Thursday, August 23, 2012

Nature Chemistry Contents September 2012 Volume 4 Number 9 pp687-764

Nature Chemistry

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TABLE OF CONTENTS

September 2012 Volume 4, Issue 9

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

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Thesis

Top

Homemade chemists   p687
Michelle Francl
doi:10.1038/nchem.1441
Michelle Francl wonders if home labs make (better) chemists.

Research Highlights

Top

Molecular machines: Intracrystalline inflation | Cluster chemistry: Filling in the blanks | 'On water' chemistry: Interfacial understanding | Polymer chemistry: Alive with light


Blogroll

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Blogroll: But is it art?   p691
See Arr Oh
doi:10.1038/nchem.1440

News and Views

Top

Medicinal chemistry: Forcing an enemy into the open   pp692 - 693
Christian Melander and David M. Margolis
doi:10.1038/nchem.1444
A series of highly active, simplified analogues of the natural product bryostatin have been prepared. They offer an improved approach for the activation of latent HIV that could, in combination with current state-of-the-art antiretroviral therapy, offer hope for eventual eradication of the infection.

See also: Article by DeChristopher et al.

Protein NMR spectroscopy: Hydrogen bonds under pressure   pp693 - 695
Gerd Nielsen and Harald Schwalbe
doi:10.1038/nchem.1443
Hydrogen bonds play a key role in defining the folding of proteins and the maintenance of their structure. A high-pressure NMR study of ubiquitin now provides unprecedented detail on the temperature and pressure dependence of its hydrogen-bond network.

See also: Article by Nisius & Grzesiek

Molecular switches: Hydrazones double down on zinc   pp695 - 696
Shawn C. Burdette
doi:10.1038/nchem.1438
Molecular engineers have long relied on a single light-driven event or chemical input to induce structural changes in switching systems. By carefully designing two hydrazone-based switches, it has now been shown that a single metal-binding event can trigger a signalling cascade that results in the isomerization of two different molecules.

See also: Article by Ray et al.

Carbohydrate recognition: A minimalistic approach to binding   pp697 - 698
Stefan Kubik
doi:10.1038/nchem.1428
Synthetic receptors with properties resembling those of carbohydrate-binding proteins are known, but they are structurally rather complex. Elaborate structures are, however, not always required to bind carbohydrates in water — much simpler compounds can be just as effective.

See also: Article by Ke et al.

Chemistry
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Perspective

Top

Design strategies for organic semiconductors beyond the molecular formula   pp699 - 704
Zachary B. Henson, Klaus Müllen and Guillermo C. Bazan
doi:10.1038/nchem.1422



Although the molecular formula gives valuable information on the properties of isolated molecules or conjugated polymers, it fails to accurately predict their collective behaviour in the solid state. This Perspective highlights the importance of organization across multiple length scales on the optical and electronic properties of organic semiconductors, and how device performances poorly reflect the capabilities of a given material.

Articles

Top

Designed, synthetically accessible bryostatin analogues potently induce activation of latent HIV reservoirs in vitro    pp705 - 710
Brian A. DeChristopher, Brian A. Loy, Matthew D. Marsden, Adam J. Schrier, Jerome A. Zack and Paul A. Wender
doi:10.1038/nchem.1395



Simplified bryostatin analogues are shown to potently induce latent HIV expression in vitro. These analogues display comparable or better potency when compared with bryostatin. Moreover, they are up to 1,000-fold more potent in inducing latent HIV expression than prostratin, the current lead preclinical candidate.
Chemical compounds
See also: News and Views by Melander & Margolis

Key stabilizing elements of protein structure identified through pressure and temperature perturbation of its hydrogen bond network   pp711 - 717
Lydia Nisius and Stephan Grzesiek
doi:10.1038/nchem.1396



The pressure- and temperature-dependent changes of various hydrogen bonds within ubiquitin have been determined at very high resolution using NMR H-bond scalar couplings. The measured perturbations show a correlation with the sequence separation between donor and acceptor residues, and indicate that certain topologically crucial H-bonds are specifically stabilized.

See also: News and Views by Nielsen & Schwalbe

A simple and accessible synthetic lectin for glucose recognition and sensing   pp718 - 723
Chenfeng Ke, Harry Destecroix, Matthew P. Crump and Anthony P. Davis
doi:10.1038/nchem.1409



Selective carbohydrate binding is a difficult task, usually accomplished by proteins (lectins) or complex synthetic analogues. It has now been achieved by a remarkably simple compound, accessible in just five steps from commercially available materials. This new receptor is highly selective for all-equatorial carbohydrates, and may be used to sense glucose through changes in anthracene fluorescence.
Chemical compounds
See also: News and Views by Kubik

Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography   pp724 - 732
Qing Hua Wang, Zhong Jin, Ki Kang Kim, Andrew J. Hilmer, Geraldine L. C. Paulus, Chih-Jen Shih, Moon-Ho Ham, Javier D. Sanchez-Yamagishi, Kenji Watanabe, Takashi Taniguchi, Jing Kong, Pablo Jarillo-Herrero and Michael S. Strano
doi:10.1038/nchem.1421



The chemical modification of graphene is important for its use in many applications. Now it is shown that the reactivity of graphene towards covalent modification varies widely depending on its underlying support substrate, and that the substrate can be patterned to induce spatial control of chemical reactions in graphene.

Highly enantioselective trapping of zwitterionic intermediates by imines   pp733 - 738
Huang Qiu, Ming Li, Li-Qin Jiang, Feng-Ping Lv, Li Zan, Chang-Wei Zhai, Michael P. Doyle and Wen-Hao Hu
doi:10.1038/nchem.1406



Reactions with unstable and highly reactive zwitterionic intermediates generated in transition-metal-catalysed processes provide new opportunities for molecular constructions. Here imines, activated by chiral organocatalysts, have been employed to trap the zwitterionic intermediates to give polyfunctionalized indole and oxindole derivatives in a single step with excellent diastereoselectivity and enantioselectivity.
Chemical compounds

In situ surface coverage analysis of RuO2-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis   pp739 - 745
Detre Teschner, Gerard Novell-Leruth, Ramzi Farra, Axel Knop-Gericke, Robert Schlögl, László Szentmiklósi, Miguel González Hevia, Hary Soerijanto, Reinhard Schomäcker, Javier Pérez-Ramírez and Núria López
doi:10.1038/nchem.1411



In heterogeneous catalytic processes the Arrhenius parameters are often found to be interrelated (compensation phenomenon). Using state-of-the-art experiments and density functional theory, the origin of compensation is studied. A similar dependence on the rate-limiting surface-coverage term is found for both apparent activation energy and prefactor terms, which can be translated into surface configurational entropy contributions.

A quantitative model for the transcription of 2D patterns into functional 3D architectures   pp746 - 750
Edvinas Orentas, Marco Lista, Nai-Ti Lin, Naomi Sakai and Stefan Matile
doi:10.1038/nchem.1429



The self-sorting of molecular building blocks should allow 2D surface patterns to be transcribed into 3D functional materials. Here, a non-empirical approach to the templated synthesis of supramolecular architectures on surfaces is reported, starting with a theoretical model and followed by comprehensive experimental validation, including direct evidence for functional relevance of the produced materials.
Chemical compounds

Anion-induced reconstitution of a self-assembling system to express a chloride-binding Co10L15 pentagonal prism   pp751 - 756
Imogen A. Riddell, Maarten M. J. Smulders, Jack K. Clegg, Yana R. Hristova, Boris Breiner, John D. Thoburn and Jonathan R. Nitschke
doi:10.1038/nchem.1407



A coordination cage has been prepared that self-assembles through second-order templation. Peripheral perchlorate or hexafluorophosphate template anions direct the formation of a hollow prism whose central pocket was able to bind a small anionic guest such as halide or azide, in a manner reminiscent to signal transduction in biological systems.

A switching cascade of hydrazone-based rotary switches through coordination-coupled proton relays   pp757 - 762
Debdas Ray, Justin T. Foy, Russell P. Hughes and Ivan Aprahamian
doi:10.1038/nchem.1408



Metal cations play an important role in biological proton relays by modulating the pKa values of surrounding amino acids. This effect has now been used to induce the isomerization of two hydrazone switches using a single input. It is found that a combination of electrostatic repulsion and conformational changes are required for the proton relay to take place.
Chemical compounds
See also: News and Views by Burdette

In Your Element

Top

Reactions coupled to palladium   p764
Matthew Hartings
doi:10.1038/nchem.1437
You would be forgiven if you thought the most important element in an organic transformation was carbon. Matthew Hartings argues that, for just over half a century in many of chemistry's most renowned organic reactions, it has actually been palladium.

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