Publications by authors named "Tsuyoshi Asahi"

Gold nanoparticles (AuNPs) have been utilized as colorimetric biosensors, where target molecule-induced AuNP aggregation can be recognized by a colour change from red to blue. Particularly, single-stranded DNA (ssDNA)-immobilized AuNPs (ssDNA-AuNPs) have been applied to genetic diagnosis due to their rapid and sequence-specific aggregation properties. However, the effect of the density of immobilized ssDNA have not been investigated yet.

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Article Synopsis
  • A new cation was created by adding methyl groups to a zwitterionic compound called squarylium, resulting in unique ion pairs with various anions.
  • The ion pairs showed different light absorption and emission properties, influenced by their arrangement into J- and H-aggregates when dispersed.
  • In solid form, the arrangement of these cation-anion pairs led to enhanced electric conductivity along a specific stacking axis, thanks to reduced electrostatic repulsion between the cations.
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Modifications in curved π-electronic systems, dipyrrolylbenzodiazepines, resulted in various derivatives with modulated electronic properties and assembly behaviour. The electron-rich pyrrole-based curved π-system exhibited C complexation in the form of a hydrogen-bonding cyclic hexamer, giving rise to solid-state photo-induced electron transfer as elucidated by transient absorption spectroscopy.

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Gold nanoparticles (AuNPs) are often used for biosensing. In particular, aptamer-modified AuNPs are often used for colorimetric molecular detection, where target molecule-induced AuNP aggregates can be recognized by a color change from red to blue. However, non-specific aggregation could be induced by various compounds, leading to false-positive results.

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In this study, charged π-electronic species are observed to develop stacking structures based on electrostatic and dispersion forces. π- π Interaction, defined herein, functions for the stacking structures consisting of charged π-electronic species and is in contrast to conventional π-π interaction, which mainly exhibits dispersion force, for electronically neutral π-electronic species. Establishing the concept of π- π interaction requires the evaluation of interionic interactions for π-electronic ion pairs.

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Intense ns pulse laser excitation to nanoparticle colloids of a photochromic diarylethene induced an amplified cycloreversion reaction. The mechanism was explained as a 'photosynergetic response' coupled with nanoscale laser heating and the photochemical reaction in nanoparticles.

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Gold nanoparticles (AuNPs) have been commonly used in molecular sensing, in the form of observation of the color change from red to blue of the AuNP solution, caused by target-molecule-induced AuNP aggregation. In this work, the changes in absorbance and scattering spectra caused by AuNP aggregation were studied using thrombin-induced AuNP aggregation as a model. We demonstrated for the first time that scattering spectra is more sensitive to the changes owing to AuNP aggregation than absorbance spectra.

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Iron-based nanoparticles (FeNPs) have unique and attractive properties such as superparamagnetism, biocompatibility, and catalytic activity. Although the synthesis of precious metal NPs from a metal in liquid and/or metal salt solution by a pulsed laser has been investigated, comparably little effort has been devoted to examine the production of FeNPs. Here we report the synthesis of carbon-shell free spherical NPs of iron oxide (magnetite) from ferrocene hexane solution by femtosecond near infrared laser pulses.

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Femtosecond excited-state dynamics of fullerene-C nanoparticles (nC) having a mean size of 50 nm dispersed in pure water was studied by means of femtosecond transient absorption spectroscopy. The intermolecular charge-transfer (CT) excited state in solid C was directly and firstly observed by femtosecond 350 nm and 420 nm excitations, and its intrinsic lifetime of 0.35 ps was found.

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We prepared stable nanodispersions of a fluorescent perylenediimide (PDI) derivative having long alkyl chains by nanosecond laser fragmentation of its microcrystalline powder in acetonitrile (ACN). The nanoparticles had cube-like or rod shapes with a mean size of 100 nm, and they dispersed stably for longer than 1 month. The prepared nanobricks exhibited absorption and fluorescence spectra characteristic of one-dimensional aggregates with cofacial stacking of PDI planes.

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We have developed a femtosecond pump-probe light scattering microspectroscopic system in which the output of a femtosecond Ti:sapphire oscillator (1 W, 82 MHz) was used as a light source; the pump light is the second harmonics (395 nm) of the laser output, and the probe light is a femtosecond white-light continuum (490-900 nm) generated with a photonic crystal fiber. Detection of the backscattered light from single nanoparticle on a glass substrate allowed us to obtain higher gain of the transient signals by ∼20 times in comparison with the conventional transmittance-mode experiment. This high-sensitivity of the backscattering detection makes it possible to examine ultrafast relaxation dynamics of excited states in organic nanoparticles, which, in general, are lower photodurability than the inorganic one.

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Hybrid materials combining gold nanoparticles (GNP) of variable diameter and an organic thin layer of photochromic diarylethenes were achieved. Solid-state photoswitching based on ring-closure/ring-opening reaction was carried out under alternate UV and visible irradiations. In addition to the spectral changes due to the photochromism itself, the surface plasmon resonance related to the GNP is significantly modified, influenced by a photoinduced change in the refractive index of its environment.

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The fabrication of silver nanoparticles covered with polymers with a well-defined core-shell structure and the quantitative evaluation of the plasmonic enhancement effect on a photochemical reaction in the vicinity of these silver nanoparticles individually dispersed in a medium are described. The photocycloreversion reaction of a diarylethene polymer in the vicinity of silver nanoparticles was enhanced by 2-6 times relative to the reaction without the nanoparticles. The promotion of the photocycloreversion reaction is due to enhancement of the electromagnetic field near the surface of the silver core.

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We newly synthesized various sized gold nanoparticles covered with photochromic polymers consisting of diarylethenes with various structures to investigate an effect of the gold nanoparticles on the photocycloreversion reaction of the diarylethene chromophores upon irradiation with visible light. The gold nanoparticles covered with the photochromic polymers exhibited reversible changes in localized surface plasmon resonance (LSPR) absorption along with the photochromic reaction depending on the diameter of the particle, the distance between the gold surface and the chromophore, and the structure of the diarylethene chromophore. The rate of the photocycloreversion reaction of the chromophores around the particle was enhanced by the gold nanoparticles and the degree of the enhancement was affected by the diameter of the particle and the distance from the gold surface, while a structural difference in the diarylethene chromophore had no effect on the degree of the enhancement.

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Stable aqueous colloids of 10-nm sized organic nanoparticles were tailored by laser ablation of microcrystalline quinacridone in water. The nanocolloids were flaky in shape and had the dimension of a width of 13 (±5) nm and a height of 1.4 (±0.

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We have studied the photochromic reaction of p-hydroxycinnamic-thiophenyl ester in the microcrystalline state. We attributed the fluorescence spectral evolution of the microcrystal, under UV irradiation, to the photoinduced trans-to-cis isomerization. The photocyclic behavior of the chromophore was demonstrated by cis-to-trans back reaction under a subsequent visible light irradiation.

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We have studied the photoinduced trans/cis isomerization of the protonated form of p-hydroxycinnamic thiophenyl ester, a model chromophore of the photoactive yellow protein (PYP), in crystalline phase, by both fluorescence and infrared spectroscopies. The conversion from trans to cis configuration is revealed by a shift of the fluorescence peak and by inspection of the infrared maker bands. The crystal packing apparently stabilizes the cis photoproduct, suggesting different environmental effects from the solvent molecules for this model chromophore in liquid solutions or from the amino acid residues for the PYP chromophore.

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Femtosecond near-infrared laser microscope was developed with a home-built cavity-dumped chromium:forsterite laser as a light source centered at 1.26 microm. Optimization of the pulse duration achieved 35 fs fwhm at the sample position of the microscope after passing through a 100x objective.

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Microcrystalline powders of spirooxazine and spiropyran compounds do not show photocoloration under steady-state illumination, whereas they undergo photochromism on intense femtosecond laser-pulse excitation. We investigated the characteristic mechanism of the crystalline photochromism by studying the photocoloration of spironaphthooxazine (SNO) and its chloro-substituted derivative (Cl-SNO) with our femtosecond diffuse-reflectance spectroscopic system. In particular, femtosecond double-pulse excitation using 390+780-nm pulses and 390+390-nm pulses, with a variable time interval between the two pulses, was applied to reveal an intermediate species involved in the photocoloration.

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Organic dye nanoparticles 1-13 nm in height and 10-45 nm in width were prepared by the reprecipitation method. With single-molecule/nanoparticle spectroscopy, two distinct types of nanoparticles were found: particles with blue emission and particles with red emission. The difference in spectral characteristics is attributed to the presence of two morphological types of particles in the samples.

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Monodispersed polymer/polydiacetylenecomposite particles were synthesized by soap-free seeded emulsion polymerization of styrene andmethyl methacrylate; the products were characterized by XRD, SEM, TEM, UV-visible spectroscopy, and single particle scattering spectroscopy. In the synthesis process, polydiacetylene nanocrystals were found to act as inhibitor, and consequently a relatively low concentration was necessary. Different monomers lead to the differences in reaction condition and particle morphology; the PMMA composite particles were simpler in preparation than polystyrene particles, but the latter havebetter spherical morphology.

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