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Nature Chemistry Contents September 2014 Volume 6 Number 9 pp 747-840

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TABLE OF CONTENTS

September 2014 Volume 6, Issue 9

Editorial
Thesis
Interview
Research Highlights
Blogroll
News and Views
Review
Articles
In Your Element
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Editorial

Top

2D or not 2D?   p747
doi:10.1038/nchem.2053
Flat is the question.

See also: Article by Kory et al. | Article by Kissel et al. | News and Views by Champness | Interview with Benjamin King and Dieter Schlüter

Thesis

Top

An ode to the atomic weights   pp749 - 750
Juris Meija
doi:10.1038/nchem.2047
They might not be fundamental constants of nature, but atomic weights are one of the foundations on which modern chemistry is built, explains Juris Meija.

Interview

Top

The chemists behind the crystals   pp751 - 753
Interview with Benjamin King and Dieter Schlüter
doi:10.1038/nchem.2033
Benjamin King and Dieter Schlüter, the corresponding authors of two Articles in this issue that describe single-crystal characterization of two-dimensional polymers, talk to Nature Chemistry about the background, challenges and prospects of their work.

See also: Article by Kory et al. | Article by Kissel et al. | News and Views by Champness | Editorial

Research Highlights

Top

Carboboration: Addition to alkynoates | Chiral separation: Molecular doormen | Antibiotics: Resistance is restored | Carbon nanomaterials: Targeted tubes

Blogroll

Top

Blogroll: Life in the lab   p755
Matthew Hartings
doi:10.1038/nchem.2036

News and Views

Top

Enzyme catalysis: Evolution made easy   pp756 - 757
Eugene J. H. Wee and Matt Trau
doi:10.1038/nchem.2046
Directed evolution is a powerful tool for the development of improved enzyme catalysts. Now, a method that enables an enzyme, its encoding DNA and a fluorescent reaction product to be encapsulated in a gel bead enables the application of directed evolution in an ultra-high-throughput format.

See also: Article by Fischlechner et al.

Two-dimensional materials: Crystallized creations in 2D   pp757 - 759
Neil R. Champness
doi:10.1038/nchem.2015
Two reports demonstrate that with the right molecules and the right crystalline arrangement, it is not only possible to create two-dimensional crystals, but also to separate them into single-molecule-thick sheets — so-called two-dimensional polymers.

See also: Article by Kory et al. | Article by Kissel et al. | Interview with Benjamin King and Dieter Schlüter | Editorial

Quantum control: May the electric force be with you   pp759 - 760
Albert Stolow
doi:10.1038/nchem.2037
Intense laser fields can apply strong forces to molecules, distorting molecular potentials. Now, these effects have been used to precisely control the branching ratios of a polyatomic photodissociation reaction.

See also: Article by Corrales et al.

Helicates: Making head-head-tails of it   pp761 - 762
Markus Albrecht
doi:10.1038/nchem.2040
Enantiomerically pure head-to-head-to-tail triple-stranded helicates synthesized using a subcomponent self-assembly approach possess high anticancer activities against cancer cell lines without significant damage to DNA and with low toxicity to bacteria.

See also: Article by Faulkner et al.

Scientific conferences: A big hello to halogen bonding   pp762 - 764
Mate Erdelyi
doi:10.1038/nchem.2042
Halogen bonding connects a wide range of subjects — from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

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Review

Top

The electron is a catalyst   pp765 - 773
Armido Studer and Dennis P. Curran
doi:10.1038/nchem.2031



This Review draws an analogy between acid-base catalysis and redox catalysis. The 'electron is a catalyst' paradigm unifies mechanistically an assortment of synthetic transformations that otherwise have little or no apparent relationship. Various radical cascades catalysed by the electron are discussed.

Articles

Top

A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization   pp774 - 778
Patrick Kissel, Daniel J. Murray, William J. Wulftange, Vincent J. Catalano and Benjamin T. King
doi:10.1038/nchem.2008



Two-dimensional synthetic polymers can be produced through solid-state topochemical polymerization, but achieving this through a single-crystal-to-single-crystal transformation has not yet been demonstrated. Now, a fluorinated Y-shaped monomer has been preorganized in a lamellar crystal, which goes through two successive single-crystal-to-single-crystal phototransformations to give a 2D polymer; single-crystal X-ray diffraction has been used to elucidate its structure.
Chemical compounds
See also: News and Views by Champness | Article by Kory et al. | Interview with Benjamin King and Dieter Schlüter | Editorial

Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction   pp779 - 784
Max J. Kory, Michael Wörle, Thomas Weber, Payam Payamyar, Stan W. van de Poll et al.
doi:10.1038/nchem.2007



Accessing synthetic two-dimensional polymers that are analogous to graphene is synthetically and analytically challenging. Now, single crystals of a simple-to-make monomer have been grown and then photopolymerized to form layered single crystals of covalently bonded two-dimensional polymer. Much like natural graphite, these crystals can be exfoliated to form thin sheets and single layers of the polymer.
Chemical compounds
See also: News and Views by Champness | Article by Kissel et al. | Interview with Benjamin King and Dieter Schlüter | Editorial

Control of ultrafast molecular photodissociation by laser-field-induced potentials   pp785 - 790
M. E. Corrales, J. González-Vázquez, G. Balerdi, I. R. Solá, R. de Nalda et al.
doi:10.1038/nchem.2006



Shaping potential energy surfaces by tailored strong laser pulses has now been shown to be a powerful method for controlling product yields in an ultrafast polyatomic photodissociation reaction. Control over the velocity of the product fragments is also achieved through the generation of light-induced conical intersections and modulating the potentials around them.

See also: News and Views by Stolow

Evolution of enzyme catalysts caged in biomimetic gel-shell beads   pp791 - 796
Martin Fischlechner, Yolanda Schaerli, Mark F. Mohamed, Santosh Patil, Chris Abell et al.
doi:10.1038/nchem.1996



Directed evolution has emerged as a powerful tool for the identification of improved enzyme catalysts. Now, gel-shell beads are introduced as compartments that cage an enzyme with its encoding DNA, constituting a new genotype–phenotype linkage. Screening of 107 gel-shell beads by flow cytometry leads to an improved phosphotriesterase bioremediation catalyst.
Chemical compounds
See also: News and Views by Wee & Trau

Asymmetric triplex metallohelices with high and selective activity against cancer cells   pp797 - 803
Alan D. Faulkner, Rebecca A. Kaner, Qasem M. A. Abdallah, Guy Clarkson, David J. Fox et al.
doi:10.1038/nchem.2024



Water-soluble metallohelices containing an antiparallel head-to-head-to-tail arrangement of strands are reported. This amphipathic functional topology is akin to that of host-defence peptides. The metallohelices show high and selective toxicity to a cancer cell line, causing dramatic changes in the cell cycle without DNA damage. In contrast, there is no significant toxicity to MRSA and Escherichia coli.
Chemical compounds
See also: News and Views by Albrecht

Template-directed covalent conjugation of DNA to native antibodies, transferrin and other metal-binding proteins   pp804 - 809
Christian B. Rosen, Anne L. B. Kodal, Jesper S. Nielsen, David H. Schaffert, Carsten Scavenius et al.
doi:10.1038/nchem.2003



Conjugation of DNA to proteins often involves a choice between either expressing recombinant proteins with a specific handle, or labelling wild-type proteins with low site-selectivity. Now preorganization of a DNA–ligand complex to a metal-binding site enables site-selective conjugation of a DNA strand to lysine residues of wild-type proteins and antibodies.

Synthesis of hydroxyphthioceranic acid using a traceless lithiation–borylation–protodeboronation strategy   pp810 - 814
Ramesh Rasappan and Varinder K. Aggarwal
doi:10.1038/nchem.2010



Coupling of carbamates with boronic esters followed by protodeboronation creates a new carbon–carbon bond, leaving behind no trace of the functional groups used to create it. Now, methodology for the protodeboronation of alkyl pinacol boronic esters has been developed and an iterative lithiation–borylation–protodeboronation strategy used in a 14-step stereocontrolled synthesis of hydroxyphthioceranic acid.
Chemical compounds

Triazolinediones enable ultrafast and reversible click chemistry for the design of dynamic polymer systems   pp815 - 821
Stijn Billiet, Kevin De Bruycker, Frank Driessen, Hannelore Goossens, Veronique Van Speybroeck et al.
doi:10.1038/nchem.2023



Macromolecular functionalization and linking are often facilitated by using ‘click’ chemistries. Now, triazolinediones have been used in ultrafast click reactions under additive-free, ambient conditions for polymer conjugation. Clicking to indoles gives an adduct that is dynamic at elevated temperatures, which produces properties such as polymer-network healing, reshaping and recycling.
Chemical compounds

A redox hydrogel protects hydrogenase from high-potential deactivation and oxygen damage   pp822 - 827
Nicolas Plumeré, Olaf Rüdiger, Alaa Alsheikh Oughli, Rhodri Williams, Jeevanthi Vivekananthan et al.
doi:10.1038/nchem.2022



Hydrogenases are efficient and promising catalysts for fuel cells; however, they suffer from oxygen sensitivity and deactivation at high potentials. Integration of hydrogenases into redox-active hydrogels provides a redox buffer and a self-activated oxygen-scavenging mechanism. This tandem protection makes the hydrogenase a possible alternative to noble metal catalysts.

High-performance Ag–Co alloy catalysts for electrochemical oxygen reduction   pp828 - 834
Adam Holewinski, Juan-Carlos Idrobo and Suljo Linic
doi:10.1038/nchem.2032



The oxygen reduction reaction limits fuel cell performance and currently requires costly electrocatalysts with high platinum content to achieve adequate power densities. Now a silver–cobalt surface alloy electrocatalyst has been developed for the oxygen reduction reaction that is stable in alkaline electrolytes and is more economical than traditional platinum-based materials.

Irreversible xenon insertion into a small-pore zeolite at moderate pressures and temperatures   pp835 - 839
Donghoon Seoung, Yongmoon Lee, Hyunchae Cynn, Changyong Park, Kwang-Yong Choi et al.
doi:10.1038/nchem.1997



Several solutions to the ‘missing xenon’ problem have been proposed that involve the selective sorption of Xe in minerals found in the Earth. It is now shown that a zeolite, Ag-natrolite, absorbs and retains 28 wt% Xe at 1.7 GPa and 250 °C, conditions found in subsurface Earth, through expulsion of metallic Ag(0).

In Your Element

Top

Californium gleaming   p840
Thomas Albrecht-Schmitt
doi:10.1038/nchem.2035
Thomas Albrecht-Schmitt explains the origin of element 98's striking green glow, and why the future for californium chemistry is just as bright.

Top
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