Synthesis of Metal Nanoparticles Stabilized by Metal−Carbon Bonds

Mirkhalaf, Fakhradin; Paprotny, J.; Schiffrin, David J.

doi:10.1021/ja058687g

Cited by 188 publications

(185 citation statements)

References 22 publications

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“…Potassium tert-butoxide was sublimed freshly before use. Allyl bromide was washed with NaHCO 3 and water, dried with MgSO 4 , and distilled freshly before use. Triphenylphosphine was recrystallized from hexanes and dried under a vacuum for 24 h over P 2 O 5 .…”

Section: Methodsmentioning

confidence: 99%

Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation

et al. 2009

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Ruthenium nanoparticles functionalized with pyrene moieties were prepared by olefin metathesis reactions of carbenestabilized nanoparticles with 1-vinylpyrene and 1-allylpyrene (referred to as RudVPy and RudAPy, respectively). 1 H NMR spectroscopic measurements showed that the surface concentration of the pyrene moieties was 26.4 and 22.9%, respectively. In fluorescence measurements, RudVPy nanoparticles exhibited two prominent emission bands at 392 and 490 nm, very similar to those of (E)-1,2-di(pyren-1-yl)ethene, suggesting that the particle-bound pyrene moieties might behave equivalently to pyrene dimers with a conjugated linker by virtue of the Rudcarbene π bonds. In sharp contrast, RudAPy nanoparticles displayed only a single emission peak at 392 nm, consistent with monomeric pyrene derivatives of 1-vinylpyrene and 1-allylpyrene. This implies that the intraparticle extended conjugation might be effectively turned off by the insertion of an sp 3 carbon into the chemical linker that bound the pyrene moieties onto the nanoparticles. In addition, RudVPy nanoparticles exhibited a rather long lifetime of the emission at 490 nm, as compared to that of the conjugated pyrene dimer, suggesting that the nanoparticles might be less prone to photobleaching. This is attributed to the neighboring organic protecting ligands that may create a more rigid chemical environment for the nanoparticle-bound pyrene moieties and thus prolong the life of the excited state, as compared to the strong electrostatic perturbations which exist in free solution when surrounded by a polar solvent.

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Section: Methodsmentioning

confidence: 99%

Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation

et al. 2009

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“…For thiol-based surface modifiers, the differences may be larger than the tunnelling conductance difference between the DNA bases, further complicating data analysis 43 . Other functional groups may be more suitable for this purpose, for example, diazo-based molecules form strong covalent carbon single bonds to gold 92 . Finally, the overall device design needs to be optimized with a view on optimum electric performance, which is, minimizing noise.…”

Section: Small-molecule Sensing By Tunnelling Currentsmentioning

confidence: 99%

Electrochemical tunnelling sensors and their potential applications

Albrecht

2012

Nat Commun

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the quantum-mechanical tunnelling effect allows charge transport across nanometre-scale gaps between conducting electrodes. application of a voltage between these electrodes leads to a measurable tunnelling current, which is highly sensitive to the gap size, the voltage applied and the medium in the gap. applied to liquid environments, this offers interesting prospects of using tunnelling currents as a sensitive tool to study fundamental interfacial processes, to probe chemical reactions at the single-molecule level and to analyse the composition of biopolymers such as Dna, rna or proteins. this offers the possibility of a new class of sensor devices with unique capabilities. E lectrochemical sensors based on measuring the tunnelling current across nanoscale electrode junctions in solution are emerging as a new class of single-molecule sensors. They combine extremely high spatial resolution with sensitivity to the electronic structure of the analyte. This opens up perspectives towards the label-free detection of small molecules, the characterization of catalytic or enzymatic processes at the single-molecule level as well as the analysis of biopolymers with sub-molecular resolution, Fig. 1. To this end, label-free, fast and inexpensive RNA and DNA sequencing may be in reach, potentially revolutionizing the way we perform gene sequencing today.Charge transfer by quantum-mechanical tunnelling is one of the most ubiquitous elementary processes in nature and features in areas as diverse as electron or hydrogen transfer in enzymatic reactions, interfacial charge transfer at metal electrodes in solution, thin-layer devices in electronics, charge transfer between crystal defects and radioactive α-decay 1 . Important applications exploiting tunnelling transport include the Esaki tunnelling diode and the scanning tunnelling microscope (STM)-both recognized with the Nobel Prize in Physics for their inventors, namely Esaki in 1973 (jointly with Josephson), and Binnig and Rohrer in 1986, respectively.'Tunnelling' refers to the transport of electrons (or other light charge carriers) across a nanometre-sized gap, a molecule or even an insulating layer between two electrodes. Upon application of a bias voltage V bias between the two electrodes, negatively charged electrons are more likely to be transported towards the positively biased electrode and a so-called 'tunnelling current' I t is detected. The latter depends exponentially on gap size, which is the reason for the high spatial resolution of STM, the applied voltage V b and the electronic structure of the medium in the gap. To this end, the electrode junction may be represented by a transmission function that characterizes the probability of electrons moving from one electrode across the gap into the second electrode, summarized over all energy levels.Hence, the more accessible the energy levels in the junction, and the better their electronic coupling to the electrodes, the higher current across the junction. This also implies that the tunnelling current is sensitive to ...

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“…Commonly used stabilizing agents include various polymers such as PVP 1,9) , and metal coordinating ligands of thiols 10) and amines 11) . Au-, Ti-, Pd-and Pt-NPs, which are stabilized by metal-carbon σ-bonds between surface metal atoms and aromatic ring moieties with long alkyl chains, can be prepared by reduction of the corresponding metal salts and the alkyl diazonium salt [12][13][14] . The chemical stability of metal-NPs is enhanced by the high bond strength of the σ-bond between the metal and carbon 13,14) .…”

Section: Introductionmentioning

confidence: 99%

Micromorphological cellular responses of MC3T3-E1 and RAW264.7 after exposure to water-dispersible silver nanoparticles stabilized by metal-carbon σ-bonds

et al. 2013

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With the continuous progress in nanomaterial development for biomedicine, the potential cytotoxicity of nanoparticles is drawing more attention and concern for clinical applications. The purpose of this study was to evaluate biological responses of new waterdispersible silver nanoparticles (Ag-NPs) stabilized by Ag-C σ-bonds in cultured murine macrophages (RAW264.7) and osteoblastlike cells (MC3T3-E1) using cell viability and morphological analyses. For RAW264.7, Ag-NPs seemed to induce cytotoxicity that was dependent on the Ag-NP concentration. However, no cytotoxic effects were observed in the MC3T3-E1 cell line. In microscopic analysis, Ag-NPs were taken up by MC3T3-E1 cells with only minor cell morphological changes, in contrast to RAW264.7 cells, in which particles aggregated in the cytoplasm and vesicles. The ability of endocytosis of macrophages may induce harmful effects due to expansion of cell vesicles compared to osteoblast-like cells with their lower uptake of Ag-NPs.

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Synthesis of Metal Nanoparticles Stabilized by Metal−Carbon Bonds

Cited by 188 publications

References 22 publications

Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation

Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation

Electrochemical tunnelling sensors and their potential applications

Micromorphological cellular responses of MC3T3-E1 and RAW264.7 after exposure to water-dispersible silver nanoparticles stabilized by metal-carbon σ-bonds

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