Influence of clay concentration on the gas barrier of clay-polymer nanobrick wall thin film assemblies

The influence of the clay deposition suspension concentration on gas barrier thin films of sodium montmorillonite (MMT) clay and branched polyethylenimine (PEI), created via layer-by-layer assembly, was investigated. Films grown with MMT suspension concentrations ranging from 0.05 to 2.0 wt % were analyzed for their growth as a function of deposited polymer-clay bilayers (BL) and their thickness, clay concentration, transparency, nanostructure, and oxygen barrier as a function of the suspension concentration. The film thickness doubles and the visible light transmission decreases less than 5% as a function of MMT concentration for 20-BL films. Atomic force and transmission electron microscope images reveal a highly aligned nanobrick wall structure, with quartz crystal microbalance measurements revealing a slight increase in the film clay concentration as the MMT suspension concentration increases. The oxygen transmission rate (OTR) through these 20-BL composites, deposited on a 179 μm poly(ethylene terephthalate) film, decreases exponentially as a function of the MMT clay concentration. A 24-BL film created with 2.0 wt % MMT has an OTR below the detection limit of commercial instrumentation (<0.005 cc/m(2)·day·atm). This study demonstrates an optimal clay suspension concentration to use when creating LbL barrier films, which minimizes deposition steps and the overall processing time.     

Time of flight mass spectrometry for quantitative data analysis in fast transient studies using a Temporal Analysis of Products (TAP) reactor

A Time of flight (ToF) mass spectrometer suitable in terms of sensitivity, detector response and time resolution, for application in fast transient Temporal Analysis of Products (TAP) kinetic catalyst characterization is reported. Technical difficulties associated with such application as well as the solutions implemented in terms of adaptations of the ToF apparatus are discussed. The performance of the ToF was validated and the full linearity of the specific detector over the full dynamic range was explored in order to ensure its applicability for the TAP application. The reported TAP-ToF setup is the first system that achieves the high level of sensitivity allowing monitoring of the full 0-200 AMU range simultaneously with sub-millisecond time resolution. In this new setup, the high sensitivity allows the use of low intensity pulses ensuring that transport through the reactor occurs in the Knudsen diffusion regime and that the data can, therefore, be fully analysed using the reported theoretical TAP models and data processing.     

Aminolevulinic acid-photodynamic therapy combined with topically applied vascular disrupting agent vadimezan leads to enhanced antitumor responses

The tumor vascular-disrupting agent (VDA) vadimezan (5,6-dimethylxanthenone-4-acetic acid, DMXAA) has been shown to potentiate the antitumor activity of photodynamic therapy (PDT) using systemically administered photosensitizers. Here, we characterized the response of subcutaneous syngeneic Colon26 murine colon adenocarcinoma tumors to PDT using the locally applied photosensitizer precursor aminolevulinic acid (ALA) in combination with a topical formulation of vadimezan. Diffuse correlation spectroscopy (DCS), a noninvasive method for monitoring blood flow, was utilized to determine tumor vascular response to treatment. In addition, correlative CD31-immunohistochemistry to visualize endothelial damage, ELISA to measure induction of tumor necrosis factor-alpha (TNF-α) and tumor weight measurements were also examined in separate animals. In our previous work, DCS revealed a selective decrease in tumor blood flow over time following topical vadimezan. ALA-PDT treatment also induced a decrease in tumor blood flow. The onset of blood flow reduction was rapid in tumors treated with both ALA-PDT and vadimezan. CD31-immunostaining of tumor sections confirmed vascular damage following topical application of vadimezan. Tumor weight measurements revealed enhanced tumor growth inhibition with combination treatment compared with ALA-PDT or vadimezan treatment alone. In conclusion, vadimezan as a topical agent enhances treatment efficacy when combined with ALA-PDT. This combination could be useful in clinical applications.     

Ligand effects in the formation of tertiary carbanions from substituted tertiary aromatic amides

Reaction of 2‐isopropyl‐(N,N‐diisopropyl)‐benzamide 5 with tBuLi in ether results in ortho deprotonation and the formation of a hemisolvate based on a tetranuclear dimer of ( 5 ‐Li_o)₂?Et₂O. The solid‐state structure exhibits a dimer core in which the amide oxygen atoms fail to stabilize the metal ions but are instead available for interaction with two metalated monomers that reside peripheral to the core. Reaction of 5 with tBuLi in the presence of the tridentate Lewis base PMDTA (N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine) takes a different course. In spite of the tertiary aliphatic group at the 2‐position in 5 , X‐ray crystallography revealed that a remarkable benzylic (lateral) deprotonation had occurred, giving the tertiary benzyllithium 5 ‐Li_l?PMDTA. The solid‐state structure reveals that amide coordination and solvation by PMDTA combine to distance the Li⁺ ion from the deprotonated α‐C of the 2‐iPr group (3.859(4) Å), thus giving an essentially flat tertiary carbanion and a highly distorted aromatic system. DFT analysis suggests that the metal ion resides closer to the carbanion center in solution. In line with this, the same (benzylic) deprotonation is noted if the reaction is attempted in the presence of tridentate diglyme, with X‐ray crystallography revealing that the metal is now closer to the tertiary carbanion (2.497(4) Å). Electrophilic quenches of lithiated 5 have allowed, for the first time, the formation of quaternary benzylic substituents by lateral lithiation.     

Hypervelocity shock standoff on spheres in air

To provide data for the validation of computational fluid dynamics models, measurements of the shock standoff distance on spheres in hypervelocity flows have been made. Test flows of air at 8.7 and 9.7 km/s were generated in the X2 expansion tunnel fitted with a Mach 10 nozzle. High-speed video images were analysed with a least-squares shape-fitting algorithm. Assuming a spherical shock shape near the nose enabled increased resolution measurements beyond the native pixel size. Normalised shock standoff distances, $\Delta $ / $D$ , in the range 0.03–0.04 were measured, with sphere diameters, $D$ , of 40, 60 and 80 mm.     

DNA-Templated Fluorescent Silver Nanoclusters Inhibit Bacterial Growth While Being Non-Toxic to Mammalian Cells

Silver has a long history of antibacterial effectiveness. The combination of atomically precise metal nanoclusters with the field of nucleic acid nanotechnology has given rise to DNA-templated silver nanoclusters (DNA-AgNCs) which can be engineered with reproducible and unique fluorescent properties and antibacterial activity. Furthermore, cytosine-rich single-stranded DNA oligonucleotides designed to fold into hairpin structures improve the stability of AgNCs and additionally modulate their antibacterial properties and the quality of observed fluorescent signals. In this work, we characterize the sequence-specific fluorescence and composition of four representative DNA-AgNCs, compare their corresponding antibacterial effectiveness at different pH, and assess cytotoxicity to several mammalian cell lines.     

Adsorption of p-nitrophenol on organoclays

In this study, organoclays were prepared through ion exchange of a single cationic surfactant, hexadecyltrimethylammonium bromide and characterised by a range of methods including X-ray diffraction (XRD) and thermogravimetric analysis. Changes in the surface properties of montmorillonite and the organoclays were observed and the basal spacings of organoclays with and without p-nitrophenol were determined using XRD. The thermal stability of both organoclays were measured using thermogravimetry. As the surfactant loading increased, the expanded basal spacings were observed, and different molecular configurations of surfactant were identified. When the surfactant loading exceeded 1.0 CEC, surfactant molecules tend to adsorb strongly on the clay surface and this resulted in increased affinity to organic compounds. The adsorbed p-nitrophenol and the surfactant decomposed simultaneously. Hence, the surfactant molecules and adsorbed p-nitrophenol are important in determining the thermal stabilities of organoclays. This study enhances the understanding of the structure and adsorption properties of organoclays and has further implications for the application of organoclays as filter materials for the removal of organic pollutants in aqueous solutions.     

Pseudocontinuity in Optimization and Nonzero-Sum Games

We enlarge the class of sufficient conditions which guarantee, on the one hand, the sequential closedness of set-valued functions defined by minimum points and by social Nash equilibria and, on the other hand, the existence of solutions for MinSup problems, using new classes of functions, called sequentially lower pseudocontinuous and sequentially upper pseudocontinuous functions. Properties and characterizations of such classes are investigated.     

The dielectrophoretic levitation and separation of latex beads in microchips.

A linear travelling wave dielectrophoretic (twDEP) microchip was fabricated and used to investigate both the levitation and the twDEP motion of latex beads as a function of applied potential and frequency, suspending medium conductivity, bead size, and surface characteristics. The surface conductance of the latex beads was characterised by measurement of the dielectrophoretic (DEP) crossover frequency. Collection of sample prior to initiation of twDEP was achieved using positive DEP forces generated by an integrated pair of parallel electrodes positioned in front of the twDEP array within the microfluidic channel. The principle of linear twDEP separation is shown using latex beads and rabbit heart cells.