Dynamics of the energy transfer involved in a diarylethene-perylenebisimide dyad: comparison between the molecule and the nanoparticle level.

Photochromic materials are widely used to achieve fluorescence photoswitching. Understanding the energy transfer processes occurring in these systems would be an advantage for their use and better optimization of their properties. In this scope, we studied a diarylethene-perylenebisimide (DAE-PBI) dyad that presents a bright red emission and a large ON-OFF contrast, both in solution and in an aqueous suspension of nanoparticles (NPs). Using ultrafast transient absorption spectroscopy, the excited state dynamics was characterized for this dyad in THF solution and compared to its behavior in NPs state. An efficient energy transfer process between the PBI fluorophore and the DAE photochromic unit in its closed form was demonstrated, occurring in a few hundreds of femtoseconds.

Non-volatile optical memory based on cooperative orientation switching: improvement of recording speed and contrast by utilizing out-of-plane orientation mode.

Herein, we report a novel strategy toward non-volatile optical memory with high-contrast, high-speed recording, and non-destructive readout capability based on the cooperative out-of-plane orientation of a fluorescent dye doped into azobenzene liquid crystalline polymer film. By employing the out-of-plane orientation switching upon irradiation with UV light and thermal heating, high-contrast turn-on fluorescence switching was successfully achieved and the optical recording was demonstrated with non-destructive fluorescence readout capability. Furthermore, the recording speed and the fluorescence on/off contrast in the present system were dramatically improved compared to the previous in-plane orientation mode.

Light-Stimulated Luminescence Control of Lead Halide-Based Perovskite Nanocrystals Coupled with Photochromic Molecules via Electron and Energy Transfer.

Photoswitchable nanomaterials are key materials in the development of advanced imaging techniques, such as super-resolution fluorescence microscopy. The combination of perovskite CsPbBr3 nanocrystals (NCs) with bright photoluminescence (PL) emission and diarylethenes (DAEs) with structural changes in response to ultraviolet (UV) and visible light is a promising candidate system. Herein, CsPbBr3 NCs are coupled with photochromic DAE molecules to control the PL emission from the NCs by light stimulation. The PL emission is successfully switched ON and OFF by alternating UV and visible light irradiation. Time-resolved PL emission studies suggest that Förster resonance energy transfer from CsPbBr3 NCs to the closed-ring form of DAE occurs after UV irradiation, and the PL emission is quenched. Upon visible-light irradiation, DAE is converted to the open-ring isomer, and the PL emission is restored. Femtosecond pump-probe spectroscopy reveals that light stimulation induces not only energy transfer but also photoinduced electron transfer in the NC-DAE pair on the picosecond timescale to form DAE radicals. Thus, it is suggested that the holes residing in the NCs react with the NCs, degrading the PL emission. Stable PL switching is realized using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a hole scavenger to avoid the reaction between the holes and NCs.

All-Visible (>500 nm)-Light-Induced Diarylethene Photochromism Based on Multiplicity Conversion via Intramolecular Energy Transfer.

Photoswitching molecules that reversibly switch upon visible-light irradiation are some of the most attractive targets for biological and imaging applications. In this study, we found a diarylethene (DAE) derivative having a covalently attached perylenebisimide (PBI) unit (DAE-PBI dyad) underwent an unexpected cyclization reaction upon irradiation with green (500-550 nm) light, where the DAE unit has no absorbance. The photoreactivity was enhanced in solvents containing heavy atoms and in the presence of oxygen. As inferred from the solvent dependence and the calculated excited-state energies of DAE and PBI units, it was suggested that the probable mechanism for this unique visible-light-induced cyclization reaction is multiplicity conversion based on intramolecular energy transfer from the excited singlet state of the PBI unit to the triplet state of DAE units (i.e., DAE-1[PBI]* → 3[DAE]*-PBI). Such a unique photoreaction mechanism with the assistance of oxygen will pave the way for new molecular design for the development of visible-light switching molecules.

Photochemical OFF/ON Cytotoxicity Switching by Using a Photochromic Surfactant with Visible Light Irradiation.

Photochemical switching of cytotoxicity by using spiropyran compounds with pyridinium and alkyl groups was investigated. The spiropyran compound, SP6, with a hexyl group as the alkyl group displayed negative photochromism, in which the hydrophilic open merocyanine form (MC form) was stable and isomerized to the hydrophobic closed spiro form (SP form) by visible light irradiation. Both MC and SP forms exhibited amphiphilicity because of the hydrophobic hexyl and hydrophilic pyridinium groups introduced. Cytotoxicity toward HeLa cells was observed for both MC and SP forms of SP6 at concentrations higher than the critical aggregation concentration of the isomers CACMC and CACSP (CACMC > CACSP), respectively. In contrast, cytotoxicity by SP6 was activated by visible light irradiation at concentrations between CACMC and CACSP; thus, photochemical switching of cytotoxicity from the OFF to ON state was achieved. Cytotoxicity was revealed to be caused by disruption of the cell membrane. The results provide an important step in developing novel next-generation photochemotherapy drugs.

Determining Factor of the Quantum Yield of the Cyclization Reaction via Triplet States for Dye-Attached Diarylethene.

The difference in the quantum yields of the cyclization reaction of two isomers of dye-attached diarylethene via the triplet state observed in the experiment [J. Phys. Chem. C 2009, 113, 11623-11627] was theoretically examined by quantum chemical calculations. By evaluating the spin-orbit couplings, we found that the ratio of the rate constants from the S1 state to the T2 state between two isomers agreed with that of the experimental quantum yield of the cyclization reaction. The difference in the spin-orbit couplings is due to the difference in the delocalization of the orbitals between diarylethene and dye. We further found that after the intersystem crossing took place the cyclization reaction via the triplet state occurred in the experiment due to the low energy barrier (∼10 kcal/mol) for the reaction.

Adsorption and release on three-dimensional graphene oxide network structures.

In this study, three-dimensional network architectures are constructed using nano-sized graphene oxide (nGO) as the building block. The cross-linking reaction of nGO is conducted in sub-micrometre water droplets in an emulsion system to control the size of the networks by restricting the reaction space. Two types of three-dimensional GO networks with different cross-linking lengths were constructed, and their methyl orange adsorption and release behaviours were investigated under external stimuli, such as thermal treatment, ultrasonic wave treatment and near-infrared light irradiation.

Efficient NIR-I fluorescence photoswitching based on giant fluorescence quenching in photochromic nanoparticles.

A photoswitchable near-infrared (NIR) fluorescent nanoparticle (NP) was designed and prepared. The NP showed a characteristic AIE property and high-contrast NIR fluorescence photoswitching with full reversibility. Such efficient NIR fluorescence photoswitching originated from the amplified fluorescence quenching mechanism based on intermolecular energy transfer in a densely packed NP state.

Reversible ON/OFF switching of photoluminescence from CsPbX3 quantum dots coated with silica using photochromic diarylethene.

Highly luminescent silica-coated CsPbX3 quantum dots (QDs) with good photostability were synthesized and coupled with photochromic diarylethene to modulate the QDs' photoluminescence (PL). Upon successive UV and visible light irradiation, the PL emission from the silica-coated CsPbX3 QDs was repeatedly quenched and restored, demonstrating the promising feasibility of the QD/diarylethene-based photoswitches.

Efficient "turn-off" fluorescence photoswitching in a highly fluorescent diarylethene single crystal.

A highly fluorescent diarylethene single crystal was successfully designed and prepared. The crystal shows efficient "turn-off" fluorescence photoswitching with full reversibility. This might have originated from the amplified fluorescence quenching due to the intermolecular energy transfer process in the densely packed and well-ordered single crystal.

Fluorescence On/Off Switching in Nanoparticles Consisting of Two Types of Diarylethenes.

Single- and double-component nanoparticles consisting of two types of diarylethenes, 1,2-bis(3-methyl-5-phenyl-2-thienyl)perfluorocyclopentene (1a) and 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene (2a), were fabricated by a reprecipitation method. Nanoparticles consisting of 1a exhibited orange or green fluorescence depending on the fabrication condition and did not undergo any photocyclization reaction. On the other hand, nanoparticles consisting of 2a underwent photoreversible photochromic reactions upon alternating irradiation with ultraviolet and visible light. Nanoparticles consisting of 1a and 2a exhibited fluorescence on/off switching with rapid switching speed and high on/off contrast, accompanying the photochromic reactions of 2a. The dependence of fluorescence on/off switching properties on Förster distance and molar fraction was observed and quantitatively evaluated by a simplified model.

Trapping and Deposition of Dye-Molecule Nanoparticles in the Nanogap of a Plasmonic Antenna.

Plasmonic nanostructures, which allow light focusing at the deep subwavelength scale, and colloidal nanoparticles with unique optoelectronic properties are nowadays fabricated with nanometer precision. However, to fully control and exploit nanoscale light-matter interactions in hybrid plasmonic-nanophotonic devices, both materials must be assembled in heterostructures with similar precision. Near-field optical forces have recently attracted much attention, as they can precisely trap and position nanoparticles at plasmonic hotspots. However, long-range attraction and the surface bonding of nanoparticles usually require other specific techniques, such as electrothermal heating and surface chemical treatments. This Letter reports on the optical trapping and deposition of dye-molecule nanoparticles in the nanogap of a gold antenna. The nanoparticles are captured by focusing a near-infrared laser beam on a targeted plasmonic antenna. This single-step deposition process requires only a few seconds under 1.4-1.8 MW·cm-2 continuous-wave illumination and shows a polarization dependence smaller than expected. Fluorescence and electronic microscopy observations suggest that nanoparticle deposition arises from a trade-off between optical and thermal effects.

Live Cell Imaging Using Photoswitchable Diarylethene-Doped Fluorescent Polymer Dots.

Fluorescence photoswitching using nanomaterials has recently emerged as a promising approach for the imaging of biological targets. However, despite intensive research efforts during the last decade, practical microscopy of biological targets using photoswitchable nanoparticles in real time remains challenging. To address this problem, we have developed live macrophage cell imaging and single particle imaging methods, using photoswitchable fluorescent diarylethene-doped polymer nanoparticles (P-dots) under Xe lamp irradiation. We established a 34-times prolonged "off-state", using P-dots doped with a diarylethene-containing methoxy substituent, upon visible-light irradiation using a Xe lamp and a green fluorescent protein filter cube. To demonstrate the practicality of doped P-dots imaging, we imaged lysosomes in macrophage cells, and observed 11-times slower recovery of the fluorescence from the "off-state" to the "on-state", indicating their potential for cellular imaging.

Wavelength-selective and high-contrast multicolour fluorescence photoswitching in a mixture of photochromic nanoparticles.

Herein, we report on wavelength-selective and high-contrast multicolour fluorescence photoswitching between white-, orange-, cyan-, and dark-colours in a mixture of two distinguishable emission-coloured photochromic nanoparticles composed of different pairs of a photoswitching unit and a fluorescence unit.

Giant Amplification of Photoswitching by a Few Photons in Fluorescent Photochromic Organic Nanoparticles.

Controlling or switching the optical signal from a large collection of molecules with the minimum of photons represents an extremely attractive concept. Promising fundamental and practical applications may be derived from such a photon-saving principle. With this aim in mind, we have prepared fluorescent photochromic organic nanoparticles (NPs), showing bright red emission, complete ON-OFF contrast with full reversibility, and excellent fatigue resistance. Most interestingly, upon successive UV and visible light irradiation, the NPs exhibit a complete fluorescence quenching and recovery at very low photochromic conversion levels (<5 %), leading to the fluorescence photoswitching of 420±20 molecules for only one converted photochromic molecule. This "giant amplification of fluorescence photoswitching" originates from efficient intermolecular energy-transfer processes within the NPs.

Anisotropic elliptical dichroism and influence of imperfection of circular polarization upon anisotropic circular dichroism.

In spite of the importance of anisotropic circular dichroism, in practice, it is difficult to get rid of the artifacts that arise from the imperfection of the circular polarization. Undesirable linear dichroism, interference of two orthogonal polarization states, and linear birefringence prevent us from making accurate measurements. We propose a theoretical method for evaluating the contributions of the first two, which are thought to be the main artifacts when specimens are not thick enough. Using the time-dependent perturbation theory and taking into account the direction of light propagation toward an orientationally fixed molecule, we formulated the transition probability of systems perturbed by arbitrarily polarized light and the absorption difference associated with two kinds of polarized light. We also formulated, as an extension of the dissymmetry factor of circular dichroism, a newly defined dissymmetry factor associated with two arbitrary polarization states. Furthermore, we considered a mixed-state of photon ensemble in which polarization states distribute at a certain width around a certain average. Although the purity of polarization and ellipticity does not correspond immediately, by considering the mixed state it is possible to treat them consistently. We used quantum statistical mechanics to describe the absorption difference for two kinds of photon ensembles and applied the consequent formula to examine the reported experimental results of single-molecule chiroptical responses under discussion in the recent past. The artifacts are theoretically suggested to be sensitive to the incident direction of elliptically polarized light and to the oriented systems, the ellipticity, and the orientation of ellipse. The mixed state has little, if any, effect when the polarization state distribution is narrow.

Molecular design strategy toward diarylethenes that photoswitch with visible light.

Photoactive molecules that reversibly switch upon visible light irradiation are one of the most attractive targets for biological as well as imaging applications. One possible approach to prepare such photoswitches is to extend π-conjugation length of molecules and shift the absorption bands to longer wavelengths. Although several attempts have been demonstrated based on this approach for diarylethene (DAE) photoswitches, photoreactivity of the DAE derivatives is dramatically suppressed when the conjugation length is extended by connecting aromatic dyes at the side positions of aryl groups in the DAE unit. In this study, we successfully prepared a visible-light reactive DAE derivative by introducing an aromatic dye at the reactive carbon atom of the DAE unit, optimizing orbital level of each component, and controlling the mutual orientation of the aromatic dye and the DAE unit. The DAE derivative (3) undergoes a photocyclization reaction upon irradiation with 560 nm light and the closed-isomer converts to the open-ring isomer upon irradiation with 405 nm light. The high photoconversion yields (>90%) were achieved for both photocyclization and photocycloreversion reactions. The photoreactivity induced by visible light irradiation and the molecular design strategy were discussed based on theoretical calculations.

Anisotropic dissymmetry factor, g: theoretical investigation on single molecule chiroptical spectroscopy.

A formula for an anisotropic dissymmetry factor g evaluating the chiroptical response of orientationally fixed molecules is derived. Incorporating zeroth- and first-order multipole expansion terms, it is applied to bridged triarylamine helicene molecules to examine the experimental results of single-molecule chiroptical spectroscopy. The ground- and excited-state wave functions and a series of transition moments required for the evaluation of the anisotropic g value are calculated using time-dependent density functional theory (TDDFT). The probability histograms obtained for simulated g values, uniformly sampled in regard to the direction of light propagation toward the fixed molecule, show that even for a given diastereomer, the dissymmetry factors have positive and negative values and can deviate from their averages to a considerable extent when the angle between the electric dipole transition moment and the propagation vector of the incident light is near 0 or 180°.

Complete ON/OFF photoswitching of the motility of a nanobiomolecular machine.

To apply motor proteins as natural nanomolecular machines to transporting systems in nanotechnology, complete temporal control over ON/OFF switching of the motility is necessary. We have studied the photoresponsive inhibition properties of azobenzene-tethered peptides for regulation of kinesin-microtubule motility. Although a compound containing a peptide having an amino acid sequence derived from the kinesin's C-terminus (a known inhibitor of kinesin's motor domain) and also featuring a terminal azobenzene unit exhibited an inhibition effect, the phototunability of this behavior upon irradiation with UV or visible light was only moderate. Unexpectedly, newly synthesized peptides featuring the reverse sequence of amino acids of the C-terminus of kinesin exhibited excellent photoresponsive inhibition. In particular, azobenzene-CONH-IPKAIQASHGR completely stopped and started the motility of kinesin-microtubules in its trans- and cis-rich states, respectively, obtained after irradiation with visible and UV light, respectively. A gliding motility system containing this photoresponsive inhibitor allowed in situ control of the motion of microtubules on a kinesin-coated glass substrate. It is expected that the present results on the photoresponsive nanomotor system open up new opportunities to design nanotransportation systems.