Thermal and optical properties of novel polyurea/silica organic–inorganic hybrid materials

Current optical polymeric materials for advanced fiber laser development are susceptible to degradation due to the heat generated in high power usage. A suitable replacement light stripping material was explored to overcome this problem by examining optical and physical properties such as transmission/absorption, refractive index, thermal conductivity, and thermal stability. The synthesis and characterization of two new polyurea/silica ORMOSILs (ORganically MOdified SILicates) suitable for high temperature (up to 300 °C) optical applications are reported herein. A one-pot, room temperature synthesis is based upon commercially available bis-isocyanates and an amino-silane. These materials exhibit the combined traits of both glass and polymer by displaying optical clarity over a wide range of wavelengths stretching from the edge of the UV (250 nm) to well into the NIR (2,000 nm), refractive indices in the visible spectrum (n = 1.50–1.63), thermal conductivities of 0.26 ± 0.09 W/mK (ORMOSIL-A) and 0.27 ± 0.07 W/mK (ORMOSIL-B), and thermal stabilities up to 300 °C. The hybrid materials were found to be easily processed into films but thick casts (>2 mm) were subject to increased rates of cracking and longer curing times. Although this is typical of sol–gel chemistries, the organic constituents of ORMOSILs reduce this effect as compared to purely inorganic sol–gels. The effect of thermal aging on the materials’ properties will also be presented as well as a comparison of these materials and the current state of the art light stripping material.     

Modeling Chemical Reactivity at the Interfaces of Emulsions: Effects of Partitioning and Temperature

Bulk phase chemistry is hardly ever a reasonable approximation to interpret chemical reactivity in compartmentalized systems, because multiphasic systems may alter the course of chemical reactions by modifying the local concentrations and orientations of reactants and by modifying their physical properties (acid-base equilibria, redox potentials, etc.), making them—or inducing them—to react in a selective manner. Exploiting multiphasic systems as beneficial reaction media requires an understanding of their effects on chemical reactivity. Chemical reactions in multiphasic systems follow the same laws as in bulk solution, and the measured or observed rate constant of bimolecular reactions can be expressed, under dynamic equilibrium conditions, in terms of the product of the rate constant and of the concentrations of reactants. In emulsions, reactants distribute between the oil, water, and interfacial regions according to their polarity. However, determining the distributions of reactive components in intact emulsions is arduous because it is physically impossible to separate the interfacial region from the oil and aqueous ones without disrupting the existing equilibria and, therefore, need to be determined in the intact emulsions. The challenge is, thus, to develop models to correctly interpret chemical reactivity. Here, we will review the application of the pseudophase kinetic model to emulsions, which allows us to model chemical reactivity under a variety of experimental conditions and, by carrying out an appropriate kinetic analysis, will provide important kineticparameters.     

Mutagenicity of Photodynamic Therapy as Compared to UVC and Ionizing Radiation in Human and Murine Lymphoblast Cell Lines

Abstract— The mutagenicity of photodynamic therapy (PDT) using red light and either Photofrin® (porfimer sodium) (PF) or aluminum phthalocyanine (AIPc) as the photosensitizer was determined at the thymidine kinase (TK) locus in the human lymphoblastic cell lines, TK6 and WTK1, and was compared to the mutagenicity of UVC and X-radia-tion in these cells as well as the mutagenicity of PDT in murine L5178Y lymphoblastic cell lines. Photodynamic therapy was found not to be mutagenic in TK6 cells, which possess an active p53 gene and which are relatively deficient in recombination and repair of DNA double-strand breaks. In contrast, PDT with either sensitizer was significantly mutagenic in WTK1 cells, which harbor an inactivating mutation in the p53 gene and are relatively efficient in recombination and double-strand break repair as compared to TK6 cells. The induced mutant frequency in WTK1 cells with PF as the photosensitizer was similar to that induced by UVC radiation but lower than that induced by X-radiation at equitoxic faiences/ doses. The mutant frequency induced by PDT in WTK1 cells with either photosensitizer was much lower than that induced in murine lymphoblasts at equitoxic fluences. The TK6 and WTK1 cells did not differ in their sensitivity to the cytotoxic effects of PDT, but the level of PDT-induced apoptosis was greater in TK6 than in WTK1 cells. These results indicate that the mutagenicity of PDT varies in different types of cells and may be related to the repair capabilities as well as the p53 status of the cells.     

Single-step affinity purification of toxic and non-toxic proteins on a fluidics platform

Single-step fusion-based affinity purification of proteins with pH-controllable linkers was carried out in a fluidic device. The linkers were previously derived from self-splicing protein elements called inteins. Two different linkers were generated to solve two distinct separation problems: one for rapid single-step affinity purification of a wide range of proteins, and the other specifically for the purification of cytotoxic proteins. Scale-down factors of 185 resulted in separations in a 27 microl bed-volume. A rotating CD format was chosen because of its simplicity in effecting fluid movement through centrifugal force without the complications associated with electro-osmosis and other pumping methods. The design and fabrication of the fluidic device and the protein purification process are described. This work, which demonstrates the purification of active proteins by two distinct fluidic separations, is widely applicable to small-scale massively parallel proteomic separations.     

Powering nanodevices with biomolecular motors

Biomolecular motors, in particular motor proteins, are ideally suited to introduce chemically powered movement of selected components into devices engineered at the micro- and nanoscale level. The design of such hybrid "bio/nano"-devices requires suitable synthetic environments, and the identification of unique applications. We discuss current approaches to utilize active transport and actuation on a molecular scale, and we give an outlook to the future.     

Synthesis, characterization and biocompatibility studies of oligosiloxane modified polythiophenes

This paper describes the preparation and characterization of homopolymers of 3-oligo(dimethylsiloxane)thiophene macromonomers, V-VIII, and copolymers with 3-methylthiophene. The thiophene macromonomers were prepared by hydrosilylation reaction between ω-(Si-H)-oligo(dimethylsiloxane), I-IV, and 3-propenylthiophene using a platinum-divinyltetramethyldisiloxane complex as the catalyst. The products were characterized by ¹H, ¹³C, ²⁹Si NMR and IR spectroscopy; DSC (differential scanning calorimetry) and GPC studies. Two distinct glass transition temperatures are observed for poly[VIII], a T_g at −79 °C corresponds to the soft oligo(dimethylsiloxane) phase and the T_g at 190 °C corresponds to the hard thiophene backbone. Homopolymers of V and VI, and copolymers may be doped with I₂ to generate electronic conductive material, a copolymer of poly[V]-co-poly[3-methylthiophene] (50/50, w/w) has an electronic conductivity value of 5 × 10⁻⁵ S/cm at 25 °C. The polymers are tractable and may be molded into thin films; a number of the polymers are soluble in organic solvents. Polythiophene modified with oligosilioxanes are biocompatibile; the polymers minimally interfere with the growth of HeLa cells.     

Electrochemistry of nano-scale bacterial surface protein layers on gold

The mechanism of the recrystallization of nano-scale bacterial surface protein layers (S-layers) on solid substrates is of fundamental interest in the understanding and engineering of biomembranes and e.g. biosensors. In this context, the influence of the charging state of the substrate had to be clarified. Therefore, the electrochemical behaviour of the S-layers on gold electrodes has been investigated by in-situ electrochemical quartz microbalance (EQMB) measurements, scanning force microscopy (SFM) and small-spot X-ray photoelectron spectroscopy (SS-XPS) of potentiostatically emersed substrates. It was shown that the negatively charged bonding sites of the S-layer units (e.g. carboxylates) can bond with positively charged Au surface atoms in the positively charged electrochemical double layer region positive of the point of zero charge ( approximately -0.8 V vs. saturated mercury-mercurous sulphate electrode). Surface conditions in other potential regions decelerated the recrystallization and fixation of S-layers. Time-resolved in-situ and ex-situ measurements demonstrated that two-dimensional S-layer crystal formation on gold electrodes can occur within few minutes in contrast to hours common in self-assembled monolayer (SAM) generation. These results proved that the recrystallization and fixation of 2D-crystalline S-layers on an electronic conductor can be influenced and controlled by direct electrochemical manipulation.