Thursday, June 20, 2013

Nature Chemistry Contents July 2013 Volume 5 Number 7 pp547-636

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TABLE OF CONTENTS

July 2013 Volume 5, Issue 7

Thesis
Research Highlights
Blogroll
News and Views
Perspective
Articles
Corrigenda
In Your Element

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Thesis

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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.

Research Highlights

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Atmospheric chemistry: Catalysis in the clouds | Cellular imaging: Buckets of binding | Polymer chemistry: Spotlight on synthesis | Pyroelectricity: Surface effects


Blogroll

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Blogroll: Digital discourse   p551
Brandon Findlay
doi:10.1038/nchem.1683

News and Views

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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

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Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron   pp559 - 565
K. Cory MacLeod and Patrick L. Holland
doi:10.1038/nchem.1620



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.

Articles

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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 and Iñaki Tuñón
doi:10.1038/nchem.1660



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 and Kenichiro Itami
doi:10.1038/nchem.1655



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 and Fernande Grandjean et al.
doi:10.1038/nchem.1630



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.
Chemical compounds
See also: News and Views by Bill

Sustained gastrointestinal activity of dendronized polymer–enzyme conjugates   pp582 - 589
Gregor Fuhrmann, Andrea Grotzky, Ružica Lukic, Simon Matoori and Paola Luciani et al.
doi:10.1038/nchem.1675



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 OnĨák, Niklas Ottosson, Robert Seidel and Uwe Hergenhahn et al.
doi:10.1038/nchem.1680



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 dicationic 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 and Frank Glorius
doi:10.1038/nchem.1669



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.
Chemical compounds
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 and Daniel K. Harris et al.
doi:10.1038/nchem.1654



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 and Mark R. Biscoe
doi:10.1038/nchem.1652



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.
Chemical compounds

Biomolecular robotics for chemomechanically driven guest delivery fuelled by intracellular ATP    pp613 - 620
Shuvendu Biswas, Kazushi Kinbara, Tatsuya Niwa, Hideki Taguchi and Noriyuki Ishii et al.
doi:10.1038/nchem.1681



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 and Alan E. Rowan et al.
doi:10.1038/nchem.1667



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 and Valerie R. Seymour et al.
doi:10.1038/nchem.1662



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.

Corrigenda

Top

Enantioselective preparation and chemoselective cross-coupling of 1,1-diboron compounds   p634
Jack Chang Hung Lee, Robert McDonald and 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 and Howard Williams et al.
doi:10.1038/nchem.1685

Competition between model protocells driven by an encapsulated catalyst   p634
Katarzyna Adamala and Jack W. Szostak
doi:10.1038/nchem.1700

In Your Element

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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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