Mark S. Workentin

Highly Efficient Electrogenerated Chemiluminescence of Au38 Nanoclusters

An investigation of mechanisms for the near-infrared (NIR) electrogenerated chemiluminescence/electrochemiluminescence (ECL) of Au38(SC2H4Ph)24 (Au38, SC2H4Ph = 2-phenylethanethiol) nanoclusters both in annihilation and coreactant paths is reported. Essentially, no ECL emission was produced in the annihilation route over the potential range of the accessible redox states of Au38, because of the short lifetime and/or low reactivity of the electrogenerated Au38 intermediates necessary for ECL. Highly efficient light emission with a nominal peak wavelength of 930 nm in the NIR region was observed in the anodic region upon addition of tri-n-propylamine (TPrA) as the coreactant. The ECL mechanisms were elucidated by means of ECL-potential curves and spooling ECL spectroscopy. It was discovered that the Au38(+*) (and also Au38(3+*)) were electrogenerated as the major excited species in the light emission processes. Benzoyl peroxide was also used as a coreactant in the cathodic potential range from which benzoate radicals, with a high oxidizing power, were formed. These radicals accepted electrons from the electrogenerated Au38(2-) HOMO, resulting in the Au38(-*) excited state that emitted light at 930 nm. The photoluminescence of the various Au38 charge states, namely, Au38(2-), Au38(-), Au38(0), Au38(+), Au38(2+), and Au38(4+), electrogenerated in situ, indicated no significant difference in the emission peak wavelength. This information allowed a careful mapping of the relevant ECL mechanisms. It was found that the ECL efficiency could reach an efficiency of 3.5 times as high as that of the Ru(bpy)3(2+)/TPrA system.

Rapid and selective lead (II) colorimetric sensor based on azacrown ether-functionalized gold nanoparticles

A gold nanoparticle (AuNPs)-based simple and fast colorimetric sensor for selective detecting of Pb(II) in aqueous solution has been developed. Monodisperse AuNPs (approx. 2.0 nm diameter) has been prepared facilely and further modified with an alkanethiol-bearing monoazacrown ether terminus. These AuNPs are shown to selectively sense Pb(2+) through color change, which is visually discernible by an appearance of the surface plasmon band (SPB) at 520 nm. The recognition mechanism is attributed to the unique structure of the monoazacrown ether attached to AuNPs and metal sandwich coordination between two azacrown ether moieties that are attached to separate nanoparticles. This inter-particle cross-linking results in an aggregation and apparent color change from brown to purple. Additionally, TEM experiments support the optical absorption data proving the aggregation between azacrown ether-capped gold nanoparticles. This AuNP-based colorimetric assay is a facile and robust method and allows fast detection of Pb(2+) at ambient temperatures. More importantly, the developed technique does not utilize enzymatic reactions, light-sensitive dye molecules, lengthy protocols or sophisticated instrumentation.

Kinetics and mechanism of the dissociative reduction of CX and XX bonds (X O, S)

Publisher Summary This chapter discusses some recent developments and methodologies that have impacted the understanding of dissociative electron transfer (ET). It focuses on the reduction of C–X and X–X bonds in which X is either oxygen or sulfur and provides insights into the nature of the intrinsic barriers for the stepwise dissociative reduction reactions as well as some interesting examples that demonstrate a need to continue to develop the present dissociative ET model. The reduction of ethers, peroxides, sulfides, and disulfides presented also provides some insights into the three-surface and two-surface models of transition from the stepwise to the concerted mechanisms. The combination of electrochemical data with other kinetic or thermodynamic approaches provides independent confirmation of the kinetic and thermodynamic data and allows the kinetic window to be extended both for highly exergonic and highly endergonic processes. It is significant to ensure that the kinetics is in the activation region in the assessment of intrinsic barriers.

Light-activated covalent formation of gold nanoparticle-graphene and gold nanoparticle-glass composites.

Monolayer protected gold nanoparticles (AuNPs) modified with a 3-aryl-3-(trifluoromethyl)diazirine functionality at its terminus (Diaz-AuNPs, 3.9 nm) were prepared and irradiated in the presence of two very different substrates, reduced graphene and glass. Upon irradiation, the terminal diazirine group loses nitrogen to generate a reactive carbene at the interface of the AuNPs that can then undergo addition or insertion reactions with functional groups on the graphene or glass surfaces, leading to the formation of graphene-AuNP and glass-AuNP hybrids, respectively. The AuNP hybrids were characterized using TEM, XRD, XPS, AFM, and UV-vis spectroscopy. Control experiments done in the absence of irradiation demonstrate that carbene activation is required for incorporation of significant AuNP onto the materials. The AuNP hybrids are robust and stable to excessive washing and centrifugation supporting the covalent nature of the interaction between the AuNP and the graphene or silicate glass substrates. Because the formation of the composite is light activated, it lends itself to photopatterning; this application is demonstrated for making the glass-AuNP composites.

NIR electrochemiluminescence from Au25− nanoclusters facilitated by highly oxidizing and reducing co-reactant radicals

The well-defined electrochemical features and optical properties of the negatively charged Au25 clusters (Au25−) provide opportunities for a photoelectrochemical study by means of electrochemiluminescence (ECL) technique. Under annihilation conditions where the Au25− is electrochemically pumped to its various oxidized and reduced forms showed no appreciable ECL light emission, due presumably to the short lifetime of the electrogenerated intermediates and their reactivity. Interestingly, in either Au25−/tri-n-propylamine (TPrA) or Au25−/benzoyl peroxide (BPO) co-reactant systems, the correspondingly highly reducing and oxidizing intermediates electrogenerated from TPrA and BPO lead to light emission at 950 and 890 nm in near-infrared (NIR) region. The ECL in the presence of various concentrations of TPrA (6.3, 12.5, 25, 50, 100 and 200 mM) and BPO (2.5, 5, 25 and 50 mM) was explicitly investigated. Along with the concentration dependence study, spooling ECL spectroscopy provided insight into the ECL mechanisms. Notably, while the Au25−* is the main light emission source with BPO, ECL in the presence of TPrA is attributed to emissions from the Au25−*, Au250* and Au25+* that are tuneable by means of the applied potential and TPrA concentration.

Kinetics of dissociative electron transfer to ascaridole and dihydroascaridole-model bicyclic endoperoxides of biological relevance.

The homogeneous and heterogeneous electron transfer (ET) reduction of ascaridole (ASC) and dihydroascaridole (DASC), two bicyclic endoperoxides, chosen as convenient models of the bridged bicyclic endoperoxides found in biologically relevant systems, were studied in aprotic media by using electrochemical methods. ET is shown to follow a concerted dissociative mechanism that leads to the distonic radical anion, which is itself reduced in a second step by an overall two-electron process. The kinetics of homogeneous ET to these endoperoxides from an extensive series of radical anion electron donors were measured as a function of the driving force of electron transfer (deltaG(o)ET). The kinetics of heterogeneous ET were also studied by convolution analysis. Together, the heterogeneous and homogeneous ET kinetic data provide the best example of the parabolic nature of the activation-driving force relationship for a concerted dissociative ET described by Savéant; the data is particularly illustrative due to the low bond-dissociation enthalpy (BDE) of the O-O bond and hence small intrinsic barriers. Analysis of the data allowed the dissociative reduction potentials (E(o)diss) to be determined as -1.2 and -1.1 Vagainst SCE for ASC and DASC, respectively. Unusually low pre-exponential factors measured in temperature-dependent kinetic studies suggest that ET to these O-O bonded systems is nonadiabatic. Analysis of ET kinetics for ASC and DASC by the Savéant model with a modification for nonadiabaticity allowed the intrinsic free energy for ET to be determined. The use of this approach and estimates for the BDE provide approximations of the reorganization energies. We suggest the methodology described herein can be used to evaluate the extent of ET to other endoperoxides of biological relevance and to provide thermochemical data not otherwise available.

Improved methodology for the preparation of water-soluble maleimide-functionalized small gold nanoparticles.

Improved methodology to prepare maleimide-functionalized, water-soluble, small (<3 nm) gold nanoparticles using a retro-Diels-Alder strategy that we developed for similar organic-soluble AuNPs is described. Importantly, our results suggest that a recent paper by Zhu, Waengler, Lennox, and Schirrmacher describing a similar strategy gave results inconsistent with the formation of the titled maleimide-modified AuNP (Zhu, J.; Waengler, C.; Lennox, R. B.; Schirrmacher, R. Langmuir2012, 28, 5508) as the major product, but consistent with the major product being an adduct derived from the hydrolysis of maleimide formed under the conditions used for the required deprotection of the maleimide. Our methodology provides an efficient and accessible route to pure maleimide-modified small AuNPs that circumvents the formation of the hydrolysis product. The maleimide-modified small AuNPs are versatile because they are soluble in water and in a wide range of organic solvents and their reactivity can now be properly exploited as a reactive moiety in Michael addition for bioconjugation studies in aqueous solution.

Facile synthesis of gold nanoparticle (AuNP)–carbon nanotube (CNT) hybrids through an interfacial Michael addition reaction

A CNT-AuNP hybrid has been synthesized through the Michael addition reaction between thiol-functionalized single-wall CNT and small water-soluble Maleimide-AuNP. The resilience and stability of this hybrid nanosystem is ensured by a covalent bond linking the nanoparticle to the CNT and by the fact that the functionalization reaction involves the organic shell of the AuNP and not its metallic core.

Diazirine-modified gold nanoparticle: template for efficient photoinduced interfacial carbene insertion reactions.

Photolysis of a 3-aryl-3-(trifluoromethyl)diazirine-modified monolayer-protected gold nanoparticles (2-C(12)MPNs), with a core size of 1.8 ± 0.3 nm, in the presence of model carbene trapping reagents leads to efficient, essentially quantitative, modification of the interface via carbene insertion reactions. The utility of carbene insertion reactions as a general approach for the modification of Au-MPNs to provide a breadth of new structures available was demonstrated using acetic acid, methanol, benzyl alcohol, phenol, benzylamine, methyl acrylate, and styrene (10a-g, respectively) as electrophilic carbene trapping agents to form the corresponding modified 3a-g-C(12)MPNs. The 1.8 ± 0.3 nm gold nanoparticles bearing a diazirine group (2-C(12)MPNs) were synthesized using the ligand exchange reaction with the requisite 3-aryl-3-(trifluoromethyl)diazirinealkylthiol. The 2-C(12)MPNs and the resulting products of the reaction on the MPN (3a-g-C(12)MPN) were fully characterized by IR, (1)H NMR, and (19)F NMR spectroscopy and, when applicable, transmission electron microscopy (TEM). Verification for the 3a-g-C(12)MPNs was accomplished by comparison of the spectral data to those of obtained for the photoreactions of 3-(3-methoxyphenyl)-3-(trifluoromethyl)-3H-diazirine as a model with 10a-g.

Thermodynamic and Kinetic Origins of Au250 Nanocluster Electrochemiluminescence

Au clusters with protecting organothiolate ligands and core diameters less than 2 nm are molecule-like structures, suitable for catalysis, optoelectronics and biology applications. The spectroscopy and electrochemistry of Au25(0) (Au25[(SCH2CH2Ph)18], SCH2CH2Ph = 2-phenylethanethiol) allowed us to construct a Latimer-type diagram for the first time, which revealed a rich photoelectrochemistry of the cluster and the unique relationship to its various oxidation states and corresponding excited states. The occurrence of cluster electrochemiluminescence (ECL) was examined in the presence of tri-n-propylamine (TPrA) as a co-reactant and was discovered to be in the near-infrared (NIR) region with peak wavelengths of 860, 865, and 960 nm, emitted by Au25(+*), Au25(0*), and Au25(-*), respectively. The light emissions, with an efficiency up to 103% relative to that of the efficient Ru(bpy)3(2+)/TPrA system, depended on the kinetics of the reactions between the electrogenerated TPrA radical and Au25(z) (z = 2+, 1+, 1-, and 2-) in the vicinity of the electrode or the bulk Au25(0). These thermodynamic and kinetic origins were further explored by means of spooling ECL and photoluminescence spectroscopy during a sweep of the potential or at a constant potential applied to the working electrode. NIR-ECL emissions of the cluster can be tuned in wavelength and intensity by adjusting the applied potential and TPrA concentration based on the above discoveries.