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Books and Arts

The human science p335

Ashutosh S. Jogalekar reviews Roald Hoffmann on the Philosophy, Art and Science of Chemistry by Jeffrey Kovac & Michael Weisberg

doi:10.1038/nchem.1334


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Blogroll

Blogroll: Arnie and artemisinin p337

doi:10.1038/nchem.1349


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News and Views

Custom labware: Chemical creativity with 3D printing pp338 - 339

R. Daniel Johnson

doi:10.1038/nchem.1333

The cost, time and expertise needed for custom fabrication is a limiting factor when it comes to the development and production of new labware. With an increase in the popularity and accessibility of three-dimensional printing techniques, that may be about to change.

Subject terms: General chemistry | Synthesis

See also: Article by Symes et al.


Infrared spectroscopy: Mapping protein–protein contacts pp339 - 341

Minhaeng Cho

doi:10.1038/nchem.1336

Obtaining detailed structural information about the interactions between amyloid-forming proteins and inhibitors can be extremely difficult. Two-dimensional infrared spectroscopy has now risen to this challenge to show the mapping of protein–protein contact sites in real time.

Subject terms: Chemical biology | Physical chemistry

See also: Article by Middleton et al.


Total synthesis: Welwitindolinone is well worth it pp341 - 343

John L. Wood

doi:10.1038/nchem.1335

Recent syntheses of the natural product 3-hydroxy-N-methylwelwitindolinone C isothiocyanate are taken as examples to answer an oft-raised question about the value of total synthesis.

Subject terms: Organic chemistry | Synthesis


Main group chemistry: A heavier-element ketone at last pp343 - 344

Philip P. Power

doi:10.1038/nchem.1309

The first heavier main-group-14-element analogue of a ketone, which contains a three-coordinate germanium atom multiply bonded to oxygen, has been prepared and characterized.

Subject term: Inorganic chemistry

See also: Article by Li et al.


Asymmetric catalysis: Correlating sterics in catalysis pp344 - 345

Scott J. Miller

doi:10.1038/nchem.1339

Recognizing that an analogy can be drawn between steric effects in drug discovery and asymmetric catalysis has led to a powerful technique that can explain and potentially predict the outcome of asymmetric reactions.

See also: Article by Harper et al.


Self-assembly: Proteins on parade pp346 - 347

John C. Sinclair

doi:10.1038/nchem.1337

A protein is modified to assemble with metal ions through judiciously designed coordination and dimerization sites. This elegantly controlled process arranges the protein into crystalline arrays — a useful form for exploring and exploiting protein properties.

Subject terms: Chemical biology | Materials chemistry

See also: Article by Brodin et al.


Magnetic anisotropy: The orientation is in the details pp347 - 348

Muralee Murugesu

doi:10.1038/nchem.1341

A detailed magnetic, structural and luminescence characterization unveils that what may have looked like mere details have a significant influence on the magnetic properties of a dysprosium complex.

Subject term: Inorganic chemistry


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Articles

Integrated 3D-printed reactionware for chemical synthesis and analysis pp349 - 354

Mark D. Symes, Philip J. Kitson, Jun Yan, Craig J. Richmond, Geoffrey J. T. Cooper, Richard W. Bowman, Turlif Vilbrandt & Leroy Cronin

doi:10.1038/nchem.1313

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A low-cost 3D printer is used to combine chemical reactions and the reactor to produce an active ‘reactionware’ system for organic and inorganic synthesis. Active elements such as catalysts can be incorporated into the walls of printed reactors, and other printed-in components that enable electrochemical and spectroscopic analysis can also be included.

Subject terms: General chemistry | Synthesis

See also: News and Views by Johnson


Two-dimensional infrared spectroscopy reveals the complex behaviour of an amyloid fibril inhibitor pp355 - 360

Chris T. Middleton, Peter Marek, Ping Cao, Chi-cheng Chiu, Sadanand Singh, Ann Marie Woys, Juan J. de Pablo, Daniel P. Raleigh & Martin T. Zanni

doi:10.1038/nchem.1293

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Molecular inhibitors of amyloid formation could help combat Alzheimer's disease, type 2 diabetes, and other major human diseases. Here, two-dimensional infrared spectroscopy and residue-specific isotope labelling are used to obtain detailed structural information on amyloid-inhibitor complexes. The unexpected behaviour observed helps to explain the moderate activity of the inhibitor studied.

Subject terms: Chemical biology | Physical chemistry

See also: News and Views by Cho


A stable germanone as the first isolated heavy ketone with a terminal oxygen atom pp361 - 365

Liangchun Li, Tomohide Fukawa, Tsukasa Matsuo, Daisuke Hashizume, Hiroyuki Fueno, Kazuyoshi Tanaka & Kohei Tamao

doi:10.1038/nchem.1305

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Heavier analogues of ketones — containing a double bond between a group 14 element and oxygen — have so far not been isolated as stable compounds. Now, a stable monomeric germanone with a highly polarized Ge=O double bond has been isolated, stabilized by rigid bulky ligands.

Subject term: Inorganic chemistry

See also: News and Views by Power


Multidimensional steric parameters in the analysis of asymmetric catalytic reactions pp366 - 374

Kaid C. Harper, Elizabeth N. Bess & Matthew S. Sigman

doi:10.1038/nchem.1297

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Many parameters have been designed to describe steric size, but few have been able to explain consistently the selectivity of asymmetric catalytic reactions. Here, Sterimol parameters — originally used to develop quantitative structure–activity relationships in medicinal chemistry — have been used to quantify enantioselectivity in a diverse collection of asymmetric catalytic reactions.

Subject terms: Catalysis | Synthesis

See also: News and Views by Miller


Metal-directed, chemically tunable assembly of one-, two- and three-dimensional crystalline protein arrays pp375 - 382

Jeffrey D. Brodin, X. I. Ambroggio, Chunyan Tang, Kristin N. Parent, Timothy S. Baker & F. Akif Tezcan

doi:10.1038/nchem.1290

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The self-assembly of proteins into ordered yet dynamic nanoscale architectures is a crucial biological process and an inspiration for supramolecular chemistry, but has remained largely inaccessible synthetically. A monomeric protein has now been prepared that assembles with zinc ions into one-, two- and three-dimensional crystalline arrays with nano- and microscale order.

Subject terms: Chemical biology | Materials chemistry

See also: News and Views by Sinclair


Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures pp383 - 388

Jonathan F. Hull, Yuichiro Himeda, Wan-Hui Wang, Brian Hashiguchi, Roy Periana, David J. Szalda, James T. Muckerman & Etsuko Fujita

doi:10.1038/nchem.1295

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When operating at near-ambient conditions, using water as a solvent, a high-turnover iridium catalyst enables a reversible hydrogen storage system that uses carbon dioxide, formate and formic acid. Proton-responsive ligands in the catalyst allow it to be turned on or off by controlling the pH of the solution.

Subject terms: Catalysis | Organometallic chemistry


Elucidation of the timescales and origins of quantum electronic coherence in LHCII pp389 - 395

Gabriela S. Schlau-Cohen, Akihito Ishizaki, Tessa R. Calhoun, Naomi S. Ginsberg, Matteo Ballottari, Roberto Bassi & Graham R. Fleming

doi:10.1038/nchem.1303

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Quantum coherence has been observed in the major light-harvesting complex of photosystem II (LHCII) from green plants. By controlling the laser pulse polarization in two-dimensional electronic spectroscopy, signals from quantum coherence have been separated from other molecular processes, offering insight into the role of quantum coherence in photosynthetic light-harvesting.

Subject terms: Chemical biology | Physical chemistry | Photochemistry


Electronic coherence lineshapes reveal hidden excitonic correlations in photosynthetic light harvesting pp396 - 404

Cathy Y. Wong, Richard M. Alvey, Daniel B. Turner, Krystyna E. Wilk, Donald A. Bryant, Paul M. G. Curmi, Robert J. Silbey & Gregory D. Scholes

doi:10.1038/nchem.1302

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Quantum beating has been observed in photosynthetic systems, suggesting that energy-transfer processes in natural light harvesting could involve quantum effects. Now, extensive beating is found in the light-harvesting protein of a cryptophyte alga, and shown to be electronic. The implications of these observations on the free-energy surfaces and exciton delocalization were investigated.

Subject terms: Physical chemistry | Chemical biology | Photochemistry


A gold-catalysed enantioselective Cope rearrangement of achiral 1,5-dienes pp405 - 409

Ryan J. Felix, Dieter Weber, Osvaldo Gutierrez, Dean J. Tantillo & Michel R. Gagné

doi:10.1038/nchem.1327

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The Cope rearrangement has been known since the 1940s but, until now, no catalytic asymmetric variant has been reported. Here, a gold(I) catalyst is shown to induce an asymmetric Cope rearrangement of achiral 1,5-dienes containing a cyclopropylidene moiety to produce vinyl cyclopropanes in high yield and good to excellent enantioselectivities.

Subject terms: Catalysis | Synthesis


Protein fold determined by paramagnetic magic-angle spinning solid-state NMR spectroscopy pp410 - 417

Ishita Sengupta, Philippe S. Nadaud, Jonathan J. Helmus, Charles D. Schwieters & Christopher P. Jaroniec

doi:10.1038/nchem.1299

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Despite recent progress, solving protein structures using solid-state NMR spectroscopy is not routine. Now, a method for the rapid determination of global protein fold is reported, based on measurements of 15N longitudinal paramagnetic relaxation enhancements in several protein variants modified with covalently attached cysteine–EDTA–Cu2+ tags.

Subject terms: Biochemistry | Physical chemistry


A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II pp418 - 423

Lele Duan, Fernando Bozoglian, Sukanta Mandal, Beverly Stewart, Timofei Privalov, Antoni Llobet & Licheng Sun

doi:10.1038/nchem.1301

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Increasing the efficiency and speed of the water-oxidation reaction is crucial to realizing light-driven water splitting. Now, a mononuclear ruthenium complex achieves fast water-oxidation catalysis with a high reaction rate of more than 300 turnovers per second, comparable to the activity of the oxygen-evolving complex in photosystem II.

Subject terms: Inorganic chemistry | Catalysis | Organometallic chemistry


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Addendum

A versatile approach to high-throughput microarrays using thiol-ene chemistry p424

Nalini Gupta, Brian F. Lin, Luis M. Campos, Michael D. Dimitriou, Sherry T. Hikita, Neil D. Treat, Matthew V. Tirrell, Dennis O. Clegg, Edward J. Kramer & Craig J. Hawker

doi:10.1038/nchem.1328


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In Your Element

The four worlds of carbon p426

Simon H. Friedman

doi:10.1038/nchem.1340

Simon H. Friedman explores the various ways in which carbon is inherently tied to our lives — beyond its elegant, treasured role in organic chemistry.


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