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.

Carbon nanotubes possess unique properties that make them potentially useful in many applications in optoelectronics. This review describes the fundamental optical behaviour of carbon nanotubes as well as their opportunities for light generation and detection, and photovoltaic energy generation.

Carbon-nanotube photonics and optoelectronics

Polymer composites are one of the most attractive near-term means to exploit the unique properties of carbon nanotubes and graphene. This is particularly true for composites aimed at electronics and photonics, where a number of promising applications have already been demonstrated. One such example is nanotube-based saturable absorbers. These can be used as all-optical switches, optical amplifier noise suppressors, or mode-lockers to generate ultrashort laser pulses. Here, we review various aspects of fabrication, characterization, device implementation and operation of nanotube-polymer composites to be used in photonic applications. We also summarize recent results on graphene-based saturable absorbers for ultrafast lasers.

Nanotube–Polymer Composites for Ultrafast Photonics

Detection of receptor-ligand interactions is generally accomplished by indirect assays such as enzyme-linked immunosorbent assay. A direct colorimetric detection method based on a polydiacetylene bilayer assembled on glass microscope slides has been developed. The bilayer is composed of a self-assembled monolayer of octadecylsilane and a Langmuir-Blodgett monolayer of polydiacetylene. The polydiacetylene layer is functionalized with an analog of sialic acid, the receptor-specific ligand for the influenza virus hemagglutinin. The sialic acid ligand serves as a molecular recognition element and the conjugated polymer backbone signals binding at the surface by a chromatic transition. The color transition is readily visible to the naked eye as a blue to red color change and can be quantified by visible absorption spectroscopy. Direct colorimetric detection by polydiacetylene films offers new possibilities for diagnostic applications and screening for new drug candidates or binding ligands.

https://science.sciencemag.org/content/sci/261/5121/585.full.pdf

Direct colorimetric detection of a receptor-ligand interaction by a polymerized bilayer assembly

The interactions of several water-soluble ionic porphyrins with different ionic or neutral surfactants in aqueous solutions were studied as a function of surfactant concentration. The interaction leads to the formation of porphyrin aggregates and/or micelle-encapsulated monomers with the exception of those porphyrin−surfactant pairs for which the interaction is Coulombically repulsive. The premicellar surfactant−porphyrin aggregate is identified by absorption and fluorescence spectroscopy, fluorescence lifetime and anisotropy, and resonance light scattering. The spectroscopic results are used to characterize the premicellar aggregates as J-type, H-type, or nonspecific aggregates. All premicellar surfactant−porphyrin aggregates dissociate to form micelle-encapsulated monomers when the surfactant concentration approaches cmc (critical micellar concentration). The interaction of tetrakis-(4-sulfanatophenyl)porphine dianion (H4TPPS2-) at pH <3.5 with cetyltrimethylammonium cation (CTAB) is described by the fo...

J- and H-aggregates of porphyrin-surfactant complexes: time-resolved fluorescence and other spectroscopic studies

Semiconductor Carbon Nanotubes as Ultrafast Switching Materials for Optical Telecommunications

To search for sublimable squaraine (SQ) dyes for fabricating thin films under vacuum, we have synthesized a series of 2,4-bis[4-(N,N-dialkylamino)-2,6-dihydroxyphenyl]squaraines [SQ(OH)4] and studied their properties. The investigation of the behavior of their Langmuir films at the air−water interface revealed that SQ(OH)4 molecules with branched N-alkyl groups such as sec-butyls and isobutyls have larger limiting areas and tend to form J-aggregates in the monolayers, whereas molecules with straight N-alkyl chains have smaller limiting areas and are apt to form H-aggregates. This behavior is attributable to the much larger steric hindrance of the branched N-butyl groups than that of the straight ones. The thermal stability of these dyes was investigated by differential thermal analysis (DTA) and thermogravimetry (TG), and their sublimation ability was evaluated through heating under vacuum. As a result, we verified that the four hydroxyls at the 2‘,6‘-positions of the two phenyl rings significantly enhanc...

Search for Squaraine Derivatives That Can Be Sublimed without Thermal Decomposition

During the process of developing organic molecules that match the wavelengths used in optical communications, we have discovered a new class of dyes, with absorption maxima at 1.1 mum, and clarified their molecular structures. The synthesis of this class of dyes was supposed to involve unexpected intramolecular tandem reactions, and the effect of alkyl substituents on such a synthesis was investigated. As a result, an effective alkyl-substituent structure for realizing a high synthetic yield and good solubility in organic solvents was found. Furthermore, thin films made of such a highly soluble dye were fabricated by solution-coating, and they exhibited a red-shifted absorption band with a maximum at approximately 1.3 mum, indicating the formation of J-like aggregates. The third-order nonlinear optical susceptibility chi(3) of these thin films at 1.3 mum, which is the wavelength used in optical communications, was measured by the Z-scan technique. The magnitude of chi(3) reaches approximately 10-7 esu. These results suggest that the solution-coated thin films of this type of dye are potential materials for optical switching at 1.3 mum and for other nonlinear optical applications.

Discovery of Novel Dyes with Absorption Maxima at 1.1 μm

We applied time-to-space conversion using femtosecond nonlinear-optical response of squarylium-dye (SQ) J-aggregates film. A pump pulse and a train of four probe pulses were illuminated on the same area (10 mm φ) of the film in direction of oblique and normal to the film plane, respectively. Due to the oblique illumination, the pump pulse met probe pulses (interval time: 1 ps) at separate places. The film picked out part of each probe pulse by its transmittance change, which was observed for a transmitted image of spatially separated four lines. Response time of the SQ J aggregates is enough for the single-shot 1 THz demultiplexing.

Terahertz demultiplexing by a single-shot time-to-space conversion using a film of squarylium dye J aggregates

A hologram recording method for recording information of signal light as holograms in an optical recording medium, which includes illuminating signal light at the optical recording medium; illuminating reference light at the optical recording medium simultaneously with the signal light such that an interference pattern is formed by the signal light and the reference light intersecting in the optical recording medium; and shifting a region in the optical recording medium at which the signal light and the reference light intersect, by shifting an illumination position of the reference light along an optical axis of the signal light, thereby recording a plurality of holograms in the recording medium.

Makoto Furuki

Papers

Semiconductor Carbon Nanotubes as Ultrafast Switching Materials for Optical Telecommunications

Search for Squaraine Derivatives That Can Be Sublimed without Thermal Decomposition

Discovery of Novel Dyes with Absorption Maxima at 1.1 μm

Terahertz demultiplexing by a single-shot time-to-space conversion using a film of squarylium dye J aggregates

Hologram recording method and hologram recording device