Featured
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Research Highlights |
Caged fluorescence
The incorporation of a small, photochemically controllable diazoketone moiety in fluorescent rhodamine dyes shows great promise in biological imaging.
- Anne Pichon
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Research Highlights |
All together now
A promising material for splitting water relies on the favourable arrangement of photosensitive and catalytic components.
- Gavin Armstrong
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Review Article |
Induction of chiral porous solids containing only achiral building blocks
The synthesis or separation of chiral compounds is crucial for many areas of chemistry, with chiral solids having important roles as catalysts or separating agents. This Review covers recent progress and future avenues for developing methods of preparing chiral solids from achiral starting materials.
- Russell E. Morris
- & Xianhui Bu
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Article |
Geometry-controlled kinetics
The time taken for a reactant to reach a target is best represented theoretically by a distribution of times. This distribution has now been calculated analytically and shows quantitatively that in the case of uncrowded environments, a reactant's starting point — in relation to the target — does not influence the search time. It does, however, have an effect in the case of crowded systems — leading to ‘geometry-controlled kinetics’.
- O. Bénichou
- , C. Chevalier
- & R. Voituriez
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Article |
Rapid preparation of flexible porous coordination polymer nanocrystals with accelerated guest adsorption kinetics
Porous coordination polymers — PCPs, also known as metal–organic framework materials — have been widely investigated for their useful properties, but controlling their size and shape in a nanocrystalline form is difficult. Now, a rapid method of preparing porous crystalline nanosized PCPs that uses a microemulsion system under ultrasonic irradiation has been reported.
- Daisuke Tanaka
- , Artur Henke
- & Juergen Groll
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Research Highlights |
Try the trication
A rationally designed highly electrophilic iridium complex excels at catalysing the formation of five-membered carbocycles.
- Stephen Davey
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Research Highlights |
Protein under glass
The water molecules surrounding a protein can be dissolved in an organic solvent to form dry, glassified microbeads of controllable size that preserve the protein's activity.
- Anne Pichon
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Article |
Assembly of a metal–organic framework by sextuple intercatenation of discrete adamantane-like cages
There has been much interest in the assembly and properties of metal–organic frameworks. Here, a new type is described in which an infinite three-dimensional polycatenane is assembled from a discrete octahedral nanocage through the interlocking of all its six vertices.
- Xiaofei Kuang
- , Xiaoyuan Wu
- & Can-Zhong Lu
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Article |
Isolation of crystalline carbene-stabilized P2-radical cations and P2-dications
N-heterocyclic carbenes have been shown to be versatile ligands for metal catalysts and even catalysts in their own right. Here, bulky N-heterocyclic carbenes are shown to stabilize paramagnetic and electron-poor species sufficiently for their crystallographic characterization.
- Olivier Back
- , Bruno Donnadieu
- & Guy Bertrand
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Research Highlights |
Peptides make the difference
Microporous crystals formed by hydrogen-bonded dipeptides show different permeabilities for argon, nitrogen and oxygen.
- Anne Pichon
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Research Highlights |
Perovskites prove potent
Strontium-doped lanthanum perovskite oxides can help to remove harmful NOx pollution from diesel exhaust.
- Neil Withers
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Article |
An organic redox electrolyte to rival triiodide/iodide in dye-sensitized solar cells
Although the triiodide/iodide redox couple works efficiently in dye-sensitized solar cells it restricts functionality by absorbing visible light. Now, a disulfide/thiolate redox couple that has negligible absorption in the visible spectral range is presented, which in conjunction with a sensitized heterojunction, displays an efficiency of 6.4% under standard illumination test conditions.
- Mingkui Wang
- , Nathalie Chamberland
- & Michael Grätzel
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Article |
Catalyst selection based on intermediate stability measured by mass spectrometry
Identifying the best catalyst for a particular reaction traditionally involves testing a wide variety of metal and ligand combinations in standard reactions. Here, the best catalyst is found by using mass spectrometry to identify the least stable — and thus most reactive — intermediate in a dynamic mixture of complexes.
- Jeroen Wassenaar
- , Eveline Jansen
- & Joost N. H. Reek
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Research Highlights |
Twice as nice
A double-reductive alkylation of amides with two different organometallic compounds allows the direct formation of a tertiary alkylamines in one pot.
- Stephen Davey
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Research Highlights |
A solid combination
An efficient heterogeneous catalyst for the conversion of glucose into fructose has been prepared by incorporating tin centres into the framework of a zeolite.
- Anne Pichon
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Blogroll |
Blogroll: Smarten up
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In Your Element |
Green bismuth
Ram Mohan looks at how bismuth — a remarkably harmless element among the toxic heavy metals in the periodic table — has sparked interest in areas varying from medicinal to industrial chemistry.
- Ram Mohan
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News & Views |
Totally tubular peptide synthesis
The convergent total synthesis of the pore-forming polytheonamide B — a linear peptide natural product — pokes holes through perceived limitations in de novo peptide synthesis, and provides access to novel synthetic membrane channels.
- Craig J. Forsyth
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News & Views |
Under control
Macrocyclic compounds can serve as hosts for smaller organic molecules, but precise control over the uptake and release of the guests remains challenging. Now, a host–guest system has been built that responds to the addition of metal ions, showing promise for drug-delivery applications.
- Werner M. Nau
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News & Views |
Without a trace
A strong acid catalyst and a small change to one reactant have transformed a 37-year-old 'curiosity' into a useful chemical reaction that has great potential in organic synthesis.
- Sarah E. Steinhardt
- & Christopher D. Vanderwal
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News & Views |
Protons on tap
Electrochemistry has so far been mostly centred around measuring factors and coefficients. Through the reversible reduction and oxidation of an electrode coating formed from three-dimensional hybrid aniline–gold nanoparticles, it has now moved on to controlling the pH of a solution, thus triggering specific reactions.
- Reginald M. Penner
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Thesis |
Nurture Chemistry
In the sink-or-swim world of academia, Bruce C. Gibb considers what support structures should be put in place for those who have only just entered the water.
- Bruce C. Gibb
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Research Highlights |
Our choice from the recent literature
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Article |
The rational design of helium bonds
Helium is a reluctant participant when it comes to chemical reactions and bonding and it is one of only two stable elements for which there are currently no known crystalline derivatives. Now, based on a computational investigation, compounds containing helium atoms that form charge-shift, rather than covalent bonds have been proposed.
- Henry S. Rzepa
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Article |
Charge-transfer-induced structural rearrangements at both sides of organic/metal interfaces
Interfaces between organic molecules and metal surfaces have a key role in determining the performance of many emerging technologies. Now an intensive experimental study — supported by calculations — of tetracyano-p-quinodimethane molecules on a copper surface, reveals structural rearrangement of both the organic molecules and the surface atoms after charge transfer across the interface.
- Tzu-Chun Tseng
- , Christian Urban
- & Rodolfo Miranda
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Research Highlights |
Stable and able
A stable water-oxidation catalyst containing a cobalt oxide core has been made.
- Neil Withers
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Research Highlights |
Sticky situation
The sliding movement of the actin–myosin protein conjugate responsible for contracting muscles can be inhibited using a dendrimer that glues them together.
- Gavin Armstrong
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Review Article |
Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls
Rare-earth metal dialkyl complexes can be readily transformed into the corresponding cationic monoalkyl species — which have been shown to catalyse a range of (co)polymerization processes — as well as into polyhydride complexes that have unique structures and a rich reaction chemistry.
- Masayoshi Nishiura
- & Zhaomin Hou
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Article |
Quantum size effects in ambient CO oxidation catalysed by ligand-protected gold clusters
Gold nanoparticles can catalyse oxidation reactions in remarkably mild conditions and have excited much interest in recent years. With experimental studies disagreeing over the size of the most active nanoparticles, density functional calculations have now shown that limiting the particle size to below two nanometres is crucial.
- Olga Lopez-Acevedo
- , Katarzyna A. Kacprzak
- & Hannu Häkkinen
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Article |
Preparation of functionalized organoaluminiums by direct insertion of aluminium to unsaturated halides
The reactivity of organoaluminium reagents makes them particularly attractive nucleophiles for a wide range of organic reactions. Here, the use of metal halide catalysts provides access to functionalized organoaluminium reagents directly from the metal. The utility of these organoaluminium reagents is then demonstrated by their reaction with a wide variety of electrophilic coupling partners.
- Tobias Blümke
- , Yi-Hung Chen
- & Paul Knochel
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Article |
Self-assembly and optically triggered disassembly of hierarchical dendron–virus complexes
Viruses are ideal templates for engineering multifunctional materials. They can exhibit multiple copies of surface ligands and encapsulate inorganic and organic materials. Here, viruses are assembled into well-defined micrometre-sized objects by the addition of dendritic linkers. The linkers are designed to decompose on irradiation, which results in the release of the original virus particles.
- Mauri A. Kostiainen
- , Oksana Kasyutich
- & Roeland J. M. Nolte
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Article |
A ‘Texas-sized’ molecular box that forms an anion-induced supramolecular necklace
Macrocyles capable of hosting other molecules inside their hollow interiors have been used extensively to make threaded complexes and interlocked molecules. Now, a relatively large and flexible tetracationic macrocycle has been shown to bind anionic guests to form pseudorotaxanes that form extended structures in solution and the solid state.
- Han-Yuan Gong
- , Brett M. Rambo
- & Jonathan L. Sessler
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Article |
High-spin ground states via electron delocalization in mixed-valence imidazolate-bridged divanadium complexes
Single-molecule magnets are clusters of metal ions linked together by organic bridges, with properties typically arising from exchange coupling of unpaired metal electrons. In mixed-valence systems, another magnetic mechanism involving itinerant electrons can also occur and induce a high-spin ground state. Now, such electron delocalization has been observed through an imidazolate bridge — a common linker in metal-organic architectures — which may enable the construction of higher spin clusters or three-dimensional magnets.
- Bettina Bechlars
- , Deanna M. D'Alessandro
- & Jeffrey R. Long
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Article |
Million-fold activation of the [Fe2(µ-O)2] diamond core for C–H bond cleavage
Although enzymes are known to use diiron centres to cleave carbon–hydrogen bonds, preparing synthetic compounds that can break these strong, stable bonds has remained notoriously difficult. Now, converting a low-spin ‘diamond core’ iron–oxo biomimetic complex into its high-spin ‘open core’ counterpart has enhanced its C–H bond cleavage ability by over a million times.
- Genqiang Xue
- , Raymond De Hont
- & Lawrence Que Jr
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Research Highlights |
Turning on hydrocarbons
The intercalation of potassium into a simple aromatic hydrocarbon results in a new class of organic superconductors.
- Neil Withers
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Research Highlights |
Sunscreen size studies
A comparison of models for the sun-protection factor, transparency and production of reactive oxygen species leads to a prediction of the optimum size of titania nanoparticles for use in sunscreen.
- Stephen Davey
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Article |
Face-directed self-assembly of an electronically active Archimedean polyoxometalate architecture
A wide range of porous framework materials has been assembled with a modular approach that takes advantage of prefabricated structural building units (SBUs). Now, it has been shown that functional all-inorganic frameworks can be made from a macrocyclic polyoxometalate SBU — that has a built-in aperture approximately 1 nm in diameter — linked together with redox-switchable metal ions.
- Scott G. Mitchell
- , Carsten Streb
- & Leroy Cronin
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Article |
Loading and selective release of cargo in DNA nanotubes with longitudinal variation
Nanotubular structures made from different materials are being investigated for applications ranging from sensing to drug delivery, but controlling how they interact with ‘cargo’ molecules has proved challenging. Now, the selective uptake, precise positioning and triggered release of gold nanoparticles has been achieved with nanotubes assembled from triangular DNA building blocks.
- Pik Kwan Lo
- , Pierre Karam
- & Hanadi F. Sleiman
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Article |
Synergistic organocatalysis in the kinetic resolution of secondary thiols with concomitant desymmetrization of an anhydride
Chiral thiols and organosulfur compounds are important in many areas of chemistry but there are relatively few methods available for their efficient enantioselective synthesis. Here, a kinetic resolution of chiral thiols is reported along with a demonstration that a concomitant desymmetrization of the acylating agent is beneficial for the selectivity of both processes.
- Aldo Peschiulli
- , Barbara Procuranti
- & Stephen J. Connon
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Research Highlights |
Carbamate tunnel syndrome
Molecular dynamics simulations have revealed important mechanistic details about how carbamate is transported from one active site to another within in an enzyme.
- Gavin Armstrong
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Research Highlights |
Electron hopping in a hairpin
Charge transport through electron hopping has been observed between π–π stacked perylene derivatives incorporated into DNA hairpin scaffolds.
- Anne Pichon
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News & Views |
Ejecting electrons from water
The interactions of electrons and water molecules are not just of great fundamental interest but are also studied to understand the role electrons have in damaging biomolecules. Now using ultrafast photoelectron spectroscopy, key details about the energy and lifetime of the hydrated electron in bulk and at an interface have been determined.
- Daniel M. Neumark
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Article |
Binding energies, lifetimes and implications of bulk and interface solvated electrons in water
The existence of solvated electrons bound at the liquid/water surface has not, until now, been proved experimentally. Here, using ultrafast photoelectron spectroscopy, the existence, vertical binding energies and lifetimes of solvated electrons bound at the water-surface/vacuum interface, and in bulk solution, have been revealed.
- Katrin R. Siefermann
- , Yaxing Liu
- & Bernd Abel
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Research Highlights |
Racemization on the rack
Thermally stable stereoisomers can be interconverted by the application of a mechanical force using ultrasound irradiation.
- Stephen Davey
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Research Highlights |
The krypton factor
A krypton difluoride coordination compound — where it acts as a ligand to a bromine atom — has been synthesized and studied.
- Neil Withers
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