Themed collection 2014 Emerging Investigators
Contributors to the Emerging Investigators Issue 2014
Structure of catalyst particles from in-situ electron microscopy: a web themed issue
Chemical consequences of mechanical bonding in catenanes and rotaxanes: isomerism, modification, catalysis and molecular machines for synthesis
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.
Metal–metal multiple bonding in C3-symmetric bimetallic complexes of the first row transition metals
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.
Linear neutral platinum–acetylide moiety: beyond the links
This feature article presents a brief review on the linear neutral platinum–acetylide moiety, trans-Pt(PR3)2(CCR′)2.
Engineering ultrasmall water-soluble gold and silver nanoclusters for biomedical applications
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.
Recent progress in the construction of cavity-cored supramolecular metallodendrimers via coordination-driven self-assembly
This feature article reviews the recent progress in the construction of cavity-cored supramolecular metallodendrimers via coordination-driven self-assembly.
Deuterated carbohydrate probes as ‘label-free’ substrates for probing nutrient uptake in mycobacteria by nuclear reaction analysis
Deuterated sugars that are transported into mycobacteria can be detected using ion beam (nuclear reaction) analysis.
Preparation of a “twisted basket” Mn4N8 cluster: a two-hydrogen-atom reduced analogue of the Mn4N8 pinned butterfly
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).
68Ga chelating bioorthogonal tetrazine polymers for the multistep labeling of cancer biomarkers
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).
Enhanced activity and stability of organophosphorus hydrolase via interaction with an amphiphilic polymer
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.
Resonance-Raman spectro-electrochemistry of intermediates in molecular artificial photosynthesis of bimetallic complexes
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.
Catalytic nanoreactors in continuous flow: hydrogenation inside single-walled carbon nanotubes using supercritical CO2
One nanometre wide carbon nanoreactors are utilised as the reaction vessel for catalytic chemical reactions on a preparative scale.
Early amyloid β-protein aggregation precedes conformational change
The aggregation of amyloid-β protein (1–42) is studied at experimental concentrations using all-atom molecular dynamics simulations.
Binding behaviors of protein on spatially controlled poly[oligo(ethylene glycol) methacrylate] brushes grafted from mixed self-assembled monolayers on gold
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 dual site catalyst for mild, selective nitrile reduction
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.
Synergetic plasmonic effect of Al and Au nanoparticles for efficiency enhancement of air processed organic photovoltaic devices
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.
Organocatalytic photoreduction of Zn(II) to zinc metal
The photoreduction of Zn(II) to Zn metal catalyzed by 8-hydroxyquinoline derivatives is reported.
Photo-tunable multicolour fluorescence imaging based on self-assembled fluorogenic nanoparticles
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.
Synthesis of squaraine dyes under mild conditions: applications for labelling and sensing of biomolecules
We report the synthesis of squaraine dyes under mild conditions by carbodiimide activation of squaric acid or semi-squaraine dyes.
Control of cytochrome c redox reactivity through off-pathway modifications in the protein hydrogen-bonding network
Mutations off the dominant electron-transfer pathways have strong effects on the redox reactivity of cytochrome c.
Charge-modulated self-assembly and growth of conjugated polyelectrolyte–polyoxometalate hybrid networks
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.
Potent, selective small molecule inhibitors of type III phosphatidylinositol-4-kinase α- but not β-inhibit the phosphatidylinositol signaling cascade and cancer cell proliferation
Synthesis of the 6,6,5,7-tetracyclic core of daphnilongeranin B
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 based on multichromophoric supramolecular light-harvesting materials
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 that displays marked reactivity toward copper– versus zinc–amyloid-β implicated in Alzheimer's disease
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.
Surface modification of metal oxides by polar molecules in a non-polar, polarizable solvent system
A simple yet general approach for modifying metal oxide surfaces using polar compounds in a non-polar polarizable solvent is presented.
Negative area compressibility in silver(I) tricyanomethanide
Under hydrostatic pressure, crystals of silver tricyanomethanide actually expand in two orthogonal directions.
Counterion effects in the catalytic stereoselective synthesis of 2,3′-pyrrolidinyl spirooxindoles
A Lewis acid-catalyzed stereoselective [3+2] annulation of crotylsilanes with iminooxindoles is reported to access 2,3′-pyrrolidinyl spirooxindoles with four stereocenters.
Manipulating the optical properties of symmetrically branched Au/Pd nanocrystals through interior design
Through interior design, the optical properties of bimetallic nanocrystals can be facilely manipulated.
Pyridine-2-thiolate bridged tin–palladium complexes with Sn(PdN2Cl2), Sn(PdN2S2), Sn(PdN2C2) and Sn(Pd2N4) skeletons
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.
Investigating magneto-chemical interactions at molecule–substrate interfaces by X-ray photo-emission electron microscopy
Seeing is believing – visualizing magnetic exchange coupling across the molecule–substrate spin-interface by X-ray photo-emission electron microscopy.
E–H (E = R3Si or H) bond activation by B(C6F5)3 and heteroarenes; competitive dehydrosilylation, hydrosilylation and hydrogenation
Addition of R3Si–H–B(C6F5)3 to heteroarenes leads to surprisingly complex and substrate dependent mixtures due to competing dehydrosilylation, hydrosilylation and hydrogenation.
C–C bond migration in the cycloisomerization of oxygen-tethered 1,6-enynes
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 featuring high-density active sites for chemical fixation of CO2 under ambient conditions
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.
Label-free luminescence switch-on detection of T4 polynucleotide kinase activity using a G-quadruplex-selective probe
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.
Enhanced oxidative stability of non-Grignard magnesium electrolytes through ligand modification
A series of non-Grignard Mg-electrolytes with various para-substituents was synthesized starting from commercially-available phenols.
A family of oxide–carbide–carbon and oxide–nitride–carbon nanocomposites
This paper describes a powerful and versatile new approach to oxide–carbide–carbon or oxide–nitride–carbon nanocomposites from sol–gel precursors.
Small molecule-based tandem solar cells with solution-processed and vacuum-processed photoactive layers
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.
A prototype point-of-use assay for measuring heavy metal contamination in water using time as a quantitative readout
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.
Direct grafting of poly(pentafluorophenyl acrylate) onto oxides: versatile substrates for reactive microcapillary printing and self-sorting modification
Poly(pentafluorophenyl acrylate) was covalently grafted to surfaces and used as a scaffold for postpolymerization modification, generating spatially controlled chemical functionality.
Group 3 metal stilbene complexes: synthesis, reactivity, and electronic structure studies
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.
Tracking chemical reactions on the surface of filamentous phage using mass spectrometry
A method based on mass spectrometry was developed to follow chemical modifications applied to phage-encoded polypeptide libraries.
A photo-induced C–O bond formation methodology to construct tetrahydroxanthones
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.
Overcharge performance of 3,7-disubstituted N-ethylphenothiazine derivatives in lithium-ion batteries
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.
Oxidative C(sp3)–H bond cleavage, C–C and CC coupling at a boron center with O2 as the oxidant mediated by platinum(II)
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.
Furan fused V-shaped organic semiconducting materials with high emission and high mobility
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 simplified culture system to examine soluble factor interactions between mammalian cells
A cell co-culture system is described that is simple to construct and is compatible with standard cellular and molecular assays.
Karrikins from plant smoke modulate bacterial quorum sensing
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.
A molecular rotor for measuring viscosity in plasma membranes of live cells
We report the viscosity imaging of the plasma membrane of live cells using a new targeted BODIPY-based molecular rotor.
A two-dimensional hydrogen bonded organic framework self-assembled from a three-fold symmetric carbamate
A hydrogen bonded organic framework displayed a capacity for accommodating and releasing guest molecules.
Catalytic intermolecular β-C–H alkenylation of α-enamino-ketones with simple alkynes
A unique strategy to synthesize β-alkenyl-α-amino-enones via catalytic C–H/alkyne coupling is described.
Targeting cancer cells with folic acid–iminoboronate fluorescent conjugates
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.
Diaryl-substituted norbornadienes with red-shifted absorption for molecular solar thermal energy storage
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.
Spectroscopic characterization of a phenolate bound FeII–O2 adduct: gauging the relative “push” effect of a phenolate axial ligand
Gauging the trans effect of phenolate.
Simple procedure for mono- and bis-end-functionalization of regioregular poly(3-hexylthiophene)s using chalcogens
Simple quenching method to synthesize mono- and bis-end-functionalized regioregular poly(3-hexylthophene)s using chalcogens is presented.
Mechanosynthesis of pharmaceutically relevant sulfonyl-(thio)ureas
Solvent-free mechanochemical coupling provides pharmaceutically relevant sulfonyl-(thio)ureas, including anti-diabetic drugs tolbutamide, chlorpropamide and glibenclamide, rapidly and in high yield.
Gold(I) mediated rearrangement of -helicene to give a benzo[cd]pyrenium cation embedded in a chiral framework
The facile gold-mediated skeletal rearrangement of -helicene into a cationic polyaromatic hydrocarbon is described.
Investigating the reactivities of a polyketide synthase module through fluorescent click chemistry
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.
Modulating guest binding in sulfonylcalixarene-based metal–organic supercontainers
A neutral metal–organic supercontainer (MOSC) has been functionalized as an anionic container, leading to enhanced adsorption capacity for polar guests.
The final unadorned tris(azolyl)borate: finishing what Trofimenko started in 1966
The final addition to the tris(azolyl)borate ligand family, tris(1,2,3-triazolyl)borate, has been synthesized.
2-(Aryl-sulfonyl)oxetanes as designer 3-dimensional fragments for fragment screening: synthesis and strategies for functionalisation
Oxetane synthesis by intramolecular C–C bond formation efficiently provides 2-sulfonyloxetanes, which are further derivatised maintaining the oxetane ring intact.
Probing morphological changes in polymersomes with magnetic birefringence
Magnetic birefringence was used for in situ monitoring of the morphological changes in diamagnetic polymersomes during shape-transformation by dialysis.
Face-on stacking and enhanced out-of-plane hole mobility in graphene-templated copper phthalocyanine
The out-of-plane hole mobility in copper phthalocyanine is enhanced by face-on molecular stacking induced by graphene-templated growth.
A fluorogenic probe for recognizing 5-hydroxylysine inspired by serine/threonine ligation
A coumarin-based non-fluorescent probe can selectively react with 5-hydroxylysine-containing peptides, leading to a fluorescent tag.
Can non-polar hydrogen atoms accept hydrogen bonds?
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.
Structural and electrochemical characterization of a cerium(IV) hydroxamate complex: implications for the beneficiation of light rare earth ores
Reaction of N-phenyl-pivalohydroxamic acid with CeIII precursors leads to a homoleptic hydroxamate complex: CeIV[tBuC(O)N(O)Ph]4.
An unprecedented CoII cuboctahedron as the secondary building unit in a Co-based metal–organic framework
A cubic metal–organic framework with an unprecedented octanuclear secondary building unit (SBU) was isolated.
Multifunctional squalene-based prodrug nanoparticles for targeted cancer therapy
Fluorescent and biotinylated squalene–gemcitabine prodrug nanoparticles exhibiting high drug payloads have been prepared and successfully used to target different cancer cell lines.
Rhodium-catalyzed carbene transfer to alkynes via 2-furylcarbenes generated from enynones
A Rh-catalyzed cyclization of enynone, cyclopropenation of an alkyne and cyclopropene rearrangement cascade is accomplished using enynones as the carbene source.
About this collection
Welcome to the ChemComm Emerging Investigators Issue 2014. Now in its fourth year, we have been overwhelmed by the community's positive response to this issue. It showcases up-and-coming scientists who are internationally recognised for making outstanding contributions to their respective fields. New articles will be added to this collection as they are published.