a class of broadly useful chemical oxidants — from O2 increases the scope of aerobic oxidation chemistry that can be achieved. Chemical compounds Decarboxylative alkylation for site-selective bioconjugation of native proteins via oxidation potentials   pp205 - 211 Steven Bloom, Chun Liu, Dominik K. Kölmel, Jennifer X. Qiao, Yong Zhang et al. doi:10.1038/nchem.2888 Selectively targeting native amino acids for late-stage protein modification is a significant challenge, but now it has been shown that photoredox catalysis can be used to specifically target protein C-termini toward decarboxylative-alkylation with Michael acceptors. This technology harnesses innate differences in side-chain oxidation potentials to select between the various functional groups typical among proteins in order to form a single modified product. Chemical compounds Phosphorylation, oligomerization and self-assembly in water under potential prebiotic conditions   pp212 - 217 Clémentine Gibard, Subhendu Bhowmik, Megha Karki, Eun-Kyong Kim and Ramanarayanan Krishnamurthy doi:10.1038/nchem.2878 Phosphorylation of (pre)biological molecules in water has been a long-sought goal in prebiotic chemistry. Now, it has been demonstrated that diamidophosphate phosphorylates nucleosides, amino acids and glycerol/fatty acids in aqueous medium, while simultaneously leading to higher-order structures such as oligonucleotides, peptides and liposomes in the same reaction mixture.   Iridium-catalysed arylation of C–H bonds enabled by oxidatively induced reductive elimination   pp218 - 224 Kwangmin Shin, Yoonsu Park, Mu-Hyun Baik and Sukbok Chang doi:10.1038/nchem.2900 The direct arylation of C–H bonds is an attractive synthetic step, but the reductive elimination of an organometallic catalyst carrying the desired C–H and aryl functionalities has remained challenging. Now, this step has been achieved by first oxidizing the iridium centre of the catalyst, which facilitates the arylation of arene C–H bonds of a range of substrates. Chemical compounds Thermally activated delayed photoluminescence from pyrenyl-functionalized CdSe quantum dots   pp225 - 230 Cédric Mongin, Pavel Moroz, Mikhail Zamkov and Felix N. Castellano doi:10.1038/nchem.2906 The ability to merge the photophysical properties of semiconductor quantum dots with those of well-understood and inexpensive molecular chromophores is important for the development of various emerging photonic and optoelectronic technologies. Now, 1-pyrenecarboxylic acid-functionalized CdSe quantum dots have been shown to undergo thermally activated delayed photoluminescence and display tunable photophysical properties.   A dual role for a polyketide synthase in dynemicin enediyne and anthraquinone biosynthesis   pp231 - 236 Douglas R. Cohen and Craig A. Townsend doi:10.1038/nchem.2876 The anthraquinone and enediyne halves of the antitumor antibiotic dynemicin A were previously thought to be assembled by two separate polyketide synthases (PKS). Now, a single polyketide synthase has been proposed to be responsible for their production, and a working model for their biosynthesis from a common octaketide intermediate has been suggested.   Labelling and determination of the energy in reactive intermediates in solution enabled by energy-dependent reaction selectivity   pp237 - 241 Hiroaki Kurouchi and Daniel A. Singleton doi:10.1038/nchem.2907 Short-lived intermediates in solution may react before undergoing thermal equilibration. This phenomenon is used here to achieve the ‘energy labelling’ of an alkoxy radical. The intermediate's excess energy varies broadly depending on how it is formed and can be determined from the observed reaction selectivity. Chemical compounds Advertisement npj Clean Water: open for submissions    An open access, online-only journal, dedicated to publishing high-quality papers that describe the significant and cutting-edge research that continues to ensure the supply of clean water to populations.   Explore the benefits of submitting your next manuscript:    Corrigendum Top Corrigendum: Structural snapshots of concerted double E-H bond activation at a transition metal centre   p242 Joseph A. B. Abdalla, Alexa Caise, Christian P. Sindlinger, Remi Tirfoin, Amber L. Thompson et al. doi:10.1038/nchem.2922   Erratum Top Erratum: Activate lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution   p242 Alexis Grimaud, Oscar Diaz-Morales, Binghong Han, Wesley T. Hong, Yueh-Lin Lee et al. doi:10.1038/nchem.2932   In Your Element Top The germination of germanium   p244 Shawn C. Burdette and Brett F. Thornton doi:10.1038/nchem.2935 Shawn C. Burdette and Brett F. Thornton explore how germanium developed from a missing element in Mendeleev's periodic table to an enabler for the information age, while retaining a nomenclature oddity.   Top Advertisement Nature Mentoring Collection  Offering advice and support to scientist mentors and their mentees  Access the Collection >>   Natureevents is a fully searchable, multi-disciplinary database designed to maximise exposure for events organisers. The contents of the Natureevents Directory are now live. The digital version is available here. Find the latest scientific conferences, courses, meetings and symposia on natureevents.com. For event advertising opportunities across the Nature Publishing Group portfolio please contact natureevents@nature.com More Nature Events

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