No abstract

We report the observation of the photorefractive effect in an organic−inorganic polymer composite photosensitized with nanosized cadmium sulfide particles, the surface of which is passivated utilizing p-thiocresol. The semiconductor nanoparticles are dispersed in a poly(N-vinylcarbazole) (PVK) polymer matrix that also acts as the charge-transport species. The ability of these particles to behave as the photosensitizer in a PVK matrix has been characterized through a dc photoconductivity experiment. In addition, for the photorefractive experiments, the second-order optically nonlinear chromophore 4-nitrophenyl-l-prolinol is also doped into the PVK matrix to elicit electro-optic response. Tricresyl phosphate is used to lower the glass-transition temperature of the material, allowing for room temperature in situ poling of the sample. In addition to the electric field dependence of the degenerate four-wave mixing diffraction efficiency, the photorefractive nature of the grating is confirmed via two-wave mixing asymmetric energy transfer. The paper also discusses briefly the methods employed in the syntheses of the capped CdS nanoparticles used in this study, which include the reverse micelle approach as well as competitive reaction chemistry. The resulting particles have been characterized using UV−vis absorption and X-ray diffraction.

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.

This work details the in situ characterization of the interface between a silicon electrode and an electrolyte using a linear fluorinated solvent molecule, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in deuterated dimethyl perfluoroglutarate (d6-PF5M2) (1.87 × 10(-2) mS cm(-1)). The solid electrolyte interphase (SEI) composition and thickness determined via in situ neutron reflectometry (NR) and ex situ X-ray photoelectron spectroscopy (XPS) were compared. The data show that SEI expansion and contraction (breathing) during electrochemical cycling were observed via both techniques; however, ex situ XPS suggests that the SEI thickness increases during Si lithiation and decreases during delithiation, while in situ NR suggests the opposite. The most likely cause of this discrepancy is the selective removal of SEI components (top 20 nm of the SEI) during the electrode rinse process, which is required to remove the electrolyte residue prior to ex situ analysis, demonstrating the necessity of performing SEI characterization in situ.

This paper reports new photorefractive polymeric nanocomposites photosensitized with HgS or PbS nanocrystals and operating at the communication wavelength of 1.3 µm. To our knowledge, it is the first report of a polymeric photorefractive medium with spectral response at a communication wavelength. The nanocomposites involving HgS are prepared by an in-situ nanochemistry approach, whereas those involving PbS were prepared using competitive nanochemistry. Photoconductivity experiments were employed in the characterization of photocharge generation quantum efficiency provided by the semiconductor nanocrystals. The photorefractive nature of the composites is confirmed using electric field dependent two-beam coupling. In the case of nanocomposite containing PbS nanocrystals, a net gain in excess of the associated absorption loss is observed.