Enhanced Photorefractivity in a Polymeric Composite Photosensitized with Carbon Nanotubes Grafted to a Photoconductive Polymer

We report on the photosensitization of photorefractive (PR) polymeric composites through the inclusion of multiwalled and singlewalled carbon nanotubes (CNTs), respectively, having poly(N -vinyl carbazole) (PVK) grafted to their surfaces. The PR nature of the holographic gratings was confirmed via the asymmetric exchange of energy in a two-beam-coupling (TBC) geometry, yielding TBC gain coefficients approaching 80 cm-1. In addition, in degenerate-four-wave- mixing experiments the prepared composites exhibited diffraction efficiencies as high as 60% and overmodulation voltages as low as ∼40 V/μm. These notable figures of merit indicate that the grafting of the PVK polymer to the various CNTs results in enhanced PR performance. The mechanism responsible for this enhancement in PR performance is investigated using a variety of experimental techniques

Photorefractivity in a Polymeric Composite Photosensitized with NiS Nanocrystals

The photorefractive performance of a polymeric composite photosensitized through the inclusion of NiS nanocrystals is described. The nanocrystals were characterized using visible-absorption spectroscopy, energy-dispersive x-ray spectroscopy, and transmission electron microscopy. We further demonstrate the ability to enhance various aspects of the composite\u27s photorefractive performance by performing ligand exchange on the nanocrystals prior to their incorporation into the polymer composite. This procedure resulted in a lowering of the overmodulation voltage from ~70 to ~50 V/µm without affecting the maximum diffraction efficiency of ~40%. An increase in the two-beam-coupling gain coefficient was similarly observed, increasing from 38 to 79 cm−1. The photoconductivities were used in determining the overall quantum efficiencies associated with the photorefractive devices. All experiments were conducted at 633 nm and the data represent a significant improvement in the photorefractive performance of inorganic-organic hybrid photorefractive materials

Charge carrier mobility in an organic-inorganic hybrid nanocomposite

Organic-inorganic hybrid materials are media for electronic and optoelectronic applications. We present a study of the electronic transport in such a modelnanoparticle-sensitizedhybridorganic-inorganic photorefractive host system, consisting of poly(N-vinylcarbazole) doped with quantum dots of cadmium sulfide, using standard time-of-flight techniques. The photocurrent transients exhibit features typical of dispersive transport in an amorphous semiconductor. The hole mobility depends strongly on the electric field and temperature indicating Poole–Frenkel-like activated hopping transport; a thickness dependence of the mobility is observed. The presence of nanoparticles does not lead to increased trapping of holes. Conversely, a surprising result is observed: the mobility actually increases with the increase of nanoparticle concentration even though it is well below the percolation limit.This study was supported by a NSF, DMR Solid State and Polymer Chemistry Grant No. DMR0075867. Partial support by a Defense Research Initiative on Nanotechnology (DURINT), Contract No. F496200110358, through the Directorate of Chemistry and Life Sciences of the Air Force Office of Scientific Research is also acknowledged

Second-Harmonic and Sum-Frequency Imaging of Organic Nanocrystals with Photon Scanning Tunneling Microscope

Second-harmonic generation and sum-frequency generation with photon scanning tunneling microscopy and shear-force detection are used to map the nonlinear optical response and the surface topograph of N-(4-nitrophenyl)-(L)-prolinol crystals with a subdiffraction-limited resolution. The domain-size dependence of the spatial feature is obtained, which shows the local orientational distribution of the optical near field radiated by nonlinear nanocrystals and reveals the difference between nanoscopic and macroscopic second-order optical nonlinearities of molecular crystals

Dynamic Correction of a Distorted Image Using a Photorefractive Polymeric Composite

We demonstrate, for the first time, the dynamic correction of aberrated images in real-time using a polymeric composite with fast response times. The current novel experimental design is capable of restoring a phase aberrated, image carrying laser beam, to nearly its original quality. The ability to reconstruct images in real-time is demonstrated through the changing of the aberrating medium at various speeds. In addition, this technique allows for the correction of images in motion, demonstrated through the oscillatory movement of the resolution target. We also have demonstrated that important parameters of the materials in the study such as response times, diffraction efficiencies and optical gains all retain high figures of merit values under the current experimental conditions. © 2004 Optical Society of America

Cytotoxicity in the Age of Nano: The Role of Fourth Period Transition Metal Oxide Nanoparticle Physicochemical Properties

A clear understanding of physicochemical factors governing nanoparticle toxicity is still in its infancy. We used a systematic approach to delineate physicochemical properties of nanoparticles that govern cytotoxicity. The cytotoxicity of fourth period metal oxide nanoparticles (NPs): TiO2, Cr2O3, Mn2O3, Fe2O3, NiO, CuO, and ZnO increases with the atomic number of the transition metal oxide. This trend was not cell-type specific, as observed in non-transformed human lung cells (BEAS-2B) and human bronchoalveolar carcinoma-derived cells (A549). Addition of NPs to the cell culture medium did not significantly alter pH. Physiochemical properties were assessed to discover the determinants of cytotoxicity: (1) point-of-zero charge (PZC) (i.e., isoelectric point) described the surface charge of NPs in cytosolic and lysosomal compartments; (2) relative number of available binding sites on the NP surface quantified by X-ray photoelectron spectroscopy was used to estimate the probability of biomolecular interactions on the particle surface; (3) band-gap energy measurements to predict electron abstraction from NPs which might lead to oxidative stress and subsequent cell death; and (4) ion dissolution. Our results indicate that cytotoxicity is a function of particle surface charge, the relative number of available surface binding sites, and metal ion dissolution from NPs. These findings provide a physicochemical basis for both risk assessment and the design of safer nanomaterials

Temperature-Dependence Studies of Photorefractive Effect in a Low Glass-Transition-Temperature Polymer Composite

The temperature dependence of the photorefractive effect in a polymer composite containing poly(9-vinycarbazole), tricresyl phosphate, buckminsterfullerene, and 4-(N,N-diethylamino)-β-nitrostyrene is presented. The photoconductive, electro-optic and photorefractive properties of the material have been studied in the temperature range of 22-61°C. An apparent increase of electro-optic modulation with temperature and its eventual saturation is observed. This behavior is attributed to the temperature activated orientational mobility of the second-order nonlinear chromophores. The polarization anisotropy between the p- and s-polarized readouts is consistent with what would be expected on the basis of directly measured effective electro-optic coefficients. By correlating the electro-optic value with the diffraction efficiency, the temperature dependence of the space-charge field is obtained and explained by temperature dependencies of the dark conductivity and the photoconductivity of the material

Sub-Millisecond Response Time in a Photorefractive Composite Operating under CW Conditions

Extensive study of photorefractive polymeric composites photosensitized with semiconductor nanocrystals has yielded data indicating that the inclusion of such nanocrystals enhances the charge-carrier mobility, and subsequently leads to a reduction in the photorefractive response time. Unfortunately, the included nanocrystals may also act as a source of deep traps, resulting in diminished diffraction efficiencies as well as reduced two beam coupling gain coefficients. Nonetheless, previous studies indicate that this problem is mitigated through the inclusion of semiconductor nanocrystals possessing a relatively narrow band-gap. Here, we fully exploit this property by doping PbS nanocrystals into a newly formulated photorefractive composite based on molecular triphenyldiamine photosensitized with C60. Through this approach, response times of 399 µs are observed, opening the door for video and other high-speed applications. It is further demonstrated that this improvement in response time occurs with little sacrifice in photorefractive efficiency, with internal diffraction efficiencies of 72% and two-beam-coupling gain coefficients of 500 cm-1 being measured. A thorough analysis of the experimental data is presented, supporting the hypothesized mechanism of enhanced charge mobility without the accompaniment of superfluous traps. It is anticipated that this approach can play a significant role in the eventual commercialization of this class of materials

Nona-Arginine Facilitates Delivery of Quantum Dots into Cells via Multiple Pathways

Semiconductor quantum dots (QDs) have recently been used to deliver and monitor biomolecules, such as drugs and proteins. However, QDs alone have a low efficiency of transport across the plasma membrane. In order to increase the efficiency, we used synthetic nona-arginine (SR9), a cell-penetrating peptide, to facilitate uptake. We found that SR9 increased the cellular uptake of QDs in a noncovalent binding manner between QDs and SR9. Further, we investigated mechanisms of QD/SR9 cellular internalization. Low temperature and metabolic inhibitors markedly inhibited the uptake of QD/SR9, indicating that internalization is an energy-dependent process. Results from both the pathway inhibitors and the RNA interference (RNAi) technique suggest that cellular uptake of QD/SR9 is predominantly a lipid raft-dependent process mediated by macropinocytosis. However, involvement of clathrin and caveolin-1 proteins in transducing QD/SR9 across the membrane cannot be completely ruled out

Specific Intracellular Uptake of Herceptin-Conjugated CdSe/ZnS Quantum Dots into Breast Cancer Cells

Herceptin, a typical monoclonal antibody, was immobilized on the surface of CdSe/ZnS core-shell quantum dots (QDs) to enhance their specific interactions with breast cancer cells (SK-BR3). the mean size of the core-shell quantum dots (28 nm), as determined by dynamic light scattering, increased to 86 nm after herceptin immobilization. the in vitro cell culture experiment showed that the keratin forming cancer cells (KB) proliferated well in the presence of herceptin-conjugated QDs (QD-Her, 5 nmol/mL), whereas most of the breast cancer cells (SK-BR3) had died. to clarify the mechanism of cell death, the interaction of SK-BR3 cells with QD-Her was examined by confocal laser scanning microscopy. as a result, the QD-Her bound specifically to the membrane of SK-BR3, which became almost saturated after 6 hours incubation. This suggests that the growth signal of breast cancer cells is inhibited completely by the specific binding of herceptin to the Her-2 receptor of SK-BR3 membrane, resulting in cell death