Themed collection 2014 Emerging Investigators

We highlight some of the less discussed consequences of mechanical bonding for the chemical behaviour of catenanes and rotaxanes, including striking recent examples where molecular motion controls chemical reactions.

Recent achievements in the area of metal–metal multiple bonding are highlighted using C₃-symmetric systems as a model to better understand the fundamental aspects of multiple bonds featuring first row transition metals.

This feature article presents a brief review on the linear neutral platinum–acetylide moiety, trans-Pt(PR₃)₂(CCR′)₂.

With some critical biological considerations, biomolecule-protected gold and silver nanoclusters were identified to be suitable for biomedical applications, and efficient synthetic strategies and potential biomedical applications of these nanoclusters were discussed.

This feature article reviews the recent progress in the construction of cavity-cored supramolecular metallodendrimers via coordination-driven self-assembly.

Deuterated sugars that are transported into mycobacteria can be detected using ion beam (nuclear reaction) analysis.

Mn₄(μ-NHPh)₄(μ-PhNNPh-κ²N,N′)₂(py)₄ (3) is synthesized via self assembly from fragments or via HAT to Mn₄(μ-NHPh)₂(μ₃-PhNNPh-κ³N,N′)₂(μ-PhNNPh-κ²N,N′)(py)₄ (2) (R = SiMe₃).

There has been significant interest in the use of bioorthogonal inverse Diels–Alder cycloadditions in molecular imaging. We have developed metal chelating tetrazine probes that extend tetrazine cycloadditions to the convenient and generator produced positron emitting isotope gallium-68 (⁶⁸Ga).

A simple approach to enhancing the activity and stability of organophosphorus hydrolase (OPH) is developed based on interactions between the hydrophobic poly(propylene oxide) (PPO) block of amphiphilic Pluronics and the enzyme.

Short lived reactive intermediates during photoinduced multielectron transfer have been studied by in situ UV-vis and RR spectro-electrochemistry revealing the impact of individual electronic transitions on the efficiency of a H₂ evolving photocatalyst.

One nanometre wide carbon nanoreactors are utilised as the reaction vessel for catalytic chemical reactions on a preparative scale.

The aggregation of amyloid-β protein (1–42) is studied at experimental concentrations using all-atom molecular dynamics simulations.

Binding behaviors of streptavidin were investigated with different lateral packing densities of biotin-functionalized non-biofouling pOEGMA brushes, synthesized by surface-initiated polymerization from mixed SAMs.

A novel ruthenium bis(pyrazolyl)borate catalyst exhibits useful reactivity in ammonia borane dehydrogenation and water oxidation. It also enables unprecedented cooperative reduction reactivity in which boron and ruthenium centers work in concert to effect surprisingly selective nitrile reduction.

Small diameter Au NPs and large diameter Al NPs are dispersed into the photoactive layer of OPVs in order to synergistically contribute to optical absorption enhancement by plasmonic and scattering effects respectively.

The photoreduction of Zn(II) to Zn metal catalyzed by 8-hydroxyquinoline derivatives is reported.

Non-fluorescent nanoparticles formed via self-assembly of a perylene-diimide behave as fluorogenic probes that give a dosage-dependent green or red fluorescence in cells. Photo-irradiation allows us to achieve multicolour labelling.

We report the synthesis of squaraine dyes under mild conditions by carbodiimide activation of squaric acid or semi-squaraine dyes.

Mutations off the dominant electron-transfer pathways have strong effects on the redox reactivity of cytochrome c.

The self-assembly of an anionic polyoxometalate (POM) with cationic π-conjugated polyelectrolytes (CPE) leads to hybrid supramolecular networks whose dimensionality is controlled by the chain length and steric charge distribution.

An efficient approach toward the synthesis of the 6,6,5,7-tetracyclic core of the daphnilongeranin B, a Daphniphyllum alkaloid, is reported.

Dye-sensitized solar cells comprised of supramolecular light-harvesting zinc-phthalocyanine⋯peryleneimide dyads on TiO₂ films generate photoelectricity throughout the 300–650 nm region with the power conversion efficiency reaching up to 2.3% and the incident-photon-to-current-efficiency up to 40% under one-sun conditions.

A small molecule was designed for reactivity toward Cu(II)–amyloid-β over Zn(II)–amyloid-β, which will expand on the development of chemical tools to uncover the role of metal–Aβ species in Alzheimer's disease.

A simple yet general approach for modifying metal oxide surfaces using polar compounds in a non-polar polarizable solvent is presented.

Under hydrostatic pressure, crystals of silver tricyanomethanide actually expand in two orthogonal directions.

A Lewis acid-catalyzed stereoselective [3+2] annulation of crotylsilanes with iminooxindoles is reported to access 2,3′-pyrrolidinyl spirooxindoles with four stereocenters.

Through interior design, the optical properties of bimetallic nanocrystals can be facilely manipulated.

Pyridine-2-thiolate tin(IV) compounds were shown to chelate Pd(0) in a pincer-like fashion with formation of penta- and hexacoordinate tin compounds.

Seeing is believing – visualizing magnetic exchange coupling across the molecule–substrate spin-interface by X-ray photo-emission electron microscopy.

Addition of R₃Si–H–B(C₆F₅)₃ to heteroarenes leads to surprisingly complex and substrate dependent mixtures due to competing dehydrosilylation, hydrosilylation and hydrogenation.

Platinum- and iridium-catalyzed cycloisomerizations have been achieved that feature unique C–C bond migrations onto the metal carbene intermediate.

A porous metal–metalloporphyrin framework, MMPF-9, which features a high density of active sites in the nanoscopic channels, can efficiently catalyze the conversion of CO₂ into cyclic carbonates under ambient conditions.

A label-free, oligonucleotide-based, switch-on luminescence detection method for T4 polynucleotide kinase activity has been developed using a novel G-quadruplex-selective luminescent Ir(III) complex probe.

A series of non-Grignard Mg-electrolytes with various para-substituents was synthesized starting from commercially-available phenols.

This paper describes a powerful and versatile new approach to oxide–carbide–carbon or oxide–nitride–carbon nanocomposites from sol–gel precursors.

A tandem solar cell device whose sub-cells are fabricated exclusively from small molecules (SMs) through both solution-processed and vacuum-processed deposition techniques is described.

The combination of aptamers, depolymerizable poly(carbamates), and paper enables selective, sensitive, and quantitative assays for heavy metal contamination of drinking water using only measurements of time as the readout.

Poly(pentafluorophenyl acrylate) was covalently grafted to surfaces and used as a scaffold for postpolymerization modification, generating spatially controlled chemical functionality.

Group 3 metal (E)-stilbene complexes supported by a ferrocene diamide ligand were synthesized and characterized. Experimental and computational results indicated that the double bond was reduced and not a phenyl ring, in contrast to a previously reported uranium (E)-stilbene complex.

A method based on mass spectrometry was developed to follow chemical modifications applied to phage-encoded polypeptide libraries.

A metal-free, photo-induced C–O bond formation methodology was developed to construct tetrahydroxanthones. This mild and efficient methodology was based on intramolecular oxygen trapping of the reactive species produced by photolytic activation of a C–Cl bond.

When an overcharging battery reaches a potential that matches the oxidation potential of redox shuttle electrolyte additives such as phenothiazine derivatives, the additives oxidize, shuttling between electrodes in radical cation and neutral forms, mitigating excess current, thus stabilizing voltage.

Platinum(II) 1,5-cyclooctanediyldi(2-pyridyl)borates react with O₂via C(sp³)–H bond cleavage and stepwise C–C and CC coupling of the borate ligand.

Dinaphtho[2,3-b:2′,3′-d]furan (DNF–V) derivatives with high blue emission in solid have been facially synthesized by using dehydration as a key step. A solution-crystallized thin film transistors based on alkylated DNF–V derivatives showed an excellent carrier mobility of more than 1 cm² V⁻¹ s⁻¹.

A cell co-culture system is described that is simple to construct and is compatible with standard cellular and molecular assays.

The discovery that plant smoke contains germination stimuli, named karrikins, has now led to the identification of a new role for these signals as quorum sensing modulators.

We report the viscosity imaging of the plasma membrane of live cells using a new targeted BODIPY-based molecular rotor.

A hydrogen bonded organic framework displayed a capacity for accommodating and releasing guest molecules.

A unique strategy to synthesize β-alkenyl-α-amino-enones via catalytic C–H/alkyne coupling is described.

Herein we present the synthesis of fluorescent 2-acetylbenzeneboronic acids that undergo B–N promoted conjugation with lysozyme and N-(2-aminoethyl) folic acid (EDA-FA), generating conjugates that are selectively recognized and internalized by cancer cells that over-express folic acid receptors.

Red-shifting the absorption of norbornadienes (NBDs), into the visible region, enables the photo-isomerization of NBDs to quadricyclanes (QCs) to be driven by sunlight.

Gauging the trans effect of phenolate.

Simple quenching method to synthesize mono- and bis-end-functionalized regioregular poly(3-hexylthophene)s using chalcogens is presented.

Solvent-free mechanochemical coupling provides pharmaceutically relevant sulfonyl-(thio)ureas, including anti-diabetic drugs tolbutamide, chlorpropamide and glibenclamide, rapidly and in high yield.

The facile gold-mediated skeletal rearrangement of [7]-helicene into a cationic polyaromatic hydrocarbon is described.

A method for monitoring in vitro polyketide synthesis has been developed whereby nonchromophoric polyketide products are made brightly fluorescent in a simple, rapid, inexpensive, and bioorthogonal manner through CuAAC with a sulforhodamine B azide derivative.

A neutral metal–organic supercontainer (MOSC) has been functionalized as an anionic container, leading to enhanced adsorption capacity for polar guests.

The final addition to the tris(azolyl)borate ligand family, tris(1,2,3-triazolyl)borate, has been synthesized.

Oxetane synthesis by intramolecular C–C bond formation efficiently provides 2-sulfonyloxetanes, which are further derivatised maintaining the oxetane ring intact.

Magnetic birefringence was used for in situ monitoring of the morphological changes in diamagnetic polymersomes during shape-transformation by dialysis.

The out-of-plane hole mobility in copper phthalocyanine is enhanced by face-on molecular stacking induced by graphene-templated growth.

A coumarin-based non-fluorescent probe can selectively react with 5-hydroxylysine-containing peptides, leading to a fluorescent tag.

A combined solution-phase and theoretical investigation reveals that Si–H can act as a fully neutral H-bond acceptor in solution, but only just.

Reaction of N-phenyl-pivalohydroxamic acid with Ce^III precursors leads to a homoleptic hydroxamate complex: Ce^IV[^tBuC(O)N(O)Ph]₄.

A cubic metal–organic framework with an unprecedented octanuclear secondary building unit (SBU) was isolated.

Fluorescent and biotinylated squalene–gemcitabine prodrug nanoparticles exhibiting high drug payloads have been prepared and successfully used to target different cancer cell lines.

A Rh-catalyzed cyclization of enynone, cyclopropenation of an alkyne and cyclopropene rearrangement cascade is accomplished using enynones as the carbene source.