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| |  | TABLE OF CONTENTS
| April 2012 Volume 4, Issue 4 |  | | |  |  Thesis
Books and Arts
Interview
Research Highlights
Blogroll
News and Views
Review
Articles
In Your Element
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| | | | Thesis |  Top | |  | | Chemical intuition or chemical institution? pp237 - 238
Bruce C. Gibb
doi:10.1038/nchem.1307
The e.e.s have had it, argues Bruce Gibb, and it's time to err on the side of e.r.
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| | Books and Arts | Top | | | | The valiant interrogator p239
David Kroll reviews The Quest for the Cure: The Science and Stories Behind the Next Generation of Medicines by Brent R. Stockwell
doi:10.1038/nchem.1316
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| | Interview | Top | | | | A chronicler of chemistry pp240 - 241
doi:10.1038/nchem.1306
Thomas Hager, author of popular science books that revisit some of the most significant developments in chemistry over the past century, talks to Nature Chemistry about the challenges of writing for a general audience, and how his dislike of chemistry was turned around by a fellow Oregonian of considerable repute.
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| | Research Highlights | Top | | | | Self-healing materials: Re-discovered repair | Supramolecular chemistry: Microfluidics for microcapsules | Asymmetric catalysis: React then repeat | Odour detection: Smelling sulfur | Hydrogen-evolution catalysts: Molybdenum mimic
| Blogroll | Top | | | | Blogroll: Scary chemicals p243
doi:10.1038/nchem.1324
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| | News and Views | Top | | | | Two-dimensional materials: Polymers stripped down pp244 - 245
Fernando J. Uribe-Romo and William R. Dichtel
doi:10.1038/nchem.1317
Two-dimensional polymers can serve to organize chemical functionality periodically over large areas, but their rational synthesis has remained limited. Now, a free-standing, single-layer polymer sheet has been prepared and isolated through a two-step procedure — a photochemical reaction within a layered organic crystal followed by exfoliation.
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See also: Article by Kissel et al.
| | | | Ion dynamics: Wired-up water pp245 - 247
David Chandler, Christoph Dellago and Phillip Geissler
doi:10.1038/nchem.1300
The splitting of water molecules into protons and hydroxide ions, and their recombination, occurs by proton transfer along hydrogen-bond wires. Now, first principle simulations of the recombination reaction reveal new atomic-scale details of the process showing that compression of the wire plays an important role.
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| | | | Polymer vesicles: Autonomous propulsion pp247 - 248
Jonathan Howse
doi:10.1038/nchem.1318
Polymer vesicles have been constructed that entrap platinum nanoparticles in their outer surface. These serve to break down a fuel of hydrogen peroxide, generating water and oxygen and in turn inducing a propulsive effect.
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See also: Article by Wilson et al.
| | | | Protein labelling: Playing tag with proteins pp248 - 250
Dante W. Romanini and Virginia W. Cornish
doi:10.1038/nchem.1325
Fluorescent labels can now be attached to a specific protein on the surface of live cells using a two-step method that reacts a norbornene — introduced using genetic encoding — with a variety of dyes.
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See also: Article by Lang et al.
| | | | Zeolite nanosystems: Imagination has no limits pp250 - 251
Javier Pérez-Ramírez
doi:10.1038/nchem.1310
The technological relevance of zeolites, the desire to improve their efficiency and the inexhaustible synthetic options to tailor their properties have triggered a permanent evolution of this superclass of materials. Two zeolite nanosystems prepared by distinct approaches reflect this and offer hope for new applications.
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| | | | Transparent conducting materials: Flexibility with a metallic skin pp252 - 253
Hideo Hosono
doi:10.1038/nchem.1312
Transparent, metallic conducting thin films are key for applications such as flatpanel displays and solar cells, and heavily electron-doped ionic oxide materials have been intensively studied for this purpose. A class of conductors that are transparent in the near-infrared region has now been developed using a topological insulator.
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See also: Article by Peng et al.
| | | | Catalysis: Temporary intramolecularity pp253 - 254
Kian L. Tan
doi:10.1038/nchem.1308
A simple aldehyde has been shown to catalyse an intermolecular hydroamination, not by activating either reaction partner, but simply by bringing them into close proximity.
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| | Review | Top | | | | Electron-transfer processes in dendrimers and their implication in biology, catalysis, sensing and nanotechnology pp255 - 267
Didier Astruc
doi:10.1038/nchem.1304
Redox sites can be incorporated within dendrimers — highly branched, well-defined macromolecules — at specific locations, such as their core, branching points, periphery or inner cavities. These dendrimers can serve to functionalize surfaces, and electron-transfer processes at their redox sites show promise for various applications ranging from metallo-protein modelling to sensing to catalysis.
Abstract | Full Text | PDF
| | Articles | Top | | | | Autonomous movement of platinum-loaded stomatocytes pp268 - 274
Daniela A. Wilson, Roeland J. M. Nolte and Jan C. M. van Hest
doi:10.1038/nchem.1281
A supramolecular system has been assembled that moves autonomously in the presence of a molecular fuel. Platinum nanoparticles entrapped in a polymer stomatocyte — a bowl-shaped polymer vesicle — catalyse the decomposition of the molecular fuel, hydrogen peroxide. The resulting generation of water and oxygen induces a directional movement of the stomatocyte.
Abstract | Full Text | PDF
See also: News and Views by Howse
| | | | Diamidocarbenes as versatile and reversible [2 + 1] cycloaddition reagents pp275 - 280
Jonathan P. Moerdyk and Christopher W. Bielawski
doi:10.1038/nchem.1267
An isolable diamidocarbene is shown to participate in reversible [2+1] cycloadditions with a variety of both electron-deficient and electron-rich olefins and aldehydes. Subsequent hydrolysis of a N,N′-diamidocyclopropane derived from styrene afforded the corresponding linear carboxylic acid, effectively establishing a metal- and carbon monoxide-free, anti-Markovnikov olefin hydrocarboxylation reaction.
Abstract | Full Text | PDF | Chemical compounds
| | | | Topological insulator nanostructures for near-infrared transparent flexible electrodes pp281 - 286
Hailin Peng, Wenhui Dang, Jie Cao, Yulin Chen, Di Wu, Wenshan Zheng, Hui Li, Zhi-Xun Shen and Zhongfan Liu
doi:10.1038/nchem.1277
Transparent conductive electrodes are widely used in modern optoelectronic devices, but they are rarely transparent in the near-infrared, limiting their use. Nanostructured bismuth selenide, a topological insulator, is now shown to be a flexible near-infrared transparent electrode.
Abstract | Full Text | PDF
See also: News and Views by Hosono
| | | | A two-dimensional polymer prepared by organic synthesis pp287 - 291
Patrick Kissel, Rolf Erni, W. Bernd Schweizer, Marta D. Rossell, Benjamin T. King, Thomas Bauer, Stephan Götzinger, A. Dieter Schlüter and Junji Sakamoto
doi:10.1038/nchem.1265
A two-dimensional polymer with internal periodicity has now been constructed. The procedure involves the rational molecular design of monomers, which first crystallize into a laminar lattice. A photo-induced polymerization then occurs laterally within each layer, and the resulting polymer crystals are subsequently delaminated into individual, free-standing two-dimensional polymers.
Abstract | Full Text | PDF | Chemical compounds
See also: News and Views by Uribe-Romo & Dichtel
| | | | Evidence that a ‘dynamic knockout’ in Escherichia coli dihydrofolate reductase does not affect the chemical step of catalysis pp292 - 297
E. Joel Loveridge, Enas M. Behiry, Jiannan Guo and Rudolf K. Allemann
doi:10.1038/nchem.1296
The connection between protein dynamics and catalysis is an issue of vigorous debate in enzymology. Conformational motions are known to be important for the physical steps in the catalytic cycle of dihydrofolate reductase, however, it is now reported that there is no evidence of a correlation between such motions and the actual chemical step, hydride transfer.
Abstract | Full Text | PDF
| | | | Genetically encoded norbornene directs site-specific cellular protein labelling via a rapid bioorthogonal reaction pp298 - 304
Kathrin Lang, Lloyd Davis, Jessica Torres-Kolbus, Chungjung Chou, Alexander Deiters and Jason W. Chin
doi:10.1038/nchem.1250
The site-specific incorporation of a norbornene amino acid into proteins via genetic code expansion, together with the synthesis of a series of tetrazine-based probes that exhibit turn-on fluorescence on their fast cycloaddition with norbornene, enables rapid protein labelling on mammalian cells.
Abstract | Full Text | PDF | Chemical compounds
See also: News and Views by Romanini & Cornish
| | | | Chemically homogeneous and thermally reversible oxidation of epitaxial graphene pp305 - 309
Md. Zakir Hossain, James E. Johns, Kirk H. Bevan, Hunter J. Karmel, Yu Teng Liang, Shinya Yoshimoto, Kozo Mukai, Tatanori Koitaya, Jun Yoshinobu, Maki Kawai, Amanda M. Lear, Larry L. Kesmodel, Steven L. Tait and Mark C. Hersam
doi:10.1038/nchem.1269
Graphene oxide produced via the standard Hummers method possesses a high degree of chemical inhomogeneity and limited reversibility. Now, it has been shown that an alternative ultra-high-vacuum approach for oxidizing epitaxial graphene yields uniform epoxy functionalization with thermal reversibility at temperatures as low as 260 °C.
Abstract | Full Text | PDF
| | | | Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation pp310 - 316
Guang Lu, Shaozhou Li, Zhen Guo, Omar K. Farha, Brad G. Hauser, Xiaoying Qi, Yi Wang, Xin Wang, Sanyang Han, Xiaogang Liu, Joseph S. DuChene, Hua Zhang, Qichun Zhang, Xiaodong Chen, Jan Ma, Say Chye Joachim Loo, Wei D. Wei, Yanhui Yang, Joseph T. Hupp and Fengwei Huo
doi:10.1038/nchem.1272
Surfactant-capped nanoparticles of various sizes, shapes and compositions have been completely enshrouded within a metal–organic framework in a controlled, well-dispersed manner. The resulting hybrid materials exhibit active properties — catalytic, magnetic and optical — arising from the nanoparticles as well as sieving and orientation effects originating from the porous framework.
Abstract | Full Text | PDF
| | | | Self-assembly of the oxy-tyrosinase core and the fundamental components of phenolic hydroxylation pp317 - 322
Cooper Citek, Christopher T. Lyons, Erik C. Wasinger and T. Daniel P. Stack
doi:10.1038/nchem.1284
A functional active-site mimic of the oxy-tyrosinase enzyme forms through self-assembly of monodentate imidazole ligands, copper(I) and oxygen at −125 °C. The fidelity of this copper–dioxygen complex to the native enzyme, its inherent stability and hydroxylation reactivity suggest that an organizational role of the protein matrix suffices to realize function.
Abstract | Full Text | PDF | Chemical compounds
| | | | Ionization of dimethyluracil dimers leads to facile proton transfer in the absence of hydrogen bonds pp323 - 329
Amir Golan, Ksenia B. Bravaya, Romas Kudirka, Oleg Kostko, Stephen R. Leone, Anna I. Krylov and Musahid Ahmed
doi:10.1038/nchem.1298
Proton transfer is usually considered in the context of hydrogen-bonding networks serving as proton-shuttling pathways. Now, an efficient ionization-induced proton transfer in the absence of hydrogen bonds has been observed in a model p-stacked system, the 1,3-dimethyluracil dimer.
Abstract | Full Text | PDF
| | | | An M18L24 stellated cuboctahedron through post-stellation of an M12L24 core pp330 - 333
Qing-Fu Sun, Sota Sato and Makoto Fujita
doi:10.1038/nchem.1285
A molecular ‘stellated polyhedron’ with concave faces — constructed by extending the faces of its counterpart polyhedron until they intersect — has now been synthesized. Ligands that constitute the square faces of a metal–organic cuboctahedral cage were decorated with pendant side chains, which reversibly coordinate to additional metal centres to give rise to the stellated cage.
Abstract | Full Text | PDF
| | In Your Element | Top | | | | Counting on copper p334
Tiberiu G. Moga
doi:10.1038/nchem.1315
Copper, routinely encountered in daily life, may at first glance seem a little unexciting. Tiberiu G. Moga relates how science, however, has not overlooked its promise.
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| | | Top | | | | | Advertisement | | Frontiers in Electronic Materials: Correlation Effects and Memristive Phenomena
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