Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

Signaling Recognition Events with Fluorescent Sensors and Switches.

The emergence of semiconductor nanocrystals as the building blocks of nanotechnology has opened up new ways to utilize them in next generation solar cells. This paper focuses on the recent developments in the utilization of semiconductor quantum dots for light energy conversion. Three major ways to utilize semiconductor dots in solar cell include (i) metal−semiconductor or Schottky junction photovoltaic cell (ii) polymer−semiconductor hybrid solar cell, and (iii) quantum dot sensitized solar cell. Modulation of band energies through size control offers new ways to control photoresponse and photoconversion efficiency of the solar cell. Various strategies to maximize photoinduced charge separation and electron transfer processes for improving the overall efficiency of light energy conversion are discussed. Capture and transport of charge carriers within the semiconductor nanocrystal network to achieve efficient charge separation at the electrode surface remains a major challenge. Directing the future resear...

http://wiki.phy.queensu.ca/shughes/images/d/d1/Quantum_Dot_Solar_Cells._Semiconductor_Nanocrystals_as_Light_Harvesters.pdf

Quantum Dot Solar Cells. Semiconductor Nanocrystals as Light Harvesters

The increasing energy demand in the near future will force us to seek environmentally clean alternative energy resources. The emergence of nanomaterials as the new building blocks to construct light energy harvesting assemblies has opened up new ways to utilize renewable energy sources. This article discusses three major ways to utilize nanostructures for the design of solar energy conversion devices:  (i) Mimicking photosynthesis with donor−acceptor molecular assemblies or clusters, (ii) semiconductor assisted photocatalysis to produce fuels such as hydrogen, and (iii) nanostructure semiconductor based solar cells. This account further highlights some of the recent developments in these areas and points out the factors that limit the efficiency optimization. Strategies to employ ordered assemblies of semiconductor and metal nanoparticles, inorganic-organic hybrid assemblies, and carbon nanostructures in the energy conversion schemes are also discussed. Directing the future research efforts toward utiliza...

Meeting the Clean Energy Demand: Nanostructure Architectures for Solar Energy Conversion

J-aggregates are of significant interest for organic materials conceived by supramolecular approaches. Their discovery in the 1930s represents one of the most important milestones in dye chemistry as well as the germination of supramolecular chemistry. The intriguing optical properties of J-aggregates (in particular, very narrow red-shifted absorption bands with respect to those of the monomer and their ability to delocalize and migrate excitons) as well as their prospect for applications have motivated scientists to become involved in this field, and numerous contributions have been published. This Review provides an overview on the J-aggregates of a broad variety of dyes (including cyanines, porphyrins, phthalocyanines, and perylene bisimides) created by using supramolecular construction principles, and discusses their optical and photophysical properties as well as their potential applications. Thus, this Review is intended to be of interest to the supramolecular, photochemistry, and materials science communities.

J-aggregates: from serendipitous discovery to supramolecular engineering of functional dye materials.

Oxidation with metal oxides—II : Oxidation of chalcone phenylhydrazones, pyrazolines, o-aminobenzylidine anils and o-hydroxy benzylidine anils with manganese dioxide

A self-assembled photoactive antenna system containing a gold nanoparticle as the central nanocore and appended fullerene moieties as the photoreceptive hydrophobic shell is designed by functionalizing a gold nanoparticle with a thiol derivative of fullerene. Upon suspension of fullerene-functionalized gold nanoparticles (Au−S−C60) in toluene we observe formation of 5−30 nm diameter clusters. The ease of suspending these nanoassemblies in organic solvents allows us to probe the excited state interactions by spectroscopic methods. The quenching of fluorescence emission as well as decreased yields of triplet excited state suggest the participation of excited singlet in the energy transfer to the gold nanocore. Application of electrophoretically deposited Au−S−C60 nanoassemblies on optically transparent electrodes in the photoelectrochemical conversion of light energy has been demonstrated.

Fullerene-Functionalized Gold Nanoparticles. A Self-Assembled Photoactive Antenna-Metal Nanocore Assembly

The infrared spectra of rare earth acetates have been studied to examine the metal-acetate bonding. The thermal decomposition of rare earth acetates as well as lead and copper acetates have been investigated in detail by employing thermogravimetric analysis and differential thermal analysis. Thermal decomposition of calcium dicarboxylates (malonate to sebacate) have been studied employing t.g.a. and d.t.a. Infrared spectra of the dicarboxylates have also been studied. Preliminary results on the products of decomposition of dicarboxylates have been reported.

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Infrared spectra and thermal decompositions of metal acetates and dicarboxylates

Preparation of Silyl- and Germylmetallic Compounds

— We describe the synthesis and photophysical studies, including measurements of quantum yields of triplet excited states and singlet oxygen generation of bis(3,5-dibromo-2,4,6-trihydroxyphenyl)squaraine (2) and bis(3,5-diiodo-2,4,6-trihydroxyphenyl)squaraine (3). These dyes exist in solution in the protonated, neutral, single and double depro-tonated forms, depending on pH. The pKa values of these dyes were found to be relatively lower than those of the parent bis(2,4,6-trihydroxyphenyl)squaraine (1). Only the single deprotonated forms (Sq) of 2 and 3 showed measurable fluorescence. In microheterogeneous media such as in the presence of β-cyclodextrin, cetyltrunethylammonium bromide and polyvinylpyrrolidone), bathochromic shifts in the absorption and emission spectra of Sq were observed with a substantial enhancement in their fluorescence yields. Triplet excited states are the main transient intermediates obtained upon 532 nm laser excitation of the various forms of 2 and 3 in methanol. These triplets have lifetimes in the range from 0.061 to 132 μs. The triplet quantum yields of double deprotonated forms are low (φT = <0.01), whereas the neutral and Sq−forms of 2 (φr = 0.12 and 0.22) and 3 (φT= 0.24 and 0.5), respectively, exhibited significant triplet yields. Quantum yields of singlet oxygen generation by Sq−forms of 2 and 3 were determined in methanol and were found to be 0.13 and 0.47, respectively, which are in good agreement with the triplet yields obtained in these systems.

Halogenated Squaraine Dyes as Potential Photochemotherapeutic Agents. Synthesis and Study of Photophysical Properties and Quantum Efficiencies of Singlet Oxygen Generation

Manapurathu V. George

Papers

Oxidation with metal oxides—II : Oxidation of chalcone phenylhydrazones, pyrazolines, o-aminobenzylidine anils and o-hydroxy benzylidine anils with manganese dioxide

Fullerene-Functionalized Gold Nanoparticles. A Self-Assembled Photoactive Antenna-Metal Nanocore Assembly

Infrared spectra and thermal decompositions of metal acetates and dicarboxylates

Preparation of Silyl- and Germylmetallic Compounds

Halogenated Squaraine Dyes as Potential Photochemotherapeutic Agents. Synthesis and Study of Photophysical Properties and Quantum Efficiencies of Singlet Oxygen Generation