Table of contents


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Editorial

Of polemics and progress p141

doi:10.1038/nchem.1294

Disagreements are common in science and can lead to better understanding, but must be handled carefully.


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Thesis

Zen and the art of molecules pp142 - 144

Michelle Francl

doi:10.1038/nchem.1279

Michelle Francl wonders what it is that makes a molecule elegant.

Subject term: General chemistry


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Blogroll

Blogroll: For safety's sake p147

doi:10.1038/nchem.1292


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News and Views

Surface chemistry: Making the right connections pp149 - 150

Neil R. Champness

doi:10.1038/nchem.1276

How do you create a molecular circuit board? Covalently coupling different molecules in a sequential manner in surface-based nanostructures opens up new possibilities and hopes for molecular electronics.

Subject terms: Nanotechnology | Surface chemistry

See also: Article by Lafferentz et al.


Chirality: Spin and gravity give a helping hand pp150 - 152

Laurence D. Barron

doi:10.1038/nchem.1278

The handedness of supramolecular helices formed from achiral monomers has been controlled by applying rotational and gravitational forces, but at the start of the assembly process only. This demonstrates that a falsely chiral influence is able to induce absolute enantioselection.

Subject terms: Physical chemistry | Supramolecular chemistry

See also: Article by Micali et al.


Radiochemistry: Flipping fluoride's reactivity pp152 - 154

Véronique Gouverneur

doi:10.1038/nchem.1280

A sophisticated palladium(IV)-based species allows nucleophilic fluoride to react as an electrophilic fluorination reagent. This long-awaited reactivity will be especially useful in the preparation of radiochemically labelled molecules for positron emission tomography studies.

Subject terms: Synthesis | Medicinal chemistry


Quantum chemistry: Quadruply bonded carbon pp154 - 155

Jörg Grunenberg

doi:10.1038/nchem.1274

Determining molecular bond orders can be a delicate and sophisticated task, especially if the electronic structure of the studied system is complex. Now, two different ab initio methods have revealed that C2 and analogous species have a fourth bond, rather than the previously assumed maximum of three.

Subject terms: Theoretical chemistry | Physical chemistry

See also: Article by Shaik et al.


Nucleic acid hybridization: Robust sequence discrimination pp155 - 157

Grégoire Altan-Bonnet & Fred Russell Kramer

doi:10.1038/nchem.1283

Careful consideration of thermodynamics has allowed the design of nucleic acid probes that are highly specific and virtually unaffected by changes in reaction conditions.

Subject terms: Analytical chemistry | Biochemistry | Nanotechnology

See also: Article by Zhang et al.


Ultrafast chemical physics: In search of molecular movies pp157 - 158

Julia A. Weinstein & Neil T. Hunt

doi:10.1038/nchem.1282

Ultrafast chemical physics follows in the explosive wake of technological innovation, using light and radiation sources to study phenomena at timescales where the boundaries between physics and chemistry dissolve. UCP 2011, the second meeting in a series, explored the current state of the art in ultrafast time-resolved spectroscopy.

Subject terms: Physical chemistry | Analytical chemistry


Metamaterials: Turning a negative into a positive pp159 - 160

Jackie Y. Ying

doi:10.1038/nchem.1275

Metamaterials are synthetic materials tailored with unusual properties that are not found in nature. It has now been predicted that they could be engineered with negative refractive index through the use of periodic structures via bottom-up self-assembly synthesis.

Subject terms: Physical chemistry | Materials chemistry


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Perspectives

Good vibrations in enzyme-catalysed reactions pp161 - 168

Sam Hay & Nigel S. Scrutton

doi:10.1038/nchem.1223

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This Perspective discusses contemporary ideas for enzymatic reactions that invoke a role for fast 'promoting' (or 'compressive') motions or vibrations that, in principle, can facilitate enzyme-catalysed reactions. With an emphasis on hydrogen-transfer reactions, experimental, theoretical and computational approaches that have lent evidence to this controversial hypothesis are discussed.

Subject terms: Biochemistry | Catalysis | Chemical biology


Taking Ockham's razor to enzyme dynamics and catalysis pp169 - 176

David R. Glowacki, Jeremy N. Harvey & Adrian J. Mulholland

doi:10.1038/nchem.1244

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Enzyme-catalysed reactions can involve significant quantum tunnelling and show kinetic isotope effects with complex temperature dependences. In this Perspective, reaction dynamics and enzyme catalysis are linked to transition-state-theory frameworks. It is shown that a multi-state model using standard transition-state theory can account for complex experimental data without invoking a role for enzyme dynamics.

Subject terms: Catalysis | Theoretical chemistry | Chemical biology


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Articles

The promoting effect of adsorbed carbon monoxide on the oxidation of alcohols on a gold catalyst pp177 - 182

Paramaconi Rodriguez, Youngkook Kwon & Marc T. M. Koper

doi:10.1038/nchem.1221

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Adsorbed carbon monoxide typically acts to poison the oxidation of alcohols on heterogeneous catalysts and electrocatalysts. Here, it is shown that carbon monoxide that has been adsorbed irreversibly on a Au(111) surface can act as a promoter for this process by enhancing the scission of C–H bonds in the alcohol to yield the corresponding aldehyde.

Subject terms: Catalysis | Physical chemistry | Electrochemistry


Darwinian evolution of an alternative genetic system provides support for TNA as an RNA progenitor pp183 - 187

Hanyang Yu, Su Zhang & John C. Chaput

doi:10.1038/nchem.1241

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The pre-RNA-world hypothesis postulates that RNA was preceded in the evolution of life by a simpler genetic material. Here, Darwinian evolution methods were used to generate a threose nucleic acid (TNA) aptamer. This result provides evidence that TNA could have served as an ancestral genetic system during an early stage of life.

Subject terms: Biochemistry | Chemical biology


Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography pp188 - 194

Tom Willhammar, Junliang Sun, Wei Wan, Peter Oleynikov, Daliang Zhang, Xiaodong Zou, Manuel Moliner, Jorge Gonzalez, Cristina Martínez, Fernando Rey & Avelino Corma

doi:10.1038/nchem.1253

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Solving the structure of zeolites is often challenging because of their small particle size. Now, electron crystallography reveals the structure of a family of complex intergrown zeolite materials. These zeolites contain unique pair-wise 12-ring channels that intersect with 10-ring channels, and are promising catalysts for converting gasoline into diesel fuel.

Subject terms: Catalysis | Materials chemistry


Quadruple bonding in C2 and analogous eight-valence electron species pp195 - 200

Sason Shaik, David Danovich, Wei Wu, Peifeng Su, Henry S. Rzepa & Philippe C. Hiberty

doi:10.1038/nchem.1263

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The bonding order of multiply bonded main-group elements is conventionally thought to be limited to triple bonds. Now, using high-level theoretical methods, it is shown that C2 and its isoelectronic molecules CN+, BN and CB are quadruply bonded, featuring not only one σ - and two π-bonds, but also one weak ‘inverted’ bond.

Subject terms: Theoretical chemistry | Physical chemistry

See also: News and Views by Grunenberg


Selection of supramolecular chirality by application of rotational and magnetic forces pp201 - 207

N. Micali, H. Engelkamp, P. G. van Rhee, P. C. M. Christianen, L. Monsù Scolaro & J. C. Maan

doi:10.1038/nchem.1264

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It is shown here that the proper combination of physical forces can induce chirality during the self-assembly of achiral molecules. Rotation and effective gravity created by high magnetic fields during the nucleation phase, together with the magnetic alignment of the nanoaggregates initially formed, control the enantioselectivity of porphyrin assemblies.

Subject terms: Physical chemistry | Supramolecular chemistry

See also: News and Views by Barron


Optimizing the specificity of nucleic acid hybridization pp208 - 214

David Yu Zhang, Sherry Xi Chen & Peng Yin

doi:10.1038/nchem.1246

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High-fidelity pairing of nucleic acid polymers is important in the development of sensors and for the application of DNA nanotechnology. Here, a set of hybridization probes is described that discriminates single-base changes with high specificity. The probes function robustly across many different temperatures, salinities and nucleic acid concentrations.

Subject terms: Biochemistry | Nanotechnology

See also: News and Views by Altan-Bonnet & Kramer


Controlling on-surface polymerization by hierarchical and substrate-directed growth pp215 - 220

L. Lafferentz, V. Eberhardt, C. Dri, C. Africh, G. Comelli, F. Esch, S. Hecht & L. Grill

doi:10.1038/nchem.1242

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The bottom-up construction of covalently linked molecular architectures on surfaces has recently been demonstrated, but only rather simple structures can be obtained in such one-step connection processes. A sequential approach has now been used to induce the selective connection of molecules with a programmed reactivity, enabling network formation with high selectivity.

Subject terms: Nanotechnology | Surface chemistry

See also: News and Views by Champness


Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation pp221 - 227

Polly L. Arnold, Guy M. Jones, Samuel O. Odoh, Georg Schreckenbach, Nicola Magnani & Jason B. Love

doi:10.1038/nchem.1270

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The oxo groups in the common trans-uranyl ion — present in the majority of known uranium compounds — are linear and inert. Now, a new reduced binuclear uranium–dioxo compound with very strong metal coupling and remarkable air stability has been formed through oxo migration and silylation.

Subject terms: Inorganic chemistry | Organometallic chemistry | Synthesis


Chemoselective synthesis of ketones and ketimines by addition of organometallic reagents to secondary amides pp228 - 234

William S. Bechara, Guillaume Pelletier & André B. Charette

doi:10.1038/nchem.1268

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To achieve chemoselective additions of organometallics to carbonyls, it is important to consider the combination of acylating agent and organometallic as a reactive pair rather than either one in isolation. Here, a chemoselective, controlled and general methodology for the conversion of secondary amides to ketones and ketimines is described.

Subject terms: Organic chemistry | Synthesis


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Erratum

Binary fluorous tagging enables the synthesis and separation of a 16-stereoisomer library of macrosphelides p235

Dennis P. Curran, Mantosh K. Sinha, Kai Zhang, Jesse J. Sabatini & Dae-Hyun Cho

doi:10.1038/nchem.1271

See also: Article by Curran et al.


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In Your Element

The deeds to deuterium p236

Dan O'Leary

doi:10.1038/nchem.1273

Dan O'Leary examines Harold Urey's decision to name the mass-2 hydrogen isotope 'deuterium'.


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