Themed collection Emerging Investigators 2012

This article reviews recent progress in the design and development of molecular complexes that can act as catalysts for the electrochemical reduction of CO₂.

We analyze the role of secondary metals in Pd-based catalysts for selective hydrogenation of alkyne-alkene mixtures and compare experimental studies, industrial documents and theoretical data performed over the last few years with our new results based on Density Functional Theory.

This review examines the range of spectroscopies applied to enzymes immobilised on electrode surfaces under conditions of direct electron exchange.

A structural perspective on distinct inhibition mechanisms of the proteasome by natural products that have been optimized throughout evolution.

pH-responsive nanogels are used as carriers for anti-GFP siRNA and IONPs. The endosomal acidic pH triggers the siRNA and IONPs release to the cytoplasm of GFP expressing HeLa cells.

Control of zinc oxide crystallite morphology and orientation in a thin film has been possible through the addition of a surfactant to the precursor.

Upon mixing of capsid protein and a conjugated polyelectrolyte virus-like particles are formed, which cluster depending on the molecular mass of this scaffold.

A rationally designed rht-MOF has been synthesized to investigate the effect of pore size and amine functionalization on CO₂ affinity.

β-Si elimination was attenuated by a cooperation of NHC-Ni and SiR₃. The scope is illustrated by a novel vinylsilane-α-olefin hydroalkenylation.

Vesicles containing complementary artificial phospholipids were aggregated and fused with the help of a Cu(I)-catalyzed 1,3-dipolar cycloaddition.

A field-effect mobility up to 0.1 cm² V^-1s^-1 has been achieved in P3HT films upon blending with dH-PTTP which forms crystals bridging large polymeric domains.

Synthesis of sulfated and unsulfated (glyco)peptide fragments of Hirudin P6 is described. The effect of O-glycosylation and tyrosine sulfation on thrombin binding and inhibitory activity was investigated.

Pressure causes solvent to be squeezed into Cu-btc, driven by compression and expansion of equatorial and axial Cu–O bonds.

Two quasi independent [Mn₇] clusters synthesized with a polypyrazolyl ligand are contained within a molecule and each exhibits SMM behavior.

Ionic currents through biological nanopores can be used to identify the four DNA bases at high alkaline pH and to measure the apparent pKa values of single nucleobases within immobilized DNA strands.

Copper-catalyzed 1,2-addition of Grignard reagents to enones has been achieved for the first time with high enantioselectivities and excellent yields.

The orthogonal amino acid reporter para-ethynylphenylalanine (PEP) allows cell-selective metabolic proteome labeling in heterogeneous cell populations.

Applying isothermal titration calorimetry (ITC), we show that weak and unspecific binding of primary alkylamines to the surface of ITO nanoparticles is sufficient to achieve long-term stabilisation against agglomeration.

Multi-purpose self-reactive branched copolymer surfactants are shown to simultaneously stabilize emulsions, self-crosslink around droplets and provide predetermined surface functionality.

An iron-catalysed, hydride-mediated reductive cross-coupling has been developed and used to prepare a range of alkanes from vinyl halides and Grignard reagents.

Polyacrylamide hydrogels can be used as chemically and physically defined substrates for bacterial cell studies.

Dinuclear Pd and Pt complexes that exhibit d⁸–d⁸ interactions with significant metal–metal bonding character between dicationic metal centers are reported.

Bromous and iodous halogen bonds are symmetric in solution as demonstrated by a combined solution NMR spectroscopic and computational investigation.

Peptide-conjugates can conveniently be synthesized by coupling of supramolecular building blocks to peptide sequences through chemoselective chemistry, and they self-assemble into fibrous structures.

Fully ab initio large-scale calculations of archetypical ionic liquids establish importance of dispersion interactions and many-body effects in Coulombic systems.

Parahydrogen induced polarisation (PHIP) of a polymer is reported which displays signal enhancements of up to 1500-fold, thus opening new potential avenues for polymeric molecular imaging.

Ru^II(arene) anticancer compounds functionalized with a maleimide moiety interact selectively with thiol-containing biomolecules.

Pyrolytic graphite particles modified with hydrogenase and an NAD⁺/NADH cycling enzyme provide a modular heterogeneous catalyst system for regenerating nicotinamide cofactors using H₂ and H⁺ as electron source or sink.

Specifically fluorinated analogs of the tumor-associated TF⁶-MUC1(20) glycopeptide antigen are prepared for glycomimetic-based vaccines and show high binding affinities towards mouse serum antibodies from immunizations with structurally related fluorinated and non-fluorinated MUC1-TTox conjugates.

Allylation of ketones is accomplished using allyl acetate, a rhodium catalyst and bis(pinacolato)diboron.

Differences in degrees of delocalization in carbocations involved in the formation of several terpene natural products are revealed.

We report a one-step photocatalytic synthesis method of dendritic silver nanostructures. Their excellent Raman enhancement allows dilute analyte detection via surface-enhanced Raman spectroscopy.

The growth and surface oxidation of single Cu nanoparticles were monitored by dark-field microscopy and plasmon resonance Rayleigh scattering spectroscopy.

The first four-coordinate titanium parent imide complex has been prepared via a transient titanium nitridyl intermediate.

Derivitization of membrane surfaces via copper-free click chemistry was achieved and characterized via an assay involving liposome biotinylation and microplate immobilization.

Sequential borylation of a first aryl iodide using a dialkylaminoborane followed by a Suzuki–Miyaura cross coupling of second aryl iodide ended up with an efficient, selective and practical synthesis of unsymmetrical biaryls.

High-nuclearity cerium oxide clusters do exist: condensation reactions starting from cerium coordination polymers result in ligand-terminated {Ce^III/IV₁₀} and {Ce^III/IV₂₂} oxide clusters, which exhibit formation and structural aspects that are partly similar and partly contrary to classical polyoxometalate chemistry.

Diverse alkyllysine-containing peptides can be readily prepared via solid-phase Dess–Martin oxidation/reductive amination. Lysine alkylation can dramatically alter ionization efficiency of peptides.

Lanthanide ions Yb³⁺ and Tb³⁺ induce pseudo-contact NMR shifts on the signals of the molecules forming the nanoparticle-coating monolayer, this allows the investigation of the average structure of the ligands in the monolayer and also the mapping of the position of other organic molecules bound to it.

The synthesized tribenzotriquinacenes carrying up to six ortho-substituents serve as models and starting materials for defective carbon networks.

The one-pot combination of ATRP with CuACC yields chemically addressable, multifunctional Giant Amphiphiles in excellent yields and polydispersity.

The synthesis and characterization of a new class of hydrogen bond surrogate α-helix mimetics, based on a thioether linkage, is described.

Two-dimensional dendritic Au nanostructures are synthesized; their unique pattern suggests strong charge repulsion among primary Au nanocrystals during aggregation.

Two stage self-assembly of novel coronene monoimide (CMI) based gels that results in resurfacing of monomer emission in the aggregated state is reported. This process is attributed to a frustrated head–head dipolar assembly forced by hydrogen bonding.

Changing the core heteroaromatic electronic structure of porphycene greatly enhances Soret two-photon absorption, via resonance enhancement with Q-band states.

[Cp₂Dy(thf)(μ-Cl)]₂ was synthesized from [Cp₂Dy(μ-Cl)]_n, which crystalizes as two polymorphs, a dimer with n = 2 and a chain-like polymer with n = ∞. All three compounds show slow relaxation of magnetization, and in [Cp₂Dy(thf)(μ-Cl)]₂ the quantum tunnelling was found to be exchange-biased.

Polyanions with controlled microstructures were synthesized by sequence-controlled copolymerization of tert-butyl 4-vinyl benzoate with N-substituted maleimides, followed by a selective hydrolytic step.

A novel class of ionic liquids (ILs), exhibiting high selectivity towards boron species as well as the ability to phase separate from water, were synthesized from N-methyl-D-glucamine.

A sensor protein presenting a pseudo-amyloid structure can preferentially detect oligomeric assemblies of Aβ1-42 wild-type and its mutants.

Thioamides quench tryptophan and tyrosine fluorescence in a distance-dependent manner and thus can be used to monitor the binding of thioamide-containing peptides to proteins.

Continuous flow synthesis of conjugated polymers resulted in excellent molecular mass distributions with significantly reduced reaction times compared to conventional batch reactions.

A series of calix[4]arene-supported Ln^III₆ clusters are synthesised under facile bench top conditions. These represent an important entry into polynuclear lanthanide cluster chemistry with these versatile ligands, and based on prior studies, suggest that a Ln^III-calix[4]arene fragment may be used in the construction of alternative assemblies.

A novel method is reported to afford macrocyclic organo-peptide hybrids via reaction between a trifunctional synthetic precursor and an intein-fusion precursor protein.

We report the design and evaluation of a library of chiral bifunctional organocatalysts in which the distance between the catalytically active units can be systematically varied.

“Caged” macromolecular building blocks can endow mesoporous thin films with light responsiveness and lead to the creation of functional hybrid ensembles with phototriggered permselective properties.

9-Fluorenylmethyl thioesters are rapidly deprotected and in situ reacted further with sulfonylazides to give N-acyl sulfonamides with 3.5% DBU/DMF at room temperature.

We describe the synthesis, characterization and manipulation of small peptide-based dynamic combinatorial libraries, in which product formation is governed both by autocatalytic efficiency of the molecules and their thermodynamic stability.

Sub-15 nm BaZr_xTi_1−xO₃ nanocrystals synthesized at room temperature exhibit noncentrosymmetric regions whose volume fraction depends on the chemical composition of the nanocrystal.

In the presence of substoichiometric Pd(OAc)₂, carboxylic acids undergo highly regio- and stereoselective additions to ynamides to provide α-acyloxyenamides.

The synthesis and reactivity of a novel uranium organometallic complex is described. Its stability is derived from saturation of the uranyl equatorial plane by “ate” complex formation.

An efficient synthetic route is proposed to produce the biosynthetic precursor for the specific labelling of Ile methyl-γ₂ groups in proteins.

A 2-nitrobenzyl ether protects a hydroxyl functional group and prevents lattice interpenetration in a cubic MOF derived from zinc(II).

An ion-selective electrode is used to measure rapid kinetics in droplet-based microfluidic devices.

A new method for the synthesis of an organic-soluble insulated molecular wire with permethylated cyclodextrin via click polymerization was developed.

A sodium zincate more accustomed to Brønsted basic applications, has been utilised in single electron transfer reactions with TEMPO and chalcone.

Reaction of [HP₇]²⁻ with one equivalent of bis(2,6-diisopropylphenyl)carbodiimide yielded the exo-functionalized cluster [P₇C(NDipp)(NHDipp)]²⁻ (Dipp = 2,6-diisopropylphenyl) - a unique example of an amidine-functionalized Zintl cluster anion.

Atom arrangement strategy for designing a turn-on ¹H magnetic resonance probe.

We highlight the impact of surfactants, routinely used in the fabrication of graphene, which can significantly influence the performance of supercapacitors.

The tambjamine alkaloids and related synthetic analogs are potent transmembrane anion tranporters promoting bicarbonate/chloride exchange in model phospholipid liposomes and discharging pH gradients in living cells.

A new approach to additions of silicon nucleophiles to imines was developed, based on the phase-transfer of phenoxides, overcoming the inability of amide adducts in promoting the reactions.