Two-color light was irradiated to azo-polymer films to investigate the mechanism of light-induced polymer movement. A collimated green light was used for inducing softening of the polymer, while a focused red light was used for inducing optical gradient force. We found from the topology change of the film that polymer movement was induced only when both green and red light were simultaneously irradiated. This finding indicated that the polymer movement was induced by optical gradient force generated by the red light under the condition that the polymer was softened by repeatable photoisomerization by the green light.
DNA changes its conformation by combining a transcription factor or transcription factor complex on specific base sequences. We investigated the conformation changes by using local surface plasmon resonance of two gold nanoparticles linked to each other via the DNA, which compose a nano-dimer. Gap distance of the nano-dimer is reduced due to the DNA conformation change or bending, then the plasmon resonance shifts to longer wavelength. By measuring the plasmon resonant wavelength, gap distance is determined with a calibration curve prepared beforehand. Hence, conformation change of DNA bound with transcription factors is evaluated at nanoscale or sub-nanoscale. For example, a bending angle was determined to be 61.3º when SOX2, one of transcription factors, was bound on a double-stranded DNA having DC5 sequence and the DNA changes conformation. Binding SOX2 and PAX6 together on DC5 sequence, bending angles were evaluated to be 61.3º at SOX2 side and 5.7º at PAX6 side, respectively. When we used DNA having a DC5-con sequence which is a little different from DC5 sequence, bending angles were evaluated to be 61.1º at SOX2 side and 2.3º at PAX6 side. Such small difference in DNA conformations can be distinguished by using the local surface plasmon resonance. We also observed DNA conformation change by binding SOX2 on DC5 in real time and duration for conformation change was determined to be less than 100 msec. Such binding of DNA and transcription factors has possibility for a driving component for nano-machines.
The investigation of light-matter interaction has had growing interest in the field of photonics. In particular, metalinsulator-metal (MIM) sensors are of interest owing to their high sensitivity compared to conventional sensor made by a single metal layer. The high resolution and low concentrations detection is a result of the sharp resonance of the surface plasmon polariton waveguide hybrid mode at the Au/water interface supported by MIM structures. In this context, we have implemented experiments and theoretical simulations to estimate the enhancement of the sensitivity of metal-insulatormetal sensors. By changing the refractive index of an aqueous solution of glucose, we found that the use of a metalinsulator-metal stack improves the figure of merit of the sensor 7.5 times compared to that of a conventional surface plasmon resonance sensor.
Light-induced patterns of surface deformations in azobenzene containing polymer films have attracted much attention because of possible applications in optical data storage and in micro/nano fabrication. It is well known that such patterns reflect the state of the incident light polarization and the light intensity distribution. Trans ↔ cis photoselective isomerization and molecular reorientation play important roles in the deformation process. Among a variety of applications utilizing light-induced mass movement in azo-polymers, sub-diffraction imaging of optical near-fields is one of the most promising applications. In this application, optical near-field distribution in the vicinity of nano structures is transferred to surface deformations of azo-polymers through light-induced mass movement, where the spatial resolution can exceed the diffraction light of light. In addition to the high spatial resolution, not only intensity distribution but also polarization state of near-fields can be measured. In this presentation, we will report on photo-induced polymer movement induced by optical near-field in the vicinity of single gold nano-particles (GNPs). A linearly polarized (Ex) laser beam was irradiated into GNPs to excite local surface plasmon resonance that enhanced the near-field around the GNPs. The findings indicated that different GNP diameters (that is, 50 nm and 80 nm) resulted in different deformation patterns on the films. The results were compared with theoretical calculations of near-field distributions, and the observations revealed that the deformation patterns were dependent on the ratio between Ex and Ey wherein each possessed a different field distribution.
When the size of metallic nanoparticles becomes smaller than 1 nm, of which nanostructures are composed of several tens of atoms, the plasmonic effect disappears and the electronic energy levels of the nanoparticles called as nanoclusters are quantized. Then, the nanoclusters can emit fluorescence of which wavelength depends on their size. We investigated synthetic method of Platinum nanoclusters (Pt NCs) that exhibit blue to yellow photoluminescence by a facile one-pot reduction method. They were synthesized from the mixture of H2PtCl6, hyper-branched polyethylenimine (PEI), and L-ascorbic acid, resulting in the formation stabilized with the amino groups in the cavities formed by coiled PEI ligands. The chain conformation of cationic polymer PEI depends on pH of solution. By controlling pH of the synthesis solution, the size of Pt NCs@PEI changes and their fluorescent wavelength can be tuned. Pt NCs@PEI were applied to the labeling of Chemokine receptors of the membrane of cancer HeLa cells and Glutamate receptors of the membrane of neural cells by binding them to an antibody via a conjugate protein for bio-imaging. They showed lower cell cytotoxicity than other nanoparticles such as Q-dots@COOH, indicating that they have better cell viability and great potential for biological applications.
Optical tweezing;by photochemistry is a novel concept in the field of optical manipulation. I discuss it in azo-polymer films through theory and experiments. I will show that optical tweezing can be obseved by a photochemical force, e.g. photoisomerization force which leads to a spring type motion. This force is derived from a harmonic light potential that moves the azo-polymer, and it is parenting to optical tweezers since it occurs in the presence of a gradient of light intensity, but it is quite different in the sense that it requires photoisomerization to occur. The azo-polymer’s motion is governed by four competing forces: the photoisomerization force, and the restoring optical gradient and elastic forces, as well as the random forces due to spontaneous diffusion.
We present experimental evidence of the generation of narrow Fano line shapes in planar multilayer
structures. The Fano line shape originates from coupling between a high loss surface plasmon
polariton mode with a low loss planar waveguide mode. The line shape is shown to depend strongly
on the structural parameters that govern the position of the waveguide mode and the coupling
strength, and to be in good agreement with results of electromagnetic calculations.
Photomigration in azo polymers is an area of research that witnessed intensive studies owing to its potential in optical manipulation; e.g. optical tweezing; the physical mechanism of which remains unsolved since its discovery about two decades ago. In this presentation, a detailed theoretical study that reproduces the phenomena associated with photomigration is presented, including the physical models and the associated master equations. I discuss polarization effects and I give the analytical solutions describing the steady-state and the dynamics of photomigration.
KEYWORDS: Polymers, Polarization, Polymer thin films, Atomic force microscopy, Near field, Near field optics, Diffraction, Absorption, Optical lithography, Glasses
We review our work on nanopatterning in azo-polymer films by single, two- and multi-phopton driven
molecular motion in solid bulk polymer. It is now known that light induced molecular movement occurs
below the polymer glass transition temperature by chromophores photoisomerization via either linear or
nonlinear absorption, and in this paper we will show that nanoscale polymer movement is induced by a
tightly focused laser beam in an azo-polymer film just at the diffraction limit of light. The deformation
pattern which is produced by photoisomerization of the azo dye is strongly dependent on the incident laser
polarization and the longitudinal focus position of the laser beam along the optical axis. The anisotropic
nanofluidity of the polymer film and the optical gradient force played important roles in the light induced
polymer movement. We explored the limits of the size of the photo-induced deformation, and we found that
the deformation depends on the laser intensity and the exposure time. The smallest deformation size
achieved was 200 nm in full width of half maximum; a value which is nearly equal to the size of the
diffraction limited laser spot. Furthermore, a nano protrusion was optically induced on the surface of the
films, beyond the limit of light diffraction, by metal tip enhanced near-filed illumination. A silver coated tip
was located inside the diffraction limited spot of a focused laser beam (460 nm), and an enhanced near-field,
with 30 nm light spot, was generated in the vicinity of the tip due to localized surface plasmons. The
incident light intensity was carefully regulated to induce surface nanodeformation by such a near-field spot.
A nano protrusion with 47 nm full width of half maximum and 7 nm height was induced. The protrusion
occurs because the film is attracted towards the tip end during irradiation. At the top of the protrusion, an
anisotropic nanomovement of the polymer occurs in a direction nearly parallel to the polarization of the
incident light, and suggests the existence at the tip end of not only a longitudinal, i.e., along the tip long axis,
but also a lateral component of the electric field of light. The azo-polymer film helps map the electric field
in the close vicinity of the tip. We also report on two-photon patterning of the films. Exposure of azo
polymer films, which absorb in the visible range
(λmax = 480 nm), to intense 920 nm irradiation leads to
polarization dependent patterning which are associated with polymer nanomovement caused by
photoselective two-photon cis ↔ trans isomerization, while irradiation at 780 nm induces multi-photon
bleaching of the azo chromophore. These wavelengths hit bleaching and isomerization pathways in the
chromophore, respectively.
We demonstrate that two-photon induced molecular orientation of diarylethene (DE) in thin films of poly-methyl-methacrylate (PMMA) and multi-photon induced anisotropic bleaching of disperse red one (DR1). We confirmed that two-photon absorption was induced in DE by measuring the quadratic dependence of isomerization rate on excitation light power, and we observed two-photon photo-orientation of DE in dichroic absorbance. Disperse red one (DR1) was orientationally bleached in PMMA by polarized multi-photon excitation. Anisotropic refractive index changes result from the nonlinear photobleaching of DR1 was detected by a polarization confocal microscope, and bit-oriented data storage was demonstrated.
We introduce the analytical theory of couples photoisomerization and photo-orientation both for individualizable and spectrally overlapping isomers, and we use it to quantify the photo-orientation movement of chromophores in polymers including photoisomerization quantum yields. We study photo-orientation processes in A - B photoisomerizable systems where B is unknown. We contrast systems where the isomers are individualizable and without thermal A implied by B isomerization, namely diarylethene and spiropyran-type chromophores in films of poly-methyl- methacrylate, respectively, and systems of nondistinguishable isomers, namely push-pull azobenzenes attached to polyurethane polymers. When diarylethene and spiropyrans are oriented by polarized excitation, the apparent optical orientation changes sign for the ultra- violet versus the visible photochemical transitions: a feature which is due to perpendicular transition dipoles of the B isomer of these chromophores. Photo-orientation reveals the symmetry nature of photoisomerization transitions. We also report on the observation of near-pure photo-orientation by photoisomerization of azo dye in polymers; an observation which is attributed to both the particular molecular structure of the polymer studied and to appropriate photoisomerization quantum yields as well as as fast trans implied by cis thermal isomerization, and is rationalized by the study of photo-orientation of a series of azo-polyurethanes each with distinct differences in the molecular structure of the unit building blocks.
The photoisomers of diarylethene and spiropyran photochromic chromophores are oriented in films of poly-methyl-methacrylate when photoisomerized by polarized light irradiation. Photo- orientation occurs in both the forth and back photoisomerization reactions. The apparent optical orientation is inverted, e.g. changes sign, for the ultra-violet versus the visible photochemical transitions of both of the chromophores studied.
We have developed a bit-oriented three-dimensional domain memory with a photorefractive crystal. A Ce-doped SBN is used to record a bit data. The ferroelectric polarization is reversed by a focused laser beam in a crystal with the temperature at 38 degrees Celsius to form a bit data. The recorded domain is stable at 15 degrees Celsius. The data is read as the refractive index change induced by spontaneous polarization via Pockels effect. We show the domain image observed with phase contrast microscope. We also show the computer simulated images. The result in experiment is in good agreement with the simulated result.
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