Tuesday, June 23, 2015

Nature Chemistry Contents July 2015 Volume 7 Number 7 pp 533 - 610

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Nature Chemistry

TABLE OF CONTENTS

July 2015 Volume 7, Issue 7

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


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Thesis

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Chemical doublespeak   pp533 - 534
Michelle Francl
doi:10.1038/nchem.2288
Michelle Francl suggests that chemists should relax and not fret over ambiguous language.

Research Highlights

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Dynamic covalent chemistry: Tales from the cryptates | Polymer folding: A right tangle | Biosynthesis: Building a biofactory | DNA duplexes: Carefully crafted crosslinks

Blogroll

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Blogroll: Patently inventive   p537
Luke Gamon
doi:10.1038/nchem.2292

News and Views

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Bioorthogonal catalysis: Rise of the nanobots   pp538 - 539
Asier Unciti-Broceta
doi:10.1038/nchem.2291
Bioorthogonal catalysis provides new ways of mediating artificial transformations in living environs. Now, researchers have developed a nanodevice whose catalytic activity can be regulated by host–guest chemistry.

See also: Article by Tonga et al.

Stereoselective synthesis: Molecular editing of carbohydrates   pp539 - 541
Andrew McNally
doi:10.1038/nchem.2289
Deoxygenation reactions have been used to convert biomass-derived carbohydrates into useful platform chemicals. Now, a method has been described that can selectively excise C–O bonds to produce valuable chiral synthons.

See also: Article by Adduci et al.

Analytical chemistry: Clamping down on cancer detection   pp541 - 542
Irina A. Gorodetskaya and Alon A. Gorodetsky
doi:10.1038/nchem.2290
An electrochemical clamp assay that enables the rapid and sensitive detection of nucleic acids containing single base mutations has now been developed. It has been shown to differentiate between cancer patient samples featuring a specific mutation, and controls from healthy donors or other cancer patients, all directly in unprocessed serum.

See also: Article by Das et al.

Nano-plasmonics: Chirality transfer takes a jump   pp543 - 544
Vladimiro Mujica
doi:10.1038/nchem.2294
The transfer of chirality is known to occur through chemical bonds. Now, chiral biomolecules have been observed to impart some of their optical properties to a spatially separated achiral dye — with the transfer mediated by plasmon resonance from an achiral metallic nanostructure.

See also: Article by Ostovar pour et al.

Chemistry
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Articles

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Simulation-guided DNA probe design for consistently ultraspecific hybridization   pp545 - 553
Juexiao Sherry Wang and David Yu Zhang
doi:10.1038/nchem.2266



The use of kinetic simulations to guide the design of competitive hybridization probe systems is shown to enable high selectivity for single-nucleotide variants. Using this approach across 44 cancer mutation/wild-type sequence pairs showed between a 200- and 3,000-fold higher binding affinity than the corresponding wild-type sequence. In combination with PCR amplification this method enabled the detection of a 1% concentration of variant alleles in human genomic DNA.

Selective, rapid and optically switchable regulation of protein function in live mammalian cells   pp554 - 561
Yu-Hsuan Tsai, Sebastian Essig, John R. James, Kathrin Lang and Jason W. Chin
doi:10.1038/nchem.2253



The rapid and selective regulation of a target protein within living cells containing closely related family members is a longstanding challenge. Now the introduction of genetically directed bioorthogonal ligand tethering (BOLT) and the demonstration of selective inhibition (iBOLT) and optical switching (photo-BOLT) of protein function in live mammalian cells addresses this challenge.
Chemical compounds

Roaming-mediated ultrafast isomerization of geminal tri-bromides in the gas and liquid phases   pp562 - 568
Andrey S. Mereshchenko, Evgeniia V. Butaeva, Veniamin A. Borin, Anna Eyzips and Alexander N. Tarnovsky
doi:10.1038/nchem.2278



Roaming — a new and unusual reaction mechanism in gas-phase chemical transformations — is now shown to occur in solution. Following ultraviolet excitation of geminal tribromides, what initially seems to be the simple fission of a bond is in fact isomerization occurring through the roaming of molecular fragments.

An electrochemical clamp assay for direct, rapid analysis of circulating nucleic acids in serum   pp569 - 575
Jagotamoy Das, Ivaylo Ivanov, Laura Montermini, Janusz Rak, Edward H. Sargent et al.
doi:10.1038/nchem.2270



The analysis of circulating cell-free nucleic acids (cfNA) in the blood of cancer patients permits the analysis of tumour mutations without requiring invasive sampling of tissue. Now, the development of an electrochemical assay that uses a collection of clamp molecules to sequester interfering cfNAs enables the accurate detection of mutated sequences in serum collected from people with lung cancer or melanoma.

See also: News and Views by Gorodetskaya & Gorodetsky

Chemoselective conversion of biologically sourced polyols into chiral synthons   pp576 - 581
Laura L. Adduci, Trandon A. Bender, Jennifer A. Dabrowski and Michel R. Gagné
doi:10.1038/nchem.2277



Biorenewable carbohydrate feedstocks can be efficiently converted into a diverse set of oxygen-functionalized chiral synthons using a combination of a tertiary silane and the catalyst B(C6F5)3. The deoxygenation mechanism involves cyclic intermediates, which provide a means of controlling chemo- and diastereoselectivity.
Chemical compounds
See also: News and Views by McNally

Triamidoamine uranium(IV)–arsenic complexes containing one-, two- and threefold U–As bonding interactions   pp582 - 590
Benedict M. Gardner, Gábor Balázs, Manfred Scheer, Floriana Tuna, Eric J. L. McInnes et al.
doi:10.1038/nchem.2279



The nature of actinide–ligand bonding is attracting attention, in particular in the context of nuclear waste separations. Structurally authenticated one-, two- and threefold uranium–arsenic bonding interactions are now reported. Computational analysis suggests the presence of polarized σ2, σ2π2, and σ2π4 in the arsenide, terminal arsinidene, and arsenido complexes, respectively.
Chemical compounds

Through-space transfer of chiral information mediated by a plasmonic nanomaterial   pp591 - 596
Saeideh Ostovar pour, Louise Rocks, Karen Faulds, Duncan Graham, Václav Parchaƈský et al.
doi:10.1038/nchem.2280



Surface-enhanced resonant Raman optical activity (SERROA) reveals the through-space transfer of chirality from biomolecules to achiral benzotriazole dye-conjugated nanotags. The chiroptical responses generated by the stereoisomers of ribose and tryptophan establish this as the basis for a stereoselective nanosensor platform.

See also: News and Views by Mujica

Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts   pp597 - 603
Gulen Yesilbag Tonga, Youngdo Jeong, Bradley Duncan, Tsukasa Mizuhara, Rubul Mout et al.
doi:10.1038/nchem.2284



Regulation of bioorthogonal catalysis in living systems is challenging because of the complex intracellular environment. Now, the activity of protein-sized bioorthogonal nanozymes has been regulated by binding a supramolecular cucurbit[7]uril ‘gate-keeper’ onto the monolayer surface. This arrangement enables the controlled activation of profluorophores and prodrugs inside living cells for imaging and therapeutic applications.

See also: News and Views by Unciti-Broceta

An eight-step gram-scale synthesis of (−)-jiadifenolide   pp604 - 607
Hai-Hua Lu, Michael D. Martinez and Ryan A. Shenvi
doi:10.1038/nchem.2283



A chemical synthesis of (–)-jiadifenolide, a small molecule neurotrophin, has been achieved in eight steps. The route relies on a stereoselective coupling of two simple butenolides to build the entire skeleton in a single step and produce one gram of the target for broad distribution to the biomedical community.
Chemical compounds

Corrigendum

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Corrigendum: Orthogonal tandem catalysis   p608
Tracy L. Lohr and Tobin J. Marks
doi:10.1038/nchem.2293

In Your Element

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Toxic thallium   p610
Anders Lennartson
doi:10.1038/nchem.2286
Anders Lennartson ponders on the contribution of thallium to society, since its main characteristic is its toxicity.

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