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Electricity has been generated from evaporation-driven water flow in films of carbon soot particles and other porous media. This paper reports the placement of carbon nanofiber mats (CNMs) on fiberglass screens for the construction of efficient water-evaporation-induced generators (WEIGs). These CNMs are prepared from carbonizing electrospun polyacrylonitrile nanofiber mats and then treating them with oxygen plasma. After electrode attachment to the two ends of a CNM, one electrode is immersed into water. Water rises in the mat due to capillary action and evaporates from the mat surface due to thermal energy provided by the environment. The steady rise of water pushes the dissociated ions of the surface functionalities upward, resulting in a streaming current and an electric potential. This paper investigates how the generated short-circuit current, Is, and open-circuit voltage, Vo, of the WEIG change with structural parameters of the CNMs. Under optimized conditions, these CNMs produce electricity at an areal power density of 83 nW/cm2, which is almost 10 times those offered by some existing ones. Thus, the easy-to-handle CNMs are an attractive porous scaffold for WEIGs.

Photoelectrochemical (PEC) water splitting converts solar light and water into oxygen and energy-rich hydrogen. WO

Porphyrin aggregates have attractive photophysical properties for phototherapy and optical imaging, including quenched photosensitization, efficient photothermal conversion, and unique absorption spectra. Although hydrophobic porphyrin photosensitizers have long been encapsulated into liposomes for drug delivery, little is known about the membrane properties of liposomes with large amphiphilic porphyrin compositions. In this paper, a porphyrin-lipid conjugate was incorporated into liposomes formed of saturated or unsaturated lipids to study the membrane composition-dependent formation of highly ordered porphyrin J-aggregates and disordered aggregates. Porphyrin-lipid readily phase-separates in saturated membranes, forming J-aggregates that are destabilized during the ripple phase below the main thermal transition. Porphyrin-lipid J-aggregates are photostable with a photothermal efficiency of 54 ± 6%, comparable to gold. Even at high porphyrin-lipid compositions, porphyrin J-aggregates coexist with a minority population of disordered aggregates, which are photodynamically active despite being fluorescently quenched. For photothermal applications, liposome formulations that encourage porphyrin-lipid phase separation should be explored for maximum J-aggregation.

Here, we demonstrated a facile method for growing nanofeatured silver (Ag) structures on a planar microelectrode platform. The nanostructures were assembled along the electrically insulating substr...

Herein, we describe the synthesis of a toroidal Au

Superatom clusters, Au

From antimicrobial studies to photonic devices, silver nanoparticles have been an exciting material, investigated for decades. Much of the efforts have been focused on tunable size, shape and optical properties of silver colloids. Although many advancements have been made there remain key limitations, including oxidation, and reactivity, especially in comparison to more stable gold nanomaterials. In this work, we present a method for stabilizing silver nanoparticles on aluminum oxide scaffolding, mitigating the oxidation and aggregation typical of silver particles, while maintaining their highly tunable plasmonic properties. Herein, alumina stabilized silver nanoparticles are subjected to photochemical shape control where the final particle morphology is dependent on whether the Al2O3 is in a solid or colloid phase. This work provides more insight into the complex mechanism(s) of nanoparticle shape control. Particles, with tunable plasmon modes achieved across the visible spectrum, provide optical properties of great relevance to the fields of chemical sensing, catalysis, and photonics while maintaining long-term stability.

Using chemically modified extracellular matrix proteins, such as collagen, in combination with light for tissue bonding reduces inflammation and minimizes scarring. However, full length animal or recombinant human collagen proteins are difficult to isolate/produce. Thus, short biomimetic collagen peptides with properties equivalent to collagen at both structural and functional levels may be ideal building blocks for the development of remotely triggered adhesives and fillers. In this work, the conjugation of self-assembling collagen-like peptides to acrylate functionalized polyethylene glycol units yielded adhesive filler materials activated by visible light through the incorporation of a photosensitizer. When tested in a murine skin wound model, the photoactivated adhesives showed reduced scar formation and promoted epithelial regeneration.

Facile, customizable platforms are important for a variety of microfluidic applications. This work presents a platform that utilizes surface tension induced pumping based on Young–Laplace pressure. The approach allows modifiable transport of fluids across surfaces without external pumping modules. The Laplace-chip is based on a superhydrophobic coating (NeverWet™) that is patterned by laser micromachining. For fast and consistent deposition of specific liquid volumes/droplets onto the “Laplace-chip” without the need for conventional fluid dispensing tools (e.g. pipette), a multiplexed droplet factory (MDF) was developed. The MDF is placed above the Laplace-chip and consists of cylindrial reservoirs that are filled by a “pour and swipe” approach. It enables the formation of hundreds of droplets (10–140 µL, 7.3% deviation) with both position and volume control as well as the simultaneous initiation of Young–Laplace induced pumping on the Laplace-chip. Furthermore, the flowrate of Young–Laplace induced pumping is adjustable through different pattern designs and dispensed droplet volumes. The Laplace-chip and MDF is used to carry out silver nanoparticle and nanocluster synthesis, where the reagent introduction rate is critical to material properties, to demonstrate flowrate controlled application possibilities. A Laplace-chip employing different channel length is employed to carry out the reduction of Ag+ to Ag0, using NaBH4. Low reducing agent concentrations and long pumping times (40–60 min) resulted in molecule-like silver cluster (AgNC) synthesis, while high reducing agent concentrations and short pumping times (5–20 min) led to the synthesis of silver nanoparticles (AgNPs).

Noble metal clusters have unique photophysical properties, especially as a new class of materials for multiphoton biomedical imaging. The previously studied Au25SR18 exhibits "giant" two-photon absorbance cross sections. Herein, we investigate the origins of the large two photon absorption for Au25SR18, as well as 10 other Au and Ag clusters using femtosecond pump/probe transient absorption spectroscopy (fsTAS). Excited state absorbance (ESA) ubiquitous to thiolated Au and Ag clusters is used herein as an optical signature of two-photon absorbances of the 11 different Au and Ag clusters, which does not require high quantum yields of emission. The large selection of clusters, studied with a single laser system, allows us to draw conclusions on the role of the particular metal, cluster size/structure, and the effects of the ligands on the ability to absorb multiple NIR photons. The use of a laser with a 1028 nm excitation also allows us to investigate the dramatic effect of excitation wavelength and explain why laser wavelength has led to large variances in the non-linear responses reported for clusters to date. We discuss the double resonance mechanism, responsible for giant two photon absorbance cross-sections, helping match properties of metal clusters with experimental conditions for maximizing signal/response in multiphoton applications.

Metal clusters of gold and silver with highly tunable optical and electronic properties are attractive candidates for next generation medical imaging and therapy. Of these two most commonly studied metals, silver clusters often exhibit superior optical properties (i.e. stronger absorbance and higher emission quantum yield). The atomically precise synthesis of these clusters is essential before their use in biological applications can be realized. However, most cluster synthetic routes result in complex mixtures, where isolation and/or characterization can become incredibly challenging. Using photochemistry, we demonstrate a synthetic route for silver thiolate clusters resulting in the isolation of a pure eighteen-atom silver cluster capped by fourteen captopril ligands, Ag18(Capt)14. The facile control over the reduction of Ag(I) salt that this photochemical route affords can be readily applied as a general synthesis for isolating other new, atomically precise clusters.

Surface-enhanced Raman scattering (SERS) enables the highly sensitive detection of (bio)chemical analytes in fluid samples, however, its application requires nanostructured gold/silver substrates, which presents a significant technical challenge. Here, we develop and apply a novel method for producing gold nanostructures for SERS application via the alternating current (AC) electrokinetic assembly of gold nanoparticles into two intricate and frequency-dependent structures: (1) nanowires, and (2) branched &ldquo, nanotrees&rdquo, that create extended sensing surfaces. We find that the growth of these nanostructures depends strongly on the parameters of the applied AC electric field (frequency and voltage) and ionic composition, specifically the electrical conductivity of the fluid. We demonstrate the sensing capabilities of these gold nanostructures via the chemical detection of rhodamine 6G, a Raman dye, and thiram, a toxic pesticide. Finally, we demonstrate how these SERS-active nanostructures can also be used as a concentration amplification device that can electrokinetically attract and specifically capture an analyte (here, streptavidin) onto the detection site.

Bis(ferrocenyl)-functionalized boron dipyrromethene (BODIPY) compound 1 featuring direct Fc-B bonds was obtained via a "prefunctionalization strategy". UV-vis absorption, electrochemical, and transient absorption experiments were performed on compound 1 and its analogues to examine the impact of ferrocenyl substitution on the electronic properties. The ferrocene units were found to have little impact on the absorption spectrum of the BODIPY unit but significantly change the excited-state dynamics.

Excited-state properties of photonic materials play an important part in dictating the photocatalytic activity. Thiol-protected gold clusters, like Au18(SR)14 and Au25(SR)18, are an emerging material of interest with unique optical and electronic properties. Au18(SR)14 clusters, in particular, have shown promise as one of the highest efficiency clusters in light harvesting, with a high emission quantum yield. In this work, the excited-state properties of Au18(SR)14 are studied in-depth by ultrafast pump/probe spectroscopy for the first time. A single model describing the optical characteristics of thiol-protected Au18(SR)14 and Au25(SR)18 clusters is offered. Excited-state dynamics analysis suggests that there are state-resolved relaxations due to the presence of multiple excited states. The populations of these excited states are shown to be solvent- and ligand-dependent.

Singlet fission converts one photoexcited singlet state to two triplet excited states and raises photoelectric conversion efficiency in photovoltaic devices. However, only a handful of chromophores have been known to undergo this process, which greatly limits the application of singlet fission in photovoltaics. We hereby identify a recently synthesized diazadiborine-pyrene ((BN)2-pyrene) as a singlet fission chromophore. Theoretical calculations indicate that it satisfies the thermodynamics criteria for singlet fission. More importantly, the calculations provide a physical chemistry insight into how the BN substitution makes this happen. Both calculation and transient absorption spectroscopy experiments indicate that the chromophore has a better absorption than pentacene. The convenient synthesis pathway of the (BN)2-pyrene suggests an in situ chromophore generation in photovoltaic devices. Two more (BN)2-pyrene isomers are proposed as singlet fission chromophores. This study sets a step forward in the cr...

Metal clusters of gold and silver with highly tunable optical and electronic properties are attractive candidates for next generation medical imaging and therapy. Of these two most commonly studied metals, silver clusters often exhibit superior optical properties (i.e. stronger absorbance and higher emission quantum yield). The atomically precise synthesis of these clusters is essential before their use in biological applications can be realized. However, most cluster synthetic routes result in complex mixtures, where isolation and/or characterization can become incredibly challenging. Using photochemistry, we demonstrate a synthetic route for silver thiolate clusters resulting in the isolation of a pure eighteen-atom silver cluster capped by fourteen captopril ligands, Ag

Gold superatom nanoclusters stabilized entirely by N-heterocyclic carbenes (NHCs) and halides are reported. The reduction of well-defined NHC-Au-Cl complexes produces clusters comprised of an icosahedral Au

Cu-deficient CuInS2 quantum dots (QDs) synthesized by varying the [Cu]:[In] ratio allow modulation of optical properties as well as identification of the radiative emission pathways. Absorption and emission spectral features showed a strong dependence on the [Cu]:[In] ratio of CuxInS2 QDs, indicating two independent optical transitions. These effects are pronounced in transient absorption spectra. The bleaching of band edge absorption and broad tail absorption bands in the subpicosecond-nanosecond time scale provide further evidence for the dual optical transitions. The recombination process as monitored by photoemission decay indicated the involvement of surface traps in addition to the bandgap and sub-bandgap transitions. Better understanding of the origin of the optical transitions and their influence on the photodynamics will enable utilization of ternary semiconductor quantum dots in display and photovoltaic devices.

p.p1 {margin: 0.0px 0.0px 0.0px 0.0px; line-height: 20.0px; font: 17.4px Helvetica; color: #000000; -webkit-text-stroke: #000000; background-color: #ffffff} span.s1 {font-kerning: none} span.s2 {font: 11.2px Helvetica; font-kerning: none} span.s3 {font-kerning: none; color: #000000} Magic number Au13 nanoclusters stabilized entirely by N-heterocyclic carbenes (NHCs) have been prepared by the bottom-up reduction of well-defined molecular NHC–Au–Cl complexes with sodium borohydride. The nature of the wingtip groups was shown to be critical in the preparation of stable clusters. The all NHC-clusters are prepared in high yield by this straight-forward method, display higher stability than related all phosphine clusters, and possess extremely high emission quantum yield. DFT analysis of these clusters based on the resolved crystal structure reveals their electronic structure as 8-electron superatoms.

N,C-chelate organoborates represent an emerging class of photoresponsive materials due to their photochromic switching at a boron center. Despite the promising applicability of such systems, little is known about the excited-state processes that lead to their unique photoreactivity, which is detrimental to the design of next-generation smart materials based on boron. As part of our ongoing effort to understand and improve the utility of these organoboron compounds, we report some of the first experimental evidence to support an excited-state mechanism for N,C-chelate organoborates. Femtosecond transient absorption spectroscopy combined with steady-state UV/vis and fluorescence measurements gives direct insight into their underlying photochemical processes, such as the formation of a common triplet charge-transfer state which either relaxes radiatively or undergoes the desired photoisomerization through a biradical intermediate. With this information, a complete mechanistic picture of the excited-state reactivity of N,C-chelate organoborates has been established, which is anticipated to lead to new smart materials with improved performance.

Silver and gold clusters have received a lot of recent attention for their use in biomedical imaging. However, crude solutions of clusters are often complex mixtures, leading to discrepancies in their identification and characterization; important factors in determining their utility in biological applications. In the present study, silver clusters were separated for analysis using reverse-phase high performance liquid chromatography, which has previously been implemented in the efficient separation of gold clusters. Using fluorescence excitation–emission matrix (EEM) spectroscopy, we have demonstrated that a certain family of glutathione-protected silver clusters, previously thought to be one optically distinct species, is better described as a complex mixture of at least three distinct silver cluster species, each possessing unique optical properties. Based on these findings, EEM spectroscopy can be implemented as a powerful technique for determining the purity of complex mixtures, especially when other techniques, including mass spectrometry, fail to provide adequate characterization of a given material.

Excited-state properties of photonic materials play an important part in dictating the photocatalytic activity. Thiol-protected gold clusters, like Au

Atomically precise gold clusters that are less than ∼1 nm in diameter are emerging as a new class of light absorbing material for harvesting solar energy. Herein, we explore the size dependent properties of glutathione-protected clusters, (Au25GSH18, Au18GSH14, Au15GSH13 and Au11GSH11) in sensitizing mesoscopic TiO2 films. The excited state properties of gold clusters are correlated with the photovoltaic performance of metal cluster sensitized solar cell. Au18GSH14 exhibit the highest photoconversion efficiency. The size dependent photovoltaic results are rationalized based on optimizing both the light absorption of the clusters as well as the size dependent excited state behavior.

Bismuth vanadate (BiVO4) with a band gap of ∼2.4 eV has emerged as one of the visible photocatalysts that can absorb light below 520 nm. The electron/hole pairs that are generated following BiVO4 band gap excitation are effective for water splitting, especially when BiVO4 is combined with other metal oxides such as WO3. We report a solution processed method for designing transparent WO3/BiVO4 heterojunction electrodes and observe a synergistic effect on the photoelectrochemical activity of WO3/BiVO4, with the combined system performing dramatically better than either individual component. Using ultrafast transient absorption spectroscopy, we elucidated the electronic interaction between WO3 and excited BiVO4. Moreover, the photocatalytic reduction of thionine by WO3/BiVO4 as well as by each individual oxide component is used to track electron injection processes and determine the energetics of the studied systems. In the composite WO3/BiVO4 film a shifted quasi-Fermi level results, due to electronic equil...

In situ light initiated synthesis of silver nanoparticles (AgNP) was employed for AgNP incorporation within the polymeric matrices of medical grade polyurethane. The resulting materials showed improved antibacterial and antibiofilm activity against Pseudomonas aeruginosa with negligible toxicity for human primary skin cells and erythrocytes., The authors would like to thank Mr Michel Grenier and Mr Christopher McTiernan for their help taking some of the pictures shown in this article and for technical support in the hemolysis project. Thanks are due to Dr May Griffith for helpful discussions. Support for this work is from a Collaborative Health Research Project grant (NSERC/CIHR Canada) to JCS and T.-F.M, NSERC's CREATE program. M. L. Marin thanks the Spanish Ministerio de Educacion, Cultura y Deporte (Programa Salvador de Madariaga) and the Distinguished Visiting Researchers Program at uOttawa for their financial support. EIA thanks UOHI startup grant #1255.

The rapid increase in efficiency of methylammonium lead halide perovskite solar cells necessitates further investigation into the nature of perovskite absorption features and optical properties. Films obtained from the deposition of solutions containing lead halides and the CH3NH3+ organic cation is known to yield the CH3NH3PbI3 perovskite structure upon annealing. In examining the precursor solution used in the processing of CH3NH3PbI3 solar cells, we find that Pb2+ readily forms plumbate complexes in the presence of excess iodide ions and exhibits characteristic absorption bands at 370 (PbI3−) and 425 nm (PbI42−). Through comparative spectral analysis of the absorption features of charge transfer complexes in the solution phase and the final solid-state perovskite films, we are able to fully classify the absorption features in the excited state of CH3NH3PbI3 across the transient absorption spectrum recorded following laser pulse excitation. In particular, we attribute the broad photoinduced absorption to a charge-transfer excited state, and show correlation between the photoinduced absorption and 480 nm bleach signals. These observations lead us to propose a band structure composed of two distinct transitions that is consistent with the various spectral features and kinetic behavior of the CH3NH3PbI3 excited state. Characterization of this unique dual excited state nature provides further insight into the optoelectronic behavior of hybrid lead halide perovskite films and thus aids in elucidating their exceptional photovoltaic properties.

Glutathione-capped gold nanoclusters (Aux-GSH NCs) are anchored along with a sensitizing squaraine dye on a TiO2 surface to evaluate the cosensitizing role of Au(x)-GSH NCs in dye-sensitized solar cells (DSSCs). Photoelectrochemical measurements show an increase in the photoconversion efficiency of DSSCs when both sensitizers are present. The observed photoelectrochemical improvements in cosensitized DSSCs are more than additive effects as evident from the increase in photovoltage (ΔV as high as 0.24 V) when Au(x)-GSH NCs are present. Electron equilibration and accumulation within gold nanoclusters increase the quasi-Fermi level of TiO2 closer to the conduction band and thus decrease the photovoltage penalty. A similar beneficial role of gold nanoclusters toward boosting the V(oc) and enhancing the efficiency of Ru(II) polypyridyl complex-sensitized solar cells is also discussed.

The optical and electronic properties of quantum dots (QDs), which are drastically affected by their size, have a major impact on their performance in devices such as solar cells. We now report the size-dependent solar cell performance for CuInS2 QDs capped with 1-dodecanethiol. Pyramidal shaped CuInS2 QDs with diameters between 2.9 and 5.3 nm have been synthesized and assembled on mesoscopic TiO2 films by electrophoretic deposition. Time-resolved emission and transient absorption spectroscopy measurements have ascertained the role of internal and surface defects in determining the solar cell performance. An increase in power conversion efficiency (PCE) was observed with the increasing size of QDs, with maximum values of 2.14 and 2.51% for 3.9 and 4.3 nm size particles, respectively. The drop in PCE observed for larger QDs (5.3 nm) is attributed to decreased charge separation following bandgap excitation. Because the origin of photocurrent generation in CuInS2 QDSC arises from the defect-dominated charge ...

A synthetically convenient and scalable SILAR (successive ion layer adsorption and reaction) method is used to make air-stable films of silver and gold nanoparticles supported on alumina scaffolds. This solution-based deposition technique yields particles devoid of insulating capping agents or ligands. The optical properties of the nanoparticle films were investigated using femtosecond transient absorption spectroscopy. A linear absorption arising from intraband excitation (775 nm laser pulse) is seen only for Au nanoparticles at low intensity. However, both Au and Ag particles exhibit plasmon resonance responses at high excitation intensity via two photon absorption of the 775 nm pump pulse. The difference in optical response to near-IR laser excitation is rationalized based on the known density of states for each metal. To demonstrate the potential applications of these films, alumina-supported Ag nanoparticles were utilized as substrates for surface enhanced Raman spectroscopy, resulting in a 65-fold enhancement in the Raman signal of the probe molecule rhodamine 6G. The exceptional stability and scalability of these SILAR films opens the door for further optical and photocatalytic studies and applications, particularly with ligand-free Ag nanoparticles that typically oxidize under ambient conditions. Additionally, isolating plasmonic and interband electronic excitations in stable AgNP under visible light irradiation could enable elucidation of the mechanisms that drive noble metal-assisted photocatalytic processes.

Visible light excitation of silver nanoparticles in the presence of polymerizable monomers and selected dyes triggers the self-assembly of nanolasers in a synthetically simple process. The new nanolasers incorporate a thin, fully organic gain medium that allows the tuning of the core absorption to a selected dye, or of the dye to a preselected core material. This versatile synthesis of surface plasmon lasers, or "spasers", has unique simplicity and enables spatial and temporal control of the nanolaser fabrication process.

The excited-state behavior of luminescent gold clusters provides new insights in understanding their photocatalytic activity in the visible region. The excited state of glutathione-protected gold nanoclusters (AuGSH), which is characterized by the long-lived excited state (τ = 780 ns), arises from the ligand-to-metal type transition. These AuGSH clusters are in a partially oxidized state (Au(I)) and are readily reduced by chemical or electrochemical methods. Interestingly, a metal core transition with short-lived lifetime (τ < 3 ps) appears along with a longer lifetime in reduced AuGSH clusters. The role of the oxidation state of gold clusters in dictating the photocatalytic reduction of methyl viologen is discussed.

In this Perspective, we explore the opportunities that plasmon excitation may offer for the practitioners in organic chemistry. Beyond the interesting physical properties and lively colors of colloidal solutions of noble metal nanostructures, excitation of plasmon transitions can trigger a variety of processes, from the simple heat delivery with pinpoint precision, to the enhanced generation of excited states in the immediate vicinity of the nanoparticle, to electron- and hole-transfer processes that can readily participate in photoredox processes. In understanding how particles are produced, what properties they have, and the diversity of nanostructures and environments in which they can be produced, we aim at providing the small steps toward a paradigm that will allow organic chemists to take advantage of the opportunities that await in the area of plasmon-assisted processes.

Due to its ∼2.4 eV band gap, BiVO4 is a very promising photoanode material for harvesting the blue portion of the solar light for photoelectrochemical (PEC) water splitting applications. In WO3/BiVO4 heterojunction films, the electrons photoexcited in BiVO4 are injected into WO3, overcoming the lower charge carriers’ diffusion properties limiting the PEC performance of BiVO4 photoanodes. Here, we investigate by ultrafast transient absorption spectroscopy the charge carrier interactions occurring at the interface between the two oxides in heterojunction systems to directly unveil their wavelength dependence. Under selective BiVO4 excitation, a favorable electron transfer from photoexcited BiVO4 to WO3 occurs immediately after excitation and leads to an increase of the trapped holes’ lifetime in BiVO4. However, a recombination channel opens when both oxides are simultaneously excited, evidenced by a shorter lifetime of trapped holes in BiVO4. PEC measurements reveal the implication of these wavelength-depen...

A hierarchy of lithographic-type imaging generating 3 μm lines incorporating subdiffraction limit features was obtained through a novel two-step reaction process. Photochemically generated ketyl radicals were used to make defined lines of silver nanoparticles. The excitation of nanoparticle surface plasmons was then used to generate highly localized heat that causes polymerization selectively on the surfaces of excited particles. The nylon-6 polymer that is generated serves as a solubility switch used to retain the features on the substrate selectively; various imaging techniques were used to establish the nature of the nylon shells. This work shows that the heat generated by plasmon excitation can be exploited to generate negative-type lithographic features with dimensions well below the diffraction limit.

Photochemistry is a powerful tool for controlled synthesis of metal nanoparticles, their modification and in many of the applications that these materials have. Plasmon transitions offer a unique way of delivering energy with exquisite spatial and temporal control and can be used to advantage where visible wavelength control is required. This account of research at the University of Ottawa summarizes details of the synthesis, modification and applications of silver nanostructures.

Multiferroics, materials that exhibit coupling between spontaneous magnetic and electric dipole ordering, have significant potential for high-density memory storage and the design of complex multistate memory elements. In this work, we have demonstrated the solvent-controlled synthesis of Cr(3+)-doped BaTiO(3) nanocrystals and investigated the effects of size and doping concentration on their structure and phase transformation using X-ray diffraction and Raman spectroscopy. The magnetic properties of these nanocrystals were studied by magnetic susceptibility, magnetic circular dichroism (MCD), and X-ray magnetic circular dichroism (XMCD) measurements. We observed that a decrease in nanocrystal size and an increase in doping concentration favor the stabilization of the paraelectric cubic phase, although the ferroelectric tetragonal phase is partly retained even in ca. 7 nm nanocrystals having the doping concentration of ca. 5%. The chromium(III) doping was determined to be a dominant factor for destabilization of the tetragonal phase. A combination of magnetic and magneto-optical measurements revealed that nanocrystalline films prepared from as-synthesized paramagnetic Cr(3+)-doped BaTiO(3) nanocrystals exhibit robust ferromagnetic ordering (up to ca. 2 μ(B)/Cr(3+)), similarly to magnetically doped transparent conducting oxides. The observed ferromagnetism increases with decreasing constituent nanocrystal size because of an enhancement in the interfacial defect concentration with increasing surface-to-volume ratio. Element-specific XMCD spectra measured by scanning transmission X-ray microscopy (STXM) confirmed with high spatial resolution that magnetic ordering arises from Cr(3+) dopant exchange interactions. The results of this work suggest an approach to the design and preparation of multiferroic perovskite materials that retain the ferroelectric phase and exhibit long-range magnetic ordering by using doped colloidal nanocrystals with optimized composition and size as functional building blocks.

Visible light exposure of films containing silver nanoparticles (AgNPs) shows that the enhanced field around AgNPs in a thin film containing an azo free radical initiator (AIBN) and a triacrylate selectively cross-links the triacrylate within the plasmonic region around the particles. The cross-linked polymer is less soluble than its precursor and behaves as a solubility switch. After the film is developed with ethanol, polymer-encapsulated nanoparticles are preserved on the surface. The 8-10 nm polymer structure that encapsulates the particles effectively maps and preserves the morphology of the plasmon field in AgNP-controlled nanostructures. © 2011 American Chemical Society. Fil: Stamplecoskie, Kevin G.. University of Ottawa; Canadá Fil: Pacioni, Natalia Lorena. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. University of Ottawa; Canadá Fil: Larson, Dayle. University of Ottawa; Canadá Fil: Scaiano, Juan C.. University of Ottawa; Canadá

The ketone-photoinduced formation of Au, Ag, and Cu nanoparticles from their corresponding ions in solution has been carried out using benzoin photoinitiators. Ketones are good photosensitizers for nanoparticle synthesis not because of the energy they can absorb or deliver, but rather because of the reducing free radicals they can generate. Efficient photochemical nanoparticle generation thus requires a careful selection of substrates and experimental conditions such that free radical generation occurs with high quantum efficiency, where metal ion precursors do not inhibit radical formation. A key consideration to achieve nanoparticle synthesis with short exposure times is to minimize excited-state quenching by metal ions. Applications of nanostructures in catalysis require control of the nanoparticle characteristics, such as dimension, morphology, and surface properties. Part of this article describes the strategies to modify photochemically prepared particles. Finally, we illustrate some of the nanoparticle applications that interest us, with some emphasis on plasmon-mediated processes.

Silver clusters too small to support a plasmon band possess interesting fluorescence properties as well as being a convenient route to studying the early stages of nanoparticle formation. Fluorescent silver clusters are synthesized in toluene solution, and the formation is monitored herein by laser flash photolysis (LFP). Kinetic analysis of the formation of the Ag clusters is consistent with the formation of the smallest possible clusters, silver dimers (Ag(2)), whereby a mechanism for the formation of these clusters is provided as well as the first reported extinction coefficient and association constant for Ag(0) to form Ag(2). The formation of Ag(2) clusters is contrasted with the formation of Ag nanoparticles in aqueous media, and the particular stability and selectivity toward Ag(2) in this system is also studied using LFP.

The optimal size of spherical silver nanoparticles (AgNPs) for off-resonance surface-enhanced Raman scattering (SERS) was found to be ∼50 nm based on the equivalent Ag content in AgNP colloids. It ...

We report the first synthesis and characterization of cobalt- and chromium-doped GaN nanowires (NWs), and compare them to manganese-doped GaN NWs. Samples were synthesized by chemical vapor deposition method, using cobalt(II) chloride and chromium(III) chloride as dopant precursors. For all three impurity dopants hexagonal, triangular, and rectangular NWs were observed. The fraction of NWs having a particular morphology depends on the initial concentration of the dopant precursors. While all three dopant ions have the identical effect on GaN NW growth and faceting, Co and Cr are incorporated at much lower concentrations than Mn. These findings suggest that the doping mechanism involves binding of the transition-metal intermediates to specific NW facets, inhibiting their growth and causing a change in the NW morphology. We discuss the doping concentrations of Mn, Co, and Cr in terms of differences in their crystal-field stabilization energies (DeltaCFSE) in their gas-phase intermediates and in substitutionally doped GaN NWs. Using iron(III) chloride and cobalt(II) acetate as dopant precursors we show that the doping concentration dependence on DeltaCFSE allows for the prediction of achievable doping concentrations for different dopant ions in GaN NWs, and for a rational choice of a suitable dopant-ion precursor. This work further demonstrates a general and rational control of GaN NW growth using transition-metal impurities.

When molecules or clusters are within the proximity of metal particles, their electronic transitions can be drastically enhanced. We have now probed the off-resonance excitation of molecule-like, glutathione-capped gold clusters (Au-GSH) in the close proximity of larger (plasmonic) Au and Ag nanoparticles. The excited state absorption spectrum of Au-GSH* is obtained with monophotonic excitation. The characteristic absorption of Au-GSH* allows us to probe the influence of excited plasmonic nanoparticles coupled with the clusters. Although infrared (775 nm) lasers pulses do not produce Au-GSH*, the excited states of these clusters are formed when coupled with metal (Au, Ag) nanoparticles. Interestingly, the coupled excitation of Au-GSH/AgNP with 775 nm laser pulses also results in an enhanced field effect, as seen from increased plasmon response of the metal nanoparticles. Transient absorption measurements confirm the synergy between these two inherently different nanomaterials, causing them to display greater excitation features. Better understanding of metal cluster-metal nanoparticle interactions will have important implications in designing light harvesting systems, and optoelectronic devices.

Metals exhibit interesting optical properties, especially in comparison to molecules and semiconductors. In contrast to molecules and semiconductors, metals support plasmons, which are a collective oscillation of many electrons in the material. When the size of these metal nanoparticles is small (

Glutathione-protected gold clusters exhibit size-dependent excited state and electron transfer properties. Larger-size clusters (e.g., Au25GSH18) with core-metal atoms display rapid (1 ps) as well as slower relaxation (~200 ns) while homoleptic clusters (e.g., Au(10-12)GSH(10-12)) exhibit only slower relaxation. These decay components have been identified as metal-metal transition and ligand-to-metal charge transfer, respectively. The short lifetime relaxation component becomes less dominant as the size of the gold cluster decreases. The long-lived excited state and ability to participate in electron transfer are integral for these clusters to serve as light-harvesting antennae. A strong correlation between the ligand-to-metal charge-transfer excited state lifetime and photocatalytic activity was evidenced from the electron transfer to methyl viologen. The photoactivity of these metal clusters shows increasing photocatalytic reduction yield (0.05-0.14) with decreasing cluster size, Au25Au18Au15Au(10-12). Gold clusters, Au18GSH14, were found to have the highest potential as a photosensitizer on the basis of the quantum yield of electron transfer and good visible light absorption properties.

Single molecule fluorescence microscopy techniques are used to complement conventional catalysis and high-throughput experiments in order to gain a complete picture of a model reaction. In these experiments a model nitroarene is reduced to an amine where, upon reduction, a red shift in absorption/emission, as well as an increase in emission, is observed. The reaction is studied under bulk reaction conditions by NMR spectroscopy and the fluorescence activation makes it possible to also study this reaction at the single molecule level. Fluorescence correlation spectroscopy is a valuable technique in supporting the proposed reaction mechanism and understanding the nature and duration of molecular 'visits' to catalytic sites, where both the starting material, nitroarene, and the amine product have an affinity for the catalyst., Thanks are due to the Natural Sciences and Engineering Council of Canada and the Canadian Foundation for Innovation for generous support. M. L. Marin thanks the Universitat Politecnica de Valencia (Programa de Apoyo a la Investigacion y Desarrollo) for financial support. Technical support from Roxanne Clement at uOttawa's Centre for Catalysis Research and Innovation is gratefully acknowledged.

Thermally denatured human serum albumin interacts with ~3.0 nm spherical AgNP enhancing the fluorescence of Trp-214 at large protein/nanoparticle ratios. However, using native HSA, no changes in the emission were observed. The observation is likely due to differences between native and denatured protein packing resulting from protein corona formation. We have also found that NH2 blocking of the protein strongly affects the ability of the protein to protect AgNP from different salts/ions such as NaCl, PBS, Hank’s buffer, Tris–HCl, MES, and DMEM. Additionally, AgNP can be readily prepared in aqueous solutions by a photochemical approach employing HSA as an in situ protecting agent. The role of the protein in this case is beyond that of protecting agent; thus, Ag+ ions and I-2959 complexation within the protein structure also affects the efficiency of AgNP formation. Blocking NH2 in HSA modified the AgNP growth profile, surface plasmon band shape, and long-term stability suggesting that amine groups are directly involved in the formation and post-stabilization of AgNP. In particular, AgNP size and shape are extensively influenced by NH2 blocking, leading primarily to cubes and plates with sizes around 5–15 nm; in contrast, spherical monodisperse 4.0 nm AgNP are observed for native HSA. The nanoparticles prepared by this protocol are non-toxic in primary cells and have remarkable antibacterial properties. Finally, surface plasmon excitation of native HSA@AgNP promoted loss of protein conformation in just 5 min, suggesting that plasmon heating causes protein denaturation using continuous light sources such as commercial LED. Fil: Alarcon, Emilio I.. University of Ottawa; Canadá Fil: Bueno Alejo, Carlos J.. University of Ottawa; Canadá Fil: Noel, Christopher W.. University of Ottawa; Canadá Fil: Stamplecoskie, Kevin G.. University of Ottawa; Canadá Fil: Pacioni, Natalia Lorena. University of Ottawa; Canadá. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Poblete, Horacio. Universidad de Talca; Chile Fil: Scaiano, Juan Cesar. University of Ottawa; Canadá

Metal nanoparticles and their plasmon excitation have been used to enhance spectroscopic transitions and chemistry on metal nanoparticle surfaces. The size and shape of the enhancement area around the nanoparticles is dependant on the size, shape, dielectric constant of the matrix and the metal. We have recently reported on the use of plasmon excitation to induce acrylic polymerization on the surface of silver nanoparticles and have made ~10 nm polymer features far below the diffraction limit using visible LED irradiation. The acrylic polymerization takes advantage of plasmon enhanced excitation of azo photoinitiators in the vicinity of nanoparticles, causing cross-linking only in the enhancement region. The formation of a cross-linked polymer on the surface of the particles causes a solubility switch, where the regions unaffected by irradiation remain soluble and can be selectively washed away leaving behind the AgNP with a polymer coating. Plasmon excitation also generates a large local temperature gradients on the surface of nanoparticles and a measureable macroscopically amount of heat. The heat generated near the surface of particles can also be used to induce thermal processes with high spatial control. This spatial and temporal control over localized heating can also be used to initiate chemistry on the surface of particles relevant to the next generation of photolithography.

Photochemical methods for free radical generation can provide a powerful tool to design new strategies for the synthesis of metal nanostructures. In particular, the Norrish type I cleavage of substituted benzoins can be employed as a source of strongly reducing radicals, described here as “caged electrons.” A key to an efficient nanostructure synthesis relies on the prevention of excited state quenching by the transition metal ions used as metal precursors; the paradigm presented here emphasizes the spatial-temporal strategies that can ensure the survival of excited states so that they can perform as efficient sources of caged electrons. Keywords: photochemistry; ketyl radicals; Norrish reaction; nanoparticles; nanostructures; noble metals; photoreduction; plasmon transition; nanotechnology