Themed collection Emerging Investigators 2013
Contributors to the Emerging Investigators Issue 2013
Locked nucleic acid: tighter is different
This viewpoint briefly reviews the impact of Locked Nucleic Acid (LNA) oligonucleotides, first described in a ChemComm paper in 1998. A number of unique applications in oligonucleotide biotechnology have been made possible by the high binding affinity and specificity of LNA, and these provide the main focus of the viewpoint.
Shape-persistent H-bonded macrocyclic aromatic pentamers
The latest advances on the design, synthesis, structure and function of shape-persistent H-bonded macrocycles are summarized.
Recent progress in research on anion-responsive pyrrole-based π-conjugated acyclic molecules
This article summarises recent progress in the study of acyclic oligopyrrole molecules that show anion-binding behaviours, focusing on dipyrrolyldiketone boron complexes.
Expanding coordination chemistry from
protein to protein assembly
Unique chemical properties of typical protein assemblies such as cages, tubes, and crystals are described in this review.
Ion-based materials comprising planar charged species
Materials comprising planar units have the propensity to form stacking assemblies with nanoscale architectures and intriguing properties.
Not a molecule, not a
polymer, not a substrate… the many faces of graphene as a chemical platform
How graphene chemical properties can be exploited to develop original science, innovative materials and new technological applications.
Dissociation and hierarchical
assembly of chiral esters on metallic surfaces
Scanning tunnelling microscopy is used to investigate the reactivity of a chiral ester on metallic surfaces at the single molecule level.
porphyrin-grafted porous silicon nanoparticles for photodynamic therapy
Non-toxic porous silicon nanoparticles carry porphyrin covalently attached to their surface inside breast cancer cells for a more efficient photodynamic effect.
Ligand discrimination of myoglobin in solution: an iron L-edge X-ray absorption study of the active centre
Iron L-edge X-ray absorption spectra of the active centre of myoglobin in the met-form, in the reduced form and upon ligation to O2, CO, NO and CN are presented.
Microwave synthesis of Au–Rh core–shell
nanoparticles and implications of the shell thickness in hydrogenation catalysis
A microwave-assisted heating method allows for the convenient and reproducible synthesis of defined Au–Rh core–shell metallic nanoparticles with tuneable shell thicknesses.
A new two-dimensional oligothiophene end-capped with alkyl cyanoacetate groups for highly efficient solution-processed organic solar cells
A new two-dimensional molecule DCA3T(VT)BDT affords a highly efficient organic solar cell with a high power conversion efficiency of 4% and a high fill factor of up to 0.63.
Enantioselective trapping of phosphoramidate ammonium ylides with
imino esters for synthesis of 2,3-diaminosuccinic acid derivatives
A highly enantioselective trapping of protic phosphoramidate ammonium ylides with α-imino esters has been developed to provide 2,3-diaminosuccinic acid derivatives.
The role of copper in catalytic performance of a Fe–Cu–Al–O
catalyst for water gas shift reaction
Catalytic in situ studies using ambient pressure X-ray photoelectron spectroscopy suggested a strong Fe3O4–Cu interface interaction which promotes catalytic activity of water gas shift on Fe–Cu–Al–O catalyst upon pretreatment in H2 at 350 °C which exhibits an activity 40% higher than a physical mixture of Fe–Al–O and Cu–Al–O catalysts.
Divergent reactivity of nitric oxide with metal–metal quintuple bonds
Reactions of NO with the quintuple bonded chromium and molybdenum amidinate dimers, respectively, gave dichromium nitrosyl nitrito amidinato complexes, and the quadruple bonded dimolybdenum nitrito amidinato species with a paddlewheel configuration.
Serum albumin enhances the membrane activity of ZnO nanoparticles
Serum albumin stabilizes the nanoscale size distribution of ZnO nanoparticles in aqueous dispersions by forming a protein corona around the particles. This in turn enhances the impact of these nanoparticles on the structure and morphology of lipid membranes.
Exploration of biosynthetic access to the shared precursor of the fusicoccane
The shared precursor of the fusicoccane family of diterpenoids was microbially synthesized on a preparative scale employing engineered yeast.
Combinatorial ionic catch-and-release
oligosaccharide synthesis (combi-ICROS)
A combinatorial ionic-liquid-supported “catch-and-release” strategy for oligosaccharide synthesis (combi-ICROS) is reported. A series of β-(1→6) glucan di-, tri- and tetra-saccharides were synthesized in one pot to showcase the versatility of the strategy.
X-ray excitable luminescent
polymer dots doped with an iridium(III) complex
Cyclometalated iridium(III) complex-doped polymer dots were synthesized and shown to emit luminescence upon X-ray irradiation.
self-assembly and selective solvent vapour annealing: simplified processing of a photovoltaic blend
Orthogonal self-assembly was exploited to optimize the nanoscale arrangement of the poorly organized phase of an acceptor in a photovoltaic blend, without affecting the ordered structures formed by the donor.
Bridging π-coordination of
pyrrole and indole over a PdI–PdI bond
π-Coordination of pyrrole or indole to a dinuclear PdI–PdI center is revealed. The dinuclear sandwich PdI–PdI complexes of pyrrole, N-methylpyrrole, or indole were synthesized and structurally characterized. Indole employs the carbons of the six-membered ring in bridging π-coordination to a PdI–PdI center.
Crystal structure and carrier transport properties of a new semiconducting 2D coordination
polymer with a 3,5-dimethylpiperidine dithiocarbamate ligand
A new semiconducting coordination polymer having an infinite 2D structure has been prepared.
Enhanced thermoelectric performance in TiNiSn-based half-Heuslers
Thermoelectric figures of merit, ZT > 0.5, have been obtained in arc-melted TiNiSn ingots containing excess Ni.
Multicomponent self-sorting of a Pd7 molecular boat and its use in catalytic Knoevenagel condensation
A unique three-component self-assembly of a cis-blocked 90° Pd(II) acceptor with a mixture of tri- and tetra-imidazole donors led to the self-sorting of a Pd7 molecular boat, which was found to catalyse Knoevenagel condensations in aqueous media.
Curcumin as an amyloid- indicator dye in E. coli
Curcumin is an amyloid-specific dye in E. coli and binds to curliated whole cells and isolated curli fibers.
Biomimetic cell-mediated three-dimensional
assembly of halloysite nanotubes
Biomimetic architectural assembly of clay nanotube shells on yeast cells was demonstrated producing viable artificial hybrid inorganic-cellular structures (armoured cells). These modified cells were preserved for one generation resulting in the intact second generation of cells with delayed germination.
Unraveling the local energetics of transport in a
polymer ion conductor
Diffusion activation energy measurements provide sub-nm insights into water and proton transport dynamics in a hydrated conducting polymer.
reduction facilitated by a trianionic pyridine(diimine) ligand
Reduction of Cp*2UI(THF) with KC8 in the presence of a pyridine(diimine) ligand (PDI) results in the formation of Cp*U(PDI)(THF), which features a triply reduced PDI ligand.
Time-programmed helix inversion in phototunable liquid crystals
Helix inversion of cholesteric liquid crystals can be time-programmed by a judicious choice of molecular dopants.
A family of simple
benzene 1,3,5-tricarboxamide (BTA) aromatic carboxylic acid hydrogels
Hydrogel forming family of benzene 1,3,5-tricarboxamide (BTA) aromatic carboxylic acid derivatives exhibiting consistent gel formation through a pH trigger.
cyclopropanes with Lawesson's and Woollins' reagents: formation of bisthiophenes and unprecedented cage-like molecules
A method to convert furan-derived donor–acceptor cyclopropanes into bisthiophenes and unusual cage-like compounds by the action of Lawesson's reagent was developed.
Controlled synthesis of non-epitaxially grown Pd@Ag core–shell
nanocrystals of interesting optical performance
Pd@Ag core–shell nanocrystals are synthesized through a seed mediated method with Ag shells formed in a non-epitaxial growth manner.
Controlled folding of a novel electroactive polyolefin via multiple sequential orthogonal intra-chain interactions
We report the synthesis of an electroactive polyolefin and demonstrate through SEC-MALS and DLS that this polymer can be folded in a controlled fashion using sequentially activated noncovalent and covalent intra-chain interactions.
N-Propargyloxycarbamate monosaccharides as metabolic chemical reporters of carbohydrate salvage pathways and
N-propargylcarbamate monosaccharides display altered metabolic preferences as metabolic chemical reporters of mammalian glycosylation.
Cyclotetraazocarbazole – a multichromic molecule
A macrocyclic multiphotochromic cyclotetraazocarbazole is presented showing a distinct color change upon irradiation, pH-change or change of temperature.
Divergent reaction pathways of tris(oxazolinyl)borato zinc and magnesium silyl compounds
A magnesium silyl and CO2 react to form a monomeric silanecarboxylate. The analogous reaction of a zinc silyl and CO2 affords a zinc formate, where the zinc silanecarboxylate is a kinetically plausible intermediate.
Aerobic oxidative N-dealkylation of tertiary amines in aqueous solution catalyzed by rhodium porphyrins
Aerobic oxidative N-dealkylation of a variety of aliphatic tertiary amines and anilines catalyzed by (TSPP)Rh(III) is achieved in aqueous solution using dioxygen as the sole oxidant.
Designer nanojunctions: orienting shaped
nanoparticles within polymer thin-film nanocomposites
We demonstrate a new method for assembling plasmonic materials by tailoring nanocrystal shape and surface chemistry to design specific nanojunctions.
Directed organization of
gold nanoparticles in polymer coatings through infrared-assisted evaporative lithography
Infrared-assisted evaporative lithography (IRAEL) is presented as an emerging technology to direct the assembly of gold nanospheres (AuNSs) into large-scale superstructures within colloidal polymeric coatings.
Redox active aluminium(III) complexes convert CO2 into MgCO3 or CaCO3 in a synthetic cycle using Mg or Ca metal
Using concomitant redox and acid–base reactivity, conversion of CO2 into MgCO3 or CaCO3, via regenerable (IP−)2Al(OH), is presented (IP = α-iminopyridine).
Surfactant controlled aggregation of conjugated polyelectrolytes
We investigate the interaction between conjugated polyelectrolytes and surfactants in solution and solid phases.
Electric field-induced hole transport in
copper(I) thiocyanate (CuSCN) thin-films processed from solution at room temperature
Hole transport is observed in thin-film transistors based on copper(I) thiocyanate (CuSCN) processed from solution at room temperature.
Light-induced stereospecific intramolecular [2+2]-cycloaddition of atropisomeric 3,4-dihydro-2-pyridones
Atropisomeric 3,4-dihydro-2-pyridones undergo stereospecific [2+2]-photocycloaddition in solution with high stereoselectivity (ee >98% and de >96%) in the product.
reduction of dioxygen catalysed by dinuclear cobalt complexes bridged by bis(terpyridyl)anthracene
We have prepared dinuclear cobalt complexes 1 and 2 linked in a co-facial configuration by bis(terpyridyl)anthracene as catalysts for chemical and electrochemical four-electron reductions of dioxygen.
Hydrometallation-asymmetric conjugate addition: application to complex molecule synthesis
This manuscript demonstrates that alkenes undergo hydrometallation-conjugate addition processes to give natural products and functionalized steroid derivatives.
Artificial repressors for controlling gene expression in bacteria
Expression of transcription activator-like effectors (TALEs) can be used to regulate Escherichia coli gene expression via inhibition of transcription events.
π-Core tailoring for new high performance thieno(bis)imide based n-type molecular semiconductors
The synthesis and characterization of two thieno(bis)imide based n-type molecular semiconductors with electron mobilities of up to 0.3 cm2 V−1 s−1 are described.
Intracellular nitric oxide delivery from stable NO-polymeric
The encapsulation of S-nitrosoglutathione into polymeric nanoparticles substantially improves NO stability in aqueous media without affecting the efficacy of intracellular delivery.
A gold(III) porphyrin complex as an anti-cancer candidate to inhibit growth of cancer-stem cells
A cytotoxic gold(III) complex of meso-tetraphenylporphyrin ([Au(TPP)]Cl, denoted gold-1a) blocks the self-renewal ability of cancer stem-like cells and shows appealing safety pharmacological profiles in rodents.
Computational insights on the mechanism of the catalytic hydrogenation with BINAP–diamine–Ru complexes: the role of base and origin of selectivity
The catalytic features of the BINAP–diamine–Ru trio uncovered at the molecular level.
Rhodium-catalyzed cysteine modification with diazo reagents
A simple rhodium(II) complex catalyzes cysteine modification with diazo reagents.
The unexpected and facile molybdenum mediated formation of tri- and tetracyclic pentathiepins from
pyrazine- alkynes and sulfur
Reported is a novel family of pentathiepino-pyrrolo[1,2-a]pyrazine derivatives formed by the reaction of alkynyl-substituted heterocyclic precursors with elemental sulfur in the presence of molybdenum oxo bis-tetrasulfide under very mild conditions.
A multimodal, β-amyloid-targeted contrast agent
A multimodal, β-amyloid-targeted contrast agent was synthesized that interacts with β-amyloid aggregates producing changes in relaxation rate and fluorescence emission.
A disulfide-linked conjugate of ferrocenyl chalcone and silicon(IV) phthalocyanine as an activatable photosensitiser
A novel disulfide-linked ferrocenyl phthalocyanine has been prepared which is activated by dithiothreitol resulting in enhanced fluorescence emission, singlet oxygen production and in vitro photocytotoxicity.
Effective phosphorescence quenching in borylated PtII ppy-type phosphors and their application as I− ion sensors in aqueous medium
The first example of I− ion sensors using borylated-PtII phosphors was reported showing high sensitivity and selectivity in aqueous medium.
Synthesis and structure of a hydrogenated zinc hemiporphyrazine
A zinc hemiporphyrazine exhibits reversible hydrogenation chemistry that may enable future applications in hemiporphyrazine-based catalysts and/or hydrogen storage devices.
The tandem intermolecular hydroalkoxylation/claisen rearrangement
The Au(I)-catalyzed intermolecular hydroalkoxylation of alkynes with allylic alcohols to provide allyl vinyl ethers that subsequently undergo Claisen rearrangement is reported.
Stereoselective synthesis of aminoindanols via an efficient cascade aza-Michael–aldol reaction
An efficient organocatalyzed aza-Michael–aldol cascade strategy for the synthesis of a variety of 3-amino-1-indanols has been developed.
Reactions of a tungsten–germylyne complex with
alcohols and arylaldehydes
Germylyne complex Cp*(CO)2WGeC(SiMe3)3 reacted with two molecules of arylaldehydes to give base-stabilised alkoxy(germylene) complexes via C–H bond activation and hydrogermylation.
Vibrational spectroscopic observation of ice dewetting on MgO(001)
Specific hydroxyl vibrations of the water monolayer on MgO(001) allowed the dewetting of ice to be probed by vibrational spectroscopies.
Internal Lewis acid assisted
ureas: tunable hydrogen bond donor catalysts
The strategic incorporation of Lewis acids on urea scaffolds yields tunable hydrogen bond donor catalysts benefiting from enhanced activity.
nanotubes: A potential 3D cathode material for Li-ion micro batteries
This work presents a novel approach for synthesizing self-supported TiOxSy nanotubes as a potential cathode material for 3D Li-ion microbatteries.
Batch to flow deoxygenation using visible light photoredox catalysis
Mild and efficient deoxygenation protocol for primary and secondary alcohols with exceptional functional group tolerance.
Formal γ-alkynylation of
ketones via Pd-catalyzed C–C cleavage
A direct Pd-catalyzed coupling of tert-cyclobutanols and bromoacetylenes via C–C cleavage gives access to rather elusive γ-alkynylated ketones.
A colorimetric logic gate based on free
gold nanoparticles and the coordination strategy between melamine and mercury ions
A colorimetric logic gate based on free gold nanoparticles is presented with melamine and Hg2+, as well as its colorimetric detection of Hg2+ with good selectivity and sensitivity.
Synthesis, structure and reactivity of cyclopropenyl-1-ylidene stabilized S(II), Se(II) and Te(II) mono- and dications
The syntheses and structural characterization of carbene-stabilized chalcogen centred mono- and dications employing a reverse electron demand onio-substitutent transfer strategy are reported.
Comparison of the predictive performance of the Bell–Evans, Taylor-expansion and statistical-mechanics models of mechanochemistry
Two simple models yield usefully accurate extrapolations of the kinetic stability of cyclobutene and cyclopropane moieties in a stretched polymer from strain-free parameters.
Schischkiniin support studies: synthetic access to 1,1′-bisindoles
Diallylated hydrazobenzenes undergo two simultaneous Mori–Ban cyclizations, providing the first general synthetic route to 1,1′-bisindoles.
A Ni@ZrO2 nanocomposite for
ethanol steam reforming: enhanced stability via strong metal– oxide interaction
This communication describes the rational design of a highly active and stable Ni@ZrO2 nanocomposite for catalytic hydrogen production via steam reforming of ethanol.
Rapid synthesis of oligomannosides with orthogonally protected monosaccharides
Synthesis of mannose building blocks with orthogonal protection leads to formation of linear/branched tri-, penta- and heptasaccharides.
About this collection
Welcome to the ChemComm Emerging Investigators Issue 2013. This is the third edition of this themed collection and is dedicated to internationally recognised, up-and-coming scientists from around the globe.