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Thesis

Salt of the Earth pp547 - 548

Bruce C. Gibb

doi:10.1038/nchem.1684

Chemical compounds are often taken for granted, argues Bruce Gibb, and the most underappreciated is one that we're all very familiar with.


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Blogroll

Blogroll: Digital discourse p551

Brandon Findlay

doi:10.1038/nchem.1683


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News and Views

Radiation chemistry: Radical water pp553 - 554

Lars G. M. Pettersson

doi:10.1038/nchem.1686

Radiation of sufficient energy can knock out a tightly bound core-electron from the inner shell of a water molecule, leaving behind a short-lived, highly excited state. Now, through electron spectroscopy and theoretical simulations, these states have been observed to undergo previously unconsidered proton-mediated processes in solution.

See also: Article by Thürmer et al.


Reaction methodology: Speed dating for reactions pp554 - 555

Ian Churcher

doi:10.1038/nchem.1689

A simple method to investigate the functional group compatibility and scope of new reaction methodology could improve the speed with which it is adopted by end-users, and have benefits in many related areas of chemical research.

See also: Article by Collins & Glorius


Single-molecule magnets: Iron lines up pp556 - 557

Eckhard Bill

doi:10.1038/nchem.1687

For more than a decade, single-molecule magnets have relied on multinuclear transition metal clusters and lanthanide compounds. Now, a mononuclear, two-coordinate iron(I) complex has shown that single transition metals can compete with the lanthanides when certain design principles from magnetochemistry are borne in mind.

See also: Article by Zadrozny et al.


Polymer chemistry: Proteins in a pill pp557 - 558

Heather D. Maynard

doi:10.1038/nchem.1691

Protein drugs are important therapies for many different diseases, but very few can be administered orally. Now, a cationic dendronized polymer has been shown to stabilize a therapeutic protein for delivery to the gut.

See also: Article by Fuhrmann et al.


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Perspective

Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron pp559 - 565

K. Cory MacLeod & Patrick L. Holland

doi:10.1038/nchem.1620

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The reduction of N2 by iron and molybdenum complexes is a rapidly moving field. This Perspective discusses the key advances in the past two years. The recent discovery of carbide at the centre of the iron-molybdenum cofactor of nitrogenase is also described, along with the most compelling areas for continued research.

Subject terms: Catalysis | Inorganic chemistry


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Articles

Studying the role of protein dynamics in an SN2 enzyme reaction using free-energy surfaces and solvent coordinates pp566 - 571

Rafael García-Meseguer, Sergio Martí, J. Javier Ruiz-Pernía, Vicent Moliner & Iñaki Tuñón

doi:10.1038/nchem.1660

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The influence of protein motions on the chemical step of enzyme reactions is a contentious issue. Now, by constructing free-energy surfaces using an explicit solvent coordinate, it is shown that, although some structural flexibility is required, protein motions can be described as equilibrium fluctuations.


Initiation of carbon nanotube growth by well-defined carbon nanorings pp572 - 576

Haruka Omachi, Takuya Nakayama, Eri Takahashi, Yasutomo Segawa & Kenichiro Itami

doi:10.1038/nchem.1655

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Carbon nanotubes (CNTs) are typically produced as a mixture of tubes with different diameters and sidewall structures — parameters that determine the optical and electronic properties of these materials. Now, it has been shown that discrete carbon nanorings can be used as templates to control the bottom-up growth of CNTs with a narrow distribution of diameters.


Magnetic blocking in a linear iron(I) complex pp577 - 581

Joseph M. Zadrozny, Dianne J. Xiao, Mihail Atanasov, Gary J. Long, Fernande Grandjean, Frank Neese & Jeffrey R. Long

doi:10.1038/nchem.1630

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Mononuclear complexes of certain lanthanide ions are known to have large magnetization reversal barriers caused by strong spin–orbit coupling. Now, careful tuning of the ligand field of a transition metal complex has engendered a comparable spin-reversal barrier — and in turn magnetic blocking at 4.5 K.

Subject term: Inorganic chemistry

See also: News and Views by Bill


Sustained gastrointestinal activity of dendronized polymer–enzyme conjugates pp582 - 589

Gregor Fuhrmann, Andrea Grotzky, Ružica Lukić, Simon Matoori, Paola Luciani, Hao Yu, Baozhong Zhang, Peter Walde, A. Dieter Schlüter, Marc A. Gauthier & Jean-Christophe Leroux

doi:10.1038/nchem.1675

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Methods for stabilizing enzymatic activity in the gastrointestinal tract are rarely investigated because of the difficulty in protecting proteins from an environment that promotes their digestion. Now, functionally diverse polymers have been conjugated to therapeutic enzymes, which lead to a substantial enhancement of their in vivo activity in the gastrointestinal tract.

See also: News and Views by Maynard


On the nature and origin of dicationic, charge-separated species formed in liquid water on X-ray irradiation pp590 - 596

Stephan Thürmer, Milan Ončák, Niklas Ottosson, Robert Seidel, Uwe Hergenhahn, Stephen E. Bradforth, Petr Slavíček & Bernd Winter

doi:10.1038/nchem.1680

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Previously unobserved types of reactive species formed on the core ionization of liquid water have been identified using a combination of liquid microjet photoemission spectroscopy and ab initio calculations. The charge-separated di-cationic species are formed within a few femtoseconds, through proton-transfer-mediated processes followed by autoionization.

See also: News and Views by Pettersson


A robustness screen for the rapid assessment of chemical reactions pp597 - 601

Karl D. Collins & Frank Glorius

doi:10.1038/nchem.1669

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For researchers to rapidly adopt new synthetic methodology, they need to gauge whether the reaction will work for their substrate — a point not easily conveyed by traditional screens of reaction scope. Here, a simple method is described to assess the likely scope and limitations of a chemical reaction beyond the idealized conditions initially reported.

See also: News and Views by Churcher


Direct probe of spectral inhomogeneity reveals synthetic tunability of single-nanocrystal spectral linewidths pp602 - 606

Jian Cui, Andrew P. Beyler, Lisa F. Marshall, Ou Chen, Daniel K. Harris, Darcy D. Wanger, Xavier Brokmann & Moungi G. Bawendi

doi:10.1038/nchem.1654

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The average single-nanocrystal spectral linewidth within an ensemble of nanocrystal emitters in solution can be directly and quantitatively measured using photon-correlation Fourier spectroscopy (S-PCFS). Variations in single-nanocrystal linewidths between batches are found to be significant and synthetically tunable, introducing new avenues for the optimization of nanocrystals for optical applications.


Stereoretentive Pd-catalysed Stille cross-coupling reactions of secondary alkyl azastannatranes and aryl halides pp607 - 612

Ling Li, Chao-Yuan Wang, Rongcai Huang & Mark R. Biscoe

doi:10.1038/nchem.1652

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A general method for the stereoretentive Pd-catalysed cross-coupling of secondary alkyl azastannatranes and aryl electrophiles is described. This work constitutes the first example of a stereoretentive cross-coupling reaction using an unactivated, isolable, optically active organometallic nucleophile.

Subject terms: Organic chemistry | Synthesis


Biomolecular robotics for chemomechanically driven guest delivery fuelled by intracellular ATP pp613 - 620

Shuvendu Biswas, Kazushi Kinbara, Tatsuya Niwa, Hideki Taguchi, Noriyuki Ishii, Sumiyo Watanabe, Kanjiro Miyata, Kazunori Kataoka & Takuzo Aida

doi:10.1038/nchem.1681

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A tubular assembly based on barrel-shaped chaperonin protein mutants, held together through coordination to magnesium ions, has been devised that carries and delivers guests into cells. The hydrolysis of ATP — present in much higher concentration inside the cell than outside — induces a conformational change in chaperonin that in turn triggers the guest release.


Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface pp621 - 627

Duncan den Boer, Min Li, Thomas Habets, Patrizia Iavicoli, Alan E. Rowan, Roeland J. M. Nolte, Sylvia Speller, David B. Amabilino, Steven De Feyter & Johannes A. A. W. Elemans

doi:10.1038/nchem.1667

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A scanning tunnelling microscope has been used to image multistep chemical reactions at a solid/liquid interface with single-molecule resolution. On reacting Mn(III) porphyrins with either O2 or a single oxygen donor, at least four distinct reaction intermediates and products were detected and their interconversion could be observed in real space and real time.


A family of zeolites with controlled pore size prepared using a top-down method pp628 - 633

Wieslaw J. Roth, Petr Nachtigall, Russell E. Morris, Paul S. Wheatley, Valerie R. Seymour, Sharon E. Ashbrook, Pavla Chlubná, Lukáš Grajciar, Miroslav Položij, Arnošt Zukal, Oleksiy Shvets & Jiří Čejka

doi:10.1038/nchem.1662

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The disassembly of a parent zeolite and its reassembly into two zeolites with targeted topologies is described. This process demonstrates that it is possible to target specific ring sizes in a zeolite by replacing one size of unit in the structure with alternative units of a different size.


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Corrigenda

Enantioselective preparation and chemoselective cross-coupling of 1,1-diboron compounds p634

Jack Chang Hung Lee, Robert McDonald & Dennis G. Hall

doi:10.1038/nchem.1679


Simultaneous structure–activity studies and arming of natural products by C–H amination reveal cellular targets of eupalmerin acetate p634

Jing Li, Justin S. Cisar, Cong-Ying Zhou, Brunilda Vera, Howard Williams, Abimael D. Rodríguez, Benjamin F. Cravatt & Daniel Romo

doi:10.1038/nchem.1685


Competition between model protocells driven by an encapsulated catalyst p634

Katarzyna Adamala & Jack W. Szostak

doi:10.1038/nchem.1700


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In Your Element

One flerovium atom at a time p636

Peter Schwerdtfeger

doi:10.1038/nchem.1688

The chemistry of element 114 seems to be in reach, yet Peter Schwerdtfeger cautions that we should expect the unexpected from this young element, which is so different to its lighter counterparts.


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