Reverse Micelle Based Synthesis of Microporous Materials in Microgravity

Formation of zincophosphates from zinc and phosphate containing reverse micelles (water droplets in hexane) has been examined. The frameworks formed resemble that made by conventional hydrothermal synthesis. Dynamics of crystal growth are however quite different, and form the main focus of this study. In particular, the formation of zincophosphate with the sodalite framework was examined in detail. The intramicellar pH was found to have a strong influence on crystal growth. Crystals with a cubic morphology were formed directly from the micelles, without an apparent intermediate amorphous phase over a period of four days by a layer-bylayer growth at the intramicellar pH of 7.6. At a pH of 6.8, an amorphous precipitate rapidly sediments in hours. Sodalite was eventually formed from this settled phase via surface diffusion and reconstruction within four days. With a rotating cell, it was possible to minimize sedimentation and crystals were found to grow epitaxially from the spherical, amorphous particles. Intermediate pH's of 7.2 led to formation of aggregated sodalite crystals prior to settling, again without any indication of an intermediate amorphous phase. These diverse pathways were possible due to changes in intramicellar supersaturation conditions by minor changes in pH. In contrast, conventional syntheses in this pH range all proceeded by similar crystallization pathways through an amorphous gel. This study establishes that synthesis of microporous frameworks is not only possible in reverse micellar systems, but they also allow examination of possible crystallization pathways

Structure and Vibrational Spectra of Mononitrated Benzo [a] Pyrenes.

The molecules benzo[a]pyrene (BaP) and 1-, 3-, and 6-nitrobenzo[a]pyrene (1-NBaP, 3-NBaP, 6-NBaP) are currently of significant interest due to their presence in respirable combustion exhaust particulates and their mutagenic and carcinogenic properties. Structure−function correlations as well as spectroscopic signatures for trace analysis are necessary for these benzo[a]pyrene derivatives. In this paper, detailed infrared and Raman spectroscopic data of BaP and its three mononitrated isomers are provided for the first time. By utilizing density functional theory (DFT, B3LYP method with 6-311+G** basis set), the molecular geometries and the vibrational spectra are calculated. Good agreement is noted between the calculated and experimental geometry for BaP, and predictions of the vibrational data for all compounds are within ∼5 cm-1 of the experimental data. Normal mode assignments are proposed with particular emphasis on the nitro group vibrations. The geometrical distortions of the BaP structure upon nitro group substitution and correlations between structural parameters and vibrational data as well as structure−function relationships related to the mutagenicity of this important class of polycyclic aromatic hydrocarbons are discussed

Mixed Ionic and Electronic Conduction in Li_3PO_4 Electrolyte for a CO_2 Gas Sensor

An electrochemical CO_2 gas sensor using Li_2CO_3 and Li_2TiO_3+TiO_2 as sensing and reference electrodes, respectively, and Li_3PO_4 as the electrolyte is the subject of this paper. The sensor response to CO_2 gas showed a systematic deviation from the prediction of the Nernst equation at low pCO_2. Based on the electromotive force (emf) measurement, the transference numbers of Li_3PO_4, a lithium-ion conductor, were estimated for different pCO_2 values, and the conduction domain boundary for Li_3PO_4 separating n-type electronic conduction from ionic conduction was constructed. The conduction domain predicts that change in the Li activity in the sensing side of the cell drives the Li_3PO_4 electrolyte to a mixed (n-type electronic and ionic) conduction region at low pCO_2. Hebb-Wagner dc polarization measurements also indicate n-type electronic conduction in Li_3PO_4 with a mixture of Li_2CO_3 and gold as a reversible electrode. The transference numbers obtained from both the emf measurement and the Hebb-Wagner polarization measurements demonstrate that the origin of the non-Nernstian behavior of the CO_2 sensor is due to the lithium mass transport from the Li_2CO_3-sensing electrode to the Li_3PO_4 electrolyte, resulting in nonstoichiometry of Li_3PO_4 at temperatures above 500°C

Silver nanoparticles embedded in zeolite membranes: release of silver ions and mechanism of antibacterial action

Amber Nagy1, Alistair Harrison2, Supriya Sabbani3, Robert S Munson, Jr2, Prabir K Dutta3, W James Waldman11Department of Pathology, The Ohio State University; 2Center for Microbial Pathogenesis, Research Institute at Nationwide Children's Hospital, 3Department of Chemistry, The Ohio State University, Columbus, OH, USABackground: The focus of this study is on the antibacterial properties of silver nanoparticles embedded within a zeolite membrane (AgNP-ZM).Methods and Results: These membranes were effective in killing Escherichia coli and were bacteriostatic against methicillin-resistant Staphylococcus aureus. E. coli suspended in Luria Bertani (LB) broth and isolated from physical contact with the membrane were also killed. Elemental analysis indicated slow release of Ag+ from the AgNP-ZM into the LB broth. The E. coli killing efficiency of AgNP-ZM was found to decrease with repeated use, and this was correlated with decreased release of silver ions with each use of the support. Gene expression microarrays revealed upregulation of several antioxidant genes as well as genes coding for metal transport, metal reduction, and ATPase pumps in response to silver ions released from AgNP-ZM. Gene expression of iron transporters was reduced, and increased expression of ferrochelatase was observed. In addition, upregulation of multiple antibiotic resistance genes was demonstrated. The expression levels of multicopper oxidase, glutaredoxin, and thioredoxin decreased with each support use, reflecting the lower amounts of Ag+ released from the membrane. The antibacterial mechanism of AgNP-ZM is proposed to be related to the exhaustion of antioxidant capacity.Conclusion: These results indicate that AgNP-ZM provide a novel matrix for gradual release of Ag+.Keywords: silver nanoparticles, zeolite, antibacterial agent, oxidative stres

Comparison of Ultrastructural Cytotoxic Effects of Carbon and Carbon/Iron Particulates on Human Monocyte-Derived Macrophages

In this study, we tested the hypothesis that the presence of iron in carbon particulates enhances ultrastructural perturbation in human monocyte-derived macrophages (MDMs) after phagocytosis. We used 1-μm synthetic carbon-based particulates, designed to simulate environmental particulates of mass median aerodynamic diameter ≤ 2.5 μm (PM(2.5)). Cultures of human MDMs or T-lymphocytes (as a nonphagocytic control) were exposed to carbon or carbon/iron particulates for various time periods and examined by transmission electron microscopy for ultrastructural changes. T-cells failed to internalize either of the particulates and showed no organelle or nuclear changes. Conversely, MDMs avidly phagocytized the particulates. MDMs treated with C particulates exhibited morphologic evidence of macrophage activation but no evidence of lysis of organelles. In contrast, MDMs treated with C/Fe particulates exhibited coalescence of particulate-containing lysosomes. This phenomenon was not observed in the case of C particulates. By 24 hr there was a tendency of the C/Fe particulates to agglomerate into loose or compact clusters. Surrounding the compact C/Fe agglomerates was a uniform zone of nearly total organelle lysis. The lytic changes diminished in proportion to the distance from the agglomerate. In such cells, the nucleus showed loss of chromatin. Although C particles induced no detectable oxidative burst on treated MDMs, C/Fe particles induced a nearly 5-fold increase in the extracellular oxidative burst by treated MDMs compared with untreated controls. Iron bound to C particles catalyzed the decomposition of hydrogen peroxide to generate hydroxyl radicals. Results of these studies suggest that, among particulates of similar size, biologic activity can vary profoundly as a function of particulate physicochemical properties

Exploitation of Unique Properties of Zeolites in the Development of Gas Sensors

The unique properties of microporous zeolites, including ion-exchange properties, adsorption, molecular sieving, catalysis, conductivity have been exploited in improving the performance of gas sensors. Zeolites have been employed as physical and chemical filters to improve the sensitivity and selectivity of gas sensors. In addition, direct interaction of gas molecules with the extraframework cations in the nanoconfined space of zeolites has been explored as a basis for developing new impedance-type gas/vapor sensors. In this review, we summarize how these properties of zeolites have been used to develop new sensing paradigms. There is a considerable breadth of transduction processes that have been used for zeolite incorporated sensors, including frequency measurements, optical and the entire gamut of electrochemical measurements. It is clear from the published literature that zeolites provide a route to enhance sensor performance, and it is expected that commercial manifestation of some of the approaches discussed here will take place. The future of zeolite-based sensors will continue to exploit its unique properties and use of other microporous frameworks, including metal organic frameworks. Zeolite composites with electronic materials, including metals will lead to new paradigms in sensing. Use of nano-sized zeolite crystals and zeolite membranes will enhance sensor properties and make possible new routes of miniaturized sensors

Photochemical charge separation in zeolites: Electron transfer dynamics, nanocrystals and zeolitic membranes. Final technical report

Aluminosilicate zeolites provide an excellent host for photochemical charge separation. Because of the constraints provided by the zeolite, the back electron transfer from the reduced acceptor to the oxidized sensitizer is slowed down. This provides the opportunity to separate the charge and use it in a subsequent reaction for water oxidation and reduction. Zeolite-based ruthenium oxide catalysts have been found to be efficient for the water splitting process. This project has demonstrated the usefulness of zeolite hosts for photolytic splitting of water

Photochemistry in Constrained Spaces: Zeolites and Layered Double Metal Hydroxides. Progress Report, August 1, 1992--September 15, 1993

The authors have continued their research in the field of preparation and reactions of photochemical systems in zeolites and layered lithium aluminates. The study on zeolite focused on faujasitic zeolites. The experimental strategy is to build Ru(bpy){sub 3}{sup 2+} inside the supercage and examine the photoelectron transfer from this entrapped complex to acceptor molecules (viologens) through the ring openings. The effort on layered lithium aluminum double hydroxides (LDH) of composition LiAl{sub 2}(OH){sub 6}{sup +}X{sup {minus}} has been on incorporation of photoactive molecules in these interlayers, with particular emphasis on pyrene and Zn porphyrins