Nature Chemistry Contents March 2018 Volume 10 Number 3 pp 245 - 372

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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! TABLE OF CONTENTS March 2018 Volume 10, Issue 3 News and Views Correction Articles In Your Element   Advertisement Live Webinar on Life Science Applications in UV/VIS Spectroscopy   Join METTLER TOLEDO's Live Webinar with Nature on Life Science Applications in UV/VIS Spectroscopy. The webinar reviews the most relevant applications that can be performed with a UV/VIS spectrophotometer with the focus on the life science market. Typical samples and applications will be highlighted with many tips and hints for optimizing measurement accuracy.   Register Now!    Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Nature Catalysis is an online-only journal that publishes research, review and comment across all areas of catalysis.  EXPLORE THE LATEST ISSUE >>    Advertisement npj Materials Degradation is a new open access journal that is now open for submissions. The journal publishes the finest content describing basic and applied research discoveries in the area of corrosion (degradation) and protection of materials.   Sign up for article e-alerts >>>   News and Views Top Biosynthesis: Reprogramming assembly lines   pp245 - 247 Binuraj R. K. Menon and Matthew Jenner doi:10.1038/nchem.2941 Rational engineering of biosynthetic assembly lines for production of new compounds is an attractive prospect, yet it presents many challenges. Learning from biology, some of the rules for expanding the chemical diversity of non-ribosomal peptides have been uncovered in two recent studies. See also: Article by Bozhüyük et al. | Article by Niquille et al. Uranium electrocatalysis: The secret is in the ring   pp247 - 249 Marinella Mazzanti doi:10.1038/nchem.2940 An arene-anchored uranium complex has recently been shown to serve as efficient electrocatalyst for the conversion of water into dihydrogen. Now, the crucial role of the arene moiety in enabling catalytic activity — unusual for uranium — has been explored, providing important insight for the design of improved electrocatalysts. See also: Article by Halter et al. Chemistry JOBS of the week Dean of the Faculty of Science The Chinese University of Hong Kong Generalist at D. E. Shaw Research D. E. Shaw Research Full Professor - Murray Goodman Endowed Chair University of California, San Diego Max Planck Director The Max Planck Society and the Max Planck Institutes PhD Program Ecole Polytechnique More Science jobs from Chemistry EVENT The 4th Int'l Conference on Organic Chemistry (COC 2018) 14.07.18 Kunming, China More science events from Correction Top Correction   p249 doi:10.1038/nchem.2939   Articles Top Engineered modular biomaterial logic gates for environmentally triggered therapeutic delivery   pp251 - 258 Barry A. Badeau, Michael P. Comerford, Christopher K. Arakawa, Jared A. Shadish and Cole A. DeForest doi:10.1038/nchem.2917 Biomaterials that respond to precise combinations of environmental cues represent an important technology for tissue engineering and next-generation drug delivery systems. Now, a modular framework to programme material degradation following Boolean logic has been demonstrated by specifying the molecular architecture and connectivity of orthogonal stimuli-labile moieties within hydrogel cross-linkers.   The role of uranium–arene bonding in H2O reduction catalysis   pp259 - 267 Dominik P. Halter, Frank W. Heinemann, Laurent Maron and Karsten Meyer doi:10.1038/nchem.2899 An arene-anchored uranium(III) complex that facilitates the electrocatalytic formation of H2 from H2O has now been shown to involve redox-cooperativity between the uranium centre and its covalently bound mesitylene ligand. The oxidative addition of H2O to the uranium catalyst is a concerted two-electron reaction — atypical for f-block metals. Chemical compounds See also: News and Views by Mazzanti Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies   pp268 - 274 Gaurav Kumar, Luke Tibbitts, Jaclyn Newell, Basu Panthi, Ahana Mukhopadhyay et al. doi:10.1038/nchem.2911 Understanding how a supporting material can change the surface chemistry of the nanoparticle catalysts that it hosts is critical to tuning catalytic properties. Experimental Hammett studies and density functional theory calculations show that differences in reactivity can be attributed to differences in the electron density at metal active sites, which arises from differences in electron donation from the support.   De novo design and engineering of non-ribosomal peptide synthetases   pp275 - 281 Kenan A. J. Bozhüyük, Florian Fleischhacker, Annabell Linck, Frank Wesche, Andreas Tietze et al. doi:10.1038/nchem.2890 Peptides derived from non-ribosomal peptide synthetases (NRPS) are an important class of pharmaceutically relevant drugs. However, no general rules for the modification of NRPS or the generation of artificial NRPS are known. Now, a new strategy for the modification of NRPS has been developed that uses defined exchange units that are fused at specific positions connecting the condensation and adenylation domains. See also: News and Views by Menon & Jenner Nonribosomal biosynthesis of backbone-modified peptides   pp282 - 287 David L. Niquille, Douglas A. Hansen, Takahiro Mori, David Fercher, Hajo Kries et al. doi:10.1038/nchem.2891 Nonribosomal peptide synthetases (NRPSs) produce vital natural products but have proven recalcitrant to biosynthetic engineering. Now, a combination of yeast surface display and fluorescence-activated cell sorting (FACS) has been used to reprogram an L-Phe-incorporating module for ?-Phe. The resulting module is highly selective and functions efficiently in NRPS pathways. See also: News and Views by Menon & Jenner Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2   pp288 - 295 Urmimala Maitra, Robert A. House, James W. Somerville, Nuria Tapia-Ruiz, Juan G. Lozano et al. doi:10.1038/nchem.2923 Alkali-metal-rich compositions (for example, Li[LixM1–x]O2) are promising battery cathode materials that exhibit oxygen redox, which provides additional charge capacity. It is thought to occur in compounds containing alkali ions in the transition metal layers and featuring Li+–O(2p)–Li+ interactions; however, now it is observed in Na2/3[Mg0.28Mn0.72]O2, in which Mg2+ ions are present in the transition metal layer.   Complex supramolecular interfacial tessellation through convergent multi-step reaction of a dissymmetric simple organic precursor   pp296 - 304 Yi-Qi Zhang, Mateusz Paszkiewicz, Ping Du, Liding Zhang, Tao Lin et al. doi:10.1038/nchem.2924 Complex interfacial supramolecular architectures promise unique physical and chemical properties, but are challenging to make. Now, it has been shown that a simple organic precursor can undergo a convergent multi-step on-surface transformation to give more complex building blocks that assemble into a semi-regular Archimedean tessellation with long-range order. Chemical compounds Endothermic singlet fission is hindered by excimer formation   pp305 - 310 Cameron B. Dover, Joseph K. Gallaher, Laszlo Frazer, Patrick C. Tapping, Anthony J. Petty, II et al. doi:10.1038/nchem.2926 Singlet fission may one day allow solar cells to produce two excited electrons with one photon. Now, by comparison of the time-resolved photoluminescence and sensitized triplet–triplet annihilation of a tetracene derivative, it has been shown that—contrary to previous reports—the excimer state is a trap, and not a necessary intermediate for singlet fission.   Substrate-driven chemotactic assembly in an enzyme cascade   pp311 - 317 Xi Zhao, Henri Palacci, Vinita Yadav, Michelle M. Spiering, Michael K. Gilson et al. doi:10.1038/nchem.2905 Enzymes that form a metabolic pathway in which the product of one enzyme is the substrate for the next have now been shown to associate through a process of sequential, directed chemotactic movement. The extent of enzyme migration is proportional to the exposure time to the substrate gradient.   Evolving artificial metalloenzymes via random mutagenesis   pp318 - 324 Hao Yang, Alan M. Swartz, Hyun June Park, Poonam Srivastava, Ken Ellis-Guardiola et al. doi:10.1038/nchem.2927 Proteins have the potential to serve as powerful scaffolds that control the catalytic activity and selectivity of organometallic centres; however, new methods are needed to optimize artificial metalloenzymes. Now, an efficient approach for evolving the activity and selectivity of artificial metalloenzymes has been demonstrated using dirhodium cyclopropanases. This approach does not require structural or mechanistic data to guide mutagenesis.   Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation   pp325 - 332 Matthew D. Marcinkowski, Matthew T. Darby, Jilei Liu, Joshua M. Wimble, Felicia R. Lucci et al. doi:10.1038/nchem.2915 A renewed interest in C–H bond activation has developed on account of the recent increased availability of shale gas. Now, using a combination of surface science, microscopy, theory and nanoparticle studies, the ability of coke-resistant Pt/Cu single-atom alloys to efficiently activate C–H bonds in alkanes has been demonstrated under realistic catalytic conditions.   Palladium-catalysed anti-Markovnikov selective oxidative amination   pp333 - 340 Daniel G. Kohler, Samuel N. Gockel, Jennifer L. Kennemur, Peter J. Waller and Kami L. Hull doi:10.1038/nchem.2904 Aminopalladation is a key step in a number of carbon–nitrogen bond-forming processes, but carrying out this step with intermolecular anti-Markovnikov selectivity has remained difficult. Such a process has now been developed by using an anionic palladium catalyst to generate terminal carbon–nitrogen bonds from alkenes. Chemical compounds Ultrafast dynamics of low-energy electron attachment via a non-valence correlation-bound state   pp341 - 346 Joshua P. Rogers, Cate S. Anstöter and Jan R. R. Verlet doi:10.1038/nchem.2912 The capture of an electron by a molecule represents one of the most fundamental chemical transformations, but its mechanism at very low energies remains unclear. Now, it is shown that low-energy electron attachment to hexafluorobenzene is mediated by a non-valence correlation-bound state of the anion.   Asymmetric transfer hydrogenation by synthetic catalysts in cancer cells   pp347 - 354 James P. C. Coverdale, Isolda Romero-Canelón, Carlos Sanchez-Cano, Guy J. Clarkson, Abraha Habtemariam et al. doi:10.1038/nchem.2918 Intracellular asymmetric transfer hydrogenation catalysis using Os(II) complexes has now been demonstrated and offers a new approach for selectively killing cancer cells. Enantiomers of Os(II) arene catalysts can penetrate cell membranes enabling the reduction of pyruvate to D- or L-lactate using formate as a hydride source, with high enantioselectivity. Chemical compounds Transferring the entatic-state principle to copper photochemistry   pp355 - 362 B. Dicke, A. Hoffmann, J. Stanek, M. S. Rampp, B. Grimm-Lebsanft et al. doi:10.1038/nchem.2916 According to the entatic-state principle, distortions of the coordination geometry of a reacting compound can optimize the energies of starting and final states to improve reaction rates. Here, the entatic-state principle is observed to apply to photoactive copper complexes that have a constrained ligand geometry, resulting in very short charge-transfer state lifetimes.   Direct observation of the influence of cardiolipin and antibiotics on lipid II binding to MurJ   pp363 - 371 Jani Reddy Bolla, Joshua B. Sauer, Di Wu, Shahid Mehmood, Timothy M. Allison et al. doi:10.1038/nchem.2919 Most steps in peptidoglycan biosynthesis are understood, but the lipid II binding properties to the flippases MurJ and FtsW remain unknown. Now, it has been shown that lipid II exhibits preferential binding to MurJ, which is modulated by ramoplanin and cardiolipins. These insights into the lipid II binding determinants suggest roles for lipids in regulating substrate binding.   Advertisement A new open access, multi-and interdisciplinary journal dedicated to publishing the finest research on both microbial biofilms and microbiomes, the journal is now open for submissions.   Explore the benefits of submitting your next research article.   In Your Element Top Rounding up lutetium   p372 Lars Ohrstrom doi:10.1038/nchem.2938 Lars Ohrstrom suspects that as time goes by, we may see more of lutetium — the last of the lanthanoids.   Top 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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