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This PDF file contains the front matter associated with SPIE Proceedings Volume 8103-0, including the Title Page, Copyright information, Table of Contents, Introduction, and the Conference Committee listing.
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The large enhancements of optical properties of the dye-intercalated DNA lead us to
apply the dye-intercalated DNA as various sensors with a high sensitivity to detect
environmentally toxic gases such as dioxine, NOx or carbon monoxide. This paper
retorts on DNA sensors for the further applications of DNA as materials. Also,
bio-medical applications of DNA sensors such as a glucose sensor are reported.
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The photophysical properties of the DNA-CTMA/Eu(tta)3(H2O)2 were investigated in order to apply them for novel
photonic materials. From absorption and CD measurements, the intercalation of Eu(tta)3(H2O)2 into DNA-CTMA
backbones was indicated. Furthermore, the emission properties of the DNA-CTMA/Eu(tta)3(H2O)2 were superior to that
of PMMA/Eu(tta)3(H2O)2 films. We expect achievements of our research help development of organic electronic device
used biomaterials as typified by DNA-hybrid materials.
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DNA is an interesting material from the viewpoint of the materials science. This paper discusses the electronic
states of the metal incorporated M-DNA complexes with several species of metal ions. M-DNA prepared by the
ordinary methanol precipitation technique has been investigated with ESR, STM and optical absorption, and
concluded that the metal ion hydrated with several water molecules locates in between the bases of a base pair
and that the divalent metal ions are incorporated into DNA in place of two Na cations as the counter ion for PO-4in the DNA backbones. Only in Fe-DNA, it was confirmed that the Fe2+ in the FeCl2 aqueous solution reacts
with DNA to form Fe-DNA complex with Fe3+, where the charge would transfer to DNA. Within 30 min, the
hydrolysis of Fe2+ to form Fe3+O(OH) did not occur in the FeCl2 aqueous solution at room temperature. The
optical absorption spectra of Fe-DNA is similar to that for FeCl3 with the ionic character, but definitely differs
from that of Fe3+O(OH) with the covalent bonding nature, suggesting the ionic character of Fe3+ in Fe-DNA.
Finally, the possible two kinds of electronic states for Zn-DNA with different bonding nature will be discussed
in relation to the recent report on Zn-DNA.
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The potential of using a DNA biopolymer in an electro-optic device is presented. A complex of DNA with the
cationic surfactant cetyltrimethylammonium-chloride (CTMA) was used to obtain an organic-soluble DNA material
(DNA-CTMA). Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) was added to the DNACTMA
to increase the electrical conductivity of the biopolymer. The CW absorbance and time-resolved
photoluminescence of the resulting DNA-CTMA and DNA-CTMA-PEDOT:PSS were investigated. Both DNA
materials have absorbance peaks at ~260 nm and a broad, Stokes shifted, photoluminescence peak around 470nm.
The photoluminescence lifetime of the materials was observed to decrease with increasing UV excitation.
Specifically, excitation with a high power ultrafast (~150fs) UV (266nm) laser pulse resulted in a drastic decrease
in the photoluminescence lifetime decreases after a few minutes. Moreover, the observed decrease was faster in an
air ambient than in a nitrogen ambient. This is most likely due to photo-oxidation that degrades the polymer surface
resulting in an increase in the non-radiative recombination. In order to investigate the photoconductivity of these
two materials, metal-biopolymer-metal (MBM) ultraviolet photodetectors with interdigitated electrodes were
fabricated and characterized. The photoresponsivity of these devices was limited by the transport dynamics within
the film. The prospects for the use of these materials in optical devices will be discussed.
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The semi-intercalation of an azo-dye Disperse Red 1 (DR1) molecule into a biopolymeric material made of
deoxyribonucleic acid (DNA) complexed with the cationic surfactant hexadecyltrimethyl-ammonium chloride
(CTMA) formulated recently1-3 has successfully explained the main experimental results4 of laser dynamic
inscription of diffraction gratings: short response time, low diffraction efficiency, single-exponential kinetics
and flat wavelength dependence.5 In this paper we generalize the analytic model of Ref.2 to account for a
more realistic dynamics of DNA-CTMA matrix. To this end we extend the model of paper5 by including into
it probabilistic features of local free volume in DNA matrix which characterize, in a simple way, the spatial
distribution of local voids which, in turn play the central role for the kinetics of photoinduced trans-cis-trans
cycles of DR1 dye under the polarized laser light illumination. We discuss a stochastic master equation which
generalizes the simple model of Ref.2 and address briefly the topic of non-exponential grating inscription in
modelling and in recent experiments.
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The process of creating natural DNA-containing bio-organic light emitting diodes is a fascinating journey from salmon
fish to the highly-efficient BiOLED. DNA from salmon sperm is used as a high-performance electron blocking layer, to
enhance the efficiency of the BiOLED over its conventional OLED counterpart. An overview of the BiOLED fabrication
process and its key steps are presented in this paper.
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A methodology that allows for the coupling of biology and electronic materials is presented, where double stranded
DNA serves as a template for electronic material growth. Self-assembled DNA structures allow for a variety of patterns
to be achieved on the nanometer size scale. These DNA architectures allow for feature sizes that are difficult to achieve
using conventional patterning techniques. Herein, the procedures for the creation of self-assembled DNA nanostructures
in aqueous and non-aqueous media are described, and these structures are subsequently deposited onto substrates of
interest. DNA self assembly under non-aqueous conditions has yet to be presented in literature, and is necessary if
unwanted oxidation of certain electronic substrates is to be avoided. Solubilization of the DNA in non-aqueous solvents
is achieved by replacing charge stabilizing salts with surfactants. Retention of DNA hierarchical structure under both
conditions will be presented by observing the structures using AFM imaging and circular dichroism spectroscopic
studies.
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We employed biopolymer DNA as a template to form J-aggregates of pseudoisocyanine (PIC), and succeeded to
optimize the conditions for their formation in solutions and solid films. The optical characteristics of J-aggregates were
investigated by absorption, fluorescence and circular dichroic (CD) spectra. For both films and solutions,
polyvinylalcohol (PVA) introduced as a matrix for the films was proved to play a role to improve the film quality. We
prepared the samples of several types of cyanine dyes systematically, finding the relationship among the molecular
conjugated length and effects from the interaction with DNA. These results show possibility of application of
J-aggregate into novel optical devices requiring optical nonlinearity or superradiant behavior.
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Whispering gallery mode optical microresonators are devices used for performing ultra-sensitive optical detection.
Although the majority of the sensor research has been focused on label-free detection strategies for diagnostics, a
whispering gallery mode device is ideally suited to perform fluorescent label-based biodetection as well. However,
previous research using optical microcavities to excite fluorescent molecules has focused on cavity quantum
electrodynamics applications and fundamental studies of the interactions of large fluorescent nanoparticles with the
resonant cavity. In the present work, a method for forming self-assembled lipid bilayers, a mimic for cell membranes,
on a spherical microresonator is developed. Solid-supported lipid bilayers, which are approximately 5nm thick, have
been shown to accurately model cell membranes, and researchers use lipid bilayers in combination with fluorescent
microscopy when developing theoretical models for the transport of molecules across the cell membrane. The bilayernature
is verified using both fluorescent resonance energy transfer and fluorescence recovery after photobleaching. The
evanescent tail of the microresonator is used to excite a Cy5-conjugated lipid located within the bilayer while the
underlying optical device behavior is characterized at 633nm and 980nm. The emission wavelength of the Cy5 dye and
the optical performance (Q factor) of the microcavity agree with theoretical predictions.
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Effect of ambient humidity on the photodegradation of melanin is investigated using an interferometric technique to
fabricate gratings on thin films. A low power 355 nm diode laser is used to fabricate gratings on melanin thin films,
while a 1 mW He-Ne laser is used to probe grating formation. Effects at several different UV intensities, ranging from 10
mW to 30 mW, and ambient humidities, ranging from 13% to 93%, are investigated on melanin thin films of two
different thicknesses; 22 nm and 40nm. It is found that humidity has a great effect on the photodegradation of melanin. It
is also found that existing gratings on melanin thin films can be enhanced by raising ambient humidity. These results
have implications in the biological evolution of many mammals; as well as implications in fabrication and effective
lifetime of organic electronics. The interferometric technique used shows great promise for fabricating grating to analyze
photodegradation of different biomolecules under varying conditions. A simple mathematical model is developed to help
explain the contribution of light intensity and ambient humidity to the photodegradation of melanin.nage.
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Measurements were carried out on salmon DNA-based films, including as-received DNA (molecular weight,
MW>2000 kDa) without and with hexacetyltrimethl-ammonium chloride (CTMA) surfactant, and sonicated DNA
of MW~200 kDa with CTMA. The test specimens were spin-coated or drop-cast films on ITO-coated quartz
slides with a gold charge-collecting electrode. To protect the films from atmospheric influences, the TOF devices
were coated with a 200-400 nm polyurethane passivation layer. A quadrupled 20 ns, pulsed Nd:YAG laser with
output at 266 nm was used for charge injection. The room temperature photoconductive transients were dispersive
to varying degrees with hole mobilities in DNA materials films ranging between 2E-5 to 6E-3 cm2/Vs for fields
ranging from 8 to 58 kV/cm. Only hole response was observed in DNA. The dispersive data were analyzed using
a simple, quasi-empirical equation for the photocurrent transient data.
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The potential of DNA-based dielectrics for energy storage applications was explored via the incorporation of high
dielectric constant (ε) ceramics such as TiO2 (rutile) and BaTiO3 in the DNA bio-polymer. The DNA-Ceramic
hybrid films were fabricated from stable suspensions of the nanoparticles in aqueous DNA solutions. Dielectric
characterization revealed that the incorporation of TiO2 (rutile) in DNA resulted in enhanced dielectric constant
(14.3 at 1 kHz for 40 wt % TiO2) relative to that of DNA in the entire frequency range of 1 kHz-1 MHz. Variable
temperature dielectric measurements, in the 20-80°C range, of both DNA-TiO2 and DNA-BaTiO3 films, revealed
that the ceramic additive stabilizes DNA against large temperature-dependent variations in both ε and the dielectric
loss factor tan δ. The bulk resistivity of the DNA-Ceramic hybrid films, in the case of both TiO2 and BaTiO3
additives in DNA, was measured to be two to three orders of magnitude higher than that of the control DNA films,
indicating their potential for utilization as insulating dielectrics in capacitor applications. As a part of a baseline
study, results based on a comparison of the temperature-dependent dielectric behavior of DNA and DNA-CTMA
complex films as well as their frequency-dependent polarization behavior, are also discussed.
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DNA-CTMA is an attractive material to explore for reconfigurable optical and electronic devices. Its dielectric
constant at microwave frequencies can be tuned by applying a DC electric field. In this work, the origin of dielectric
tunability and other ferroelectric-like behavior observed in DNA-CTMA films is investigated. Results suggest that
the dominant polarization mechanism is ionic in nature and is caused by intentionally retaining excess ions in the
DNA-CTMA precipitate during processing.
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Recent examples of our works in the field of molecular engineering of chromophores for two-photon photodynamic
therapy (PDT), and their vectorization into biological medium are presented and discussed. In a first section of this
article, we show that a commercial amphiphilic diblock copolymer can be used as a micellar container for efficient
delivery of s standard two-photon PDT sensitizer into cells. In a second section, we show how a simple molecular
engineering strategy can be used to improve the performances of two-photon PDT sensitizer in the biological
transparency-window.
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All optical switching has been studied using the Optical Kerr Effect (OKE) configuration in a biopolymer matrix
containing a photochromic molecule. The biopolymer system consisted of a deoxyribonucleic acid blended with cationic
surfactant molecule cetyltrimethyl-ammonium chloride suitable for optical quality thin film fabrication. The excitation
beams inducing birefringence were delivered from a continuous wave laser at 473 and chopped using a variable
frequency chopper. Additionally auxiliary nanosecond pulses coming from Nd:YAG laser were used. The birefringence
was instantaneously monitored by a weak non-absorbed light from a cw He-Ne laser working at 632.8 nm under crossed
polarizer system. Excellent switching times in the range of microseconds and full reversibility of the studied processes
have been observed.ïýïýïý
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We succeeded to generate tunable laser emissions from hemicyanine dye, (4-[4-(dimethylamino)stylyl]-1-
dococylpyridnium bromide) doped in DNA-surfactant complex through three methods. First, we constructed Littrow
type cavity containing hemicyanine and DNA-CTMA complex solutions and observed tunable laser oscillation. Next, we
showed a tunable laser oscillation from ethanol solutions of hemicyanine and DNA-CTMA complex under pumping of
two interfering beams which formed a distributed feedback grating of population. Finally, we fabricated a thin film
composed of hemicyanine and DNA-CTMA complex, and demonstrated tunable laser oscillation under pumping with
two interfering beams. We evaluated the durability of the tunable thin film laser by continuous operation, and confirmed
the lifetime of more than one hour.
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