Preparation and characterization of zeolite beta–polyurethane composite membranes

Incorporation of zeolite into polyurethane (PU) membranes was investigated by using as‐synthesized and calcined zeolite beta particles at two different loading contents (0.1 and 1 wt %). The chemical interaction between the zeolite beta crystals and PU was observed by ATR‐FTIR spectroscopy. The SEM results suggested that the calcined zeolite beta crystals were more homogeneously dispersed in the composite membranes than the as‐synthesized zeolite beta crystals. DMA results demonstrated that all composite membranes had higher storage modulus in the rubbery state and higher stability towards thermal and mechanical degradation with respect to the control groups. Tensile testing results also showed increased tensile strength and elongation at break for all composite membranes. This study suggests that incorporating zeolite beta in its as‐synthesized or calcined forms and at different amounts can be applied as an alternative method for tailoring the mechanical properties of PU membranes without changing its structural characteristics. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Study of zeolite influence on analytical characteristics of urea biosensor based on ion-selective field-effect transistors

A possibility of the creation of potentiometric biosensor by adsorption of enzyme urease on zeolite was investigated. Several variants of zeolites (nano beta, calcinated nano beta, silicalite, and nano L) were chosen for experiments. The surface of pH-sensitive field-effect transistors was modified with particles of zeolites, and then the enzyme was adsorbed. As a control, we used the method of enzyme immobilization in glutaraldehyde vapour (without zeolites). It was shown that all used zeolites can serve as adsorbents (with different effectiveness). The biosensors obtained by urease adsorption on zeolites were characterized by good analytical parameters (signal reproducibility, linear range, detection limit and the minimal drift factor of a baseline). In this work, it was shown that modification of the surface of pH-sensitive field-effect transistors with zeolites can improve some characteristics of biosensors.     

Conductometric enzyme biosensors based on natural zeolite clinoptilolite for urea determination

Highly sensitive conductometric urea biosensors were developed by exploiting the successful combination of ammonium-sieving and ion exchange properties of clinoptilolite, with a unique biorecognition capacity of urease. To optimize the performance of urea biosensors based on clinoptilolite, the dependences of their analytical signals on pH, buffer capacity and ionic strength of phosphate buffer solution (PBS) were studied. Optimum pH for urea biosensors was found within the range of pH 6.0–7.0. The dependences of biosensors responses on buffer capacity and ionic strength of PBS were of the same profile as those obtained for the urea biosensor which was not modified with clinoptilolite.Analytical characteristics of urea biosensors based on clinoptilolite were evaluated by determination of the sensitivity, linear and dynamic ranges, detection limit, the apparent Michaelis–Menten constant and the response time. The optimum features in terms of sensitivity, dynamic range, and detection limit (20.36 μS/mM, 0–64 mM, and 10^?6 M, respectively) were found for the urea biosensor, based on a primary layer of clinoptilolite followed by a secondary layer of urease and clinoptilolite in a single bioselective membrane. The apparent Michaelis–Menten constants K_m for the developed urea biosensors based on clinoptilolite varied from 2.73 to 5.67 mM. These values differed significantly from the value of K_m for the urea biosensor which was not modified with zeolite (1.89 mM). All types of zeolite-modified biosensors showed high operational and storage stability.     

The catalytic activity of space versus terrestrial synthesized zeolite Beta catalysts in the Meerwein Ponndorf Verley Reactions: Support for PFAL as the Lewis active site for cis-alcohol selectivity

The Lewis activity of the Meerwein-Ponndorf-Verley (MPV) reactions is hypothesized to be due to partial framework aluminum (PFAl) that is either octahedrally or tri-coordinated. Crystals grown in the free-fall environment of low earth orbit (LEO) are more uniform; that is, have fewer lattice “defects” compared to those grown in a gravity field (i.e., on earth). Therefore, crystals grown in orbit should be less catalytically active relative to their earth grown counterparts. The catalytic activity towards the MPV reaction, and the associated IR and XPS spectrum for zeolite Beta that was synthesized on earth (1g) and aboard the International Space Station (10⁻³–10⁻⁵g) were compared in their as-synthesized forms, and after applying heat treatment protocols designed to stress the crystal structure to generate Lewis acid sites (i.e., tri and octahedrally coordinated PFAl). The activity of the MPV reaction and cis-alcohol selectivity over the heat-treated flight samples was observed to be lower than the identically heat-treated terrestrial zeolite Beta samples. Higher MPV activity as well as cis-alcohol selectivity is related to both a higher number of partial framework Al atoms (PFAl), and a constrained pore volume. As PFAl are created by the destruction of the framework upon heat treatment, flight samples were shown to be thermally more stable with fewer lattice defects and less associated stress in zeolite Beta crystals. The changes observed in the IR spectra, as well as the XPS Al Auger and 2p peaks, of the terrestrial samples support this conclusion. Additionally, the flight samples showed higher tr-alcohol selectivity, which implies more pore volume and less channel blockage. This is consistent with the fact that crystals grown in space have less stress, fewer lattice defects, and thus there are fewer channel obstructions.     

On properties at interfaces of friction welded near-nanostructured Al 5083 alloys

Equal-channel angular pressing is a material processing method that allows very high strains to be imposed, which leads to extreme work hardening and micro-structural refinement, with minimal change of external sample dimensions. It offers possibilities of good mechanical properties, such as high strength and ductility, while allowing flexibility of choice of alloy composition for better corrosion behavior, lower materials costs, and so on. This study characterizes for the first time the microstructure and properties of aluminum friction welded after severe plastic deformation via the equal-channel angular pressing method. In this study, 5,083 aluminum alloys, which were exposed to severe plastic deformation using square cross-sectional equal-channel angular pressing die, were joined with friction welding method. It was found that tensile and fatigue strengths of severe plastic deformed and welded specimens were higher than those of the purchased specimens. Hardness values were also consistent with the strength results. However, the refining of grain size as shown from microstructures results in a significant increase in hardness and mechanical properties.     

Titanosilicate ETS-10 as a Lewis acid catalyst in the Meerwein–Ponndorf–Verley (MPV) reaction

The potential of ETS-10 as a Lewis acid catalyst was investigated using the MPV reaction at one atmosphere total pressure and 273 K. ETS-10 was hypothesized to be a potential Lewis acid catalyst as it has titanium in octahedral symmetry, which is the symmetry shown in zeolite Beta to be the most active site for the Lewis acid catalyzed Meerwein–Ponndorf–Verley (MPV) reaction. The MPV reaction is a hydrogen transfer reaction that can be used for obtaining information about the structure and performance of catalysts by comparing the product selectivities and catalytic activities. Due to their similar structures, the catalytic activity of ETS-10 was compared to zeolite Beta samples that were space-grown (flight, fewer defects) and to their earth-grown terrestrial controls. The higher tr-alcohol selectivity (i.e., trans-4-tert-butylcyclohexanol, ∼80% vs. 40%) observed over ETS-10 was attributed to a larger volume being available in the pores of ETS-10 compared to the zeolite Beta samples. By-product formation (i.e., 4-tert-butylcyclohexene) was significantly less over ETS-10 (∼5%) in comparison with the zeolite Beta samples (flight and control; ∼35%). These results reaffirm the octahedral symmetry as the Lewis active site for the MPV reaction, and illustrate that ETS-10 is a good catalyst for MPV type reactions.     

US and CT findings in the diagnosis of tuberculous peritonitis

PURPOSE: To evaluate the ultrasonographic and CT findings of tuberculous peritonitis. MATERIAL AND METHODS: Ultrasonographic and CT findings of 11 patients with the ascitic type of tuberculous peritonitis were reviewed. RESULTS: All patients had ascites, and ultrasonography (US) demonstrated fine complete and incomplete mobile septations in 10 patients. In 5 of them, the ascites had a lattice-like appearance. Diffuse regular peritoneal thickening was detected in all patients by CT and in 10 patients by US. CT demonstrated infiltration of the greater omentum in 9 patients, whereas US showed omental thickening in only 5 patients. CONCLUSION: Peritoneal and omental thickening detected by CT and ascites with fine, mobile septations shown by US strongly suggest the ascitic type of tuberculous peritonitis. The 2 imaging modalities should be used together for accurate diagnosis of tuberculous peritonitis.     

Effect of different modifications of BEA-zeolites on operational characteristics of conductometric biosensor

Effect of different modifications of zeolite Na⁺-BEA on working characteristics of urease-based conductometric biosensor was studied. As the biosensor sensitive elements were used bioselective membranes based on urease and various zeolites immobilised with bovine serum albumin on the surface of conductometric transducers. Influence of zeolites on sensitivity of urea biosensor was investigated as well as reproducibility of biosensor signal and reproducibility of activity of the bioselective element after different variants of urease immobilisation on the surface of conductometric transducer. The biosensors based on zeolites (NH₄⁺-BEA 30 and H⁺-BEA 30) were shown to be the most sensitive. Concentration of these zeolites in the bioselective membrane was optimized. Use of zeolites modified with methyl viologen and silver was ascertained to be of no prospect for urea conductometric biosensors. It was demonstrated that characteristics of urea biosensors can be regulated, varying zeolites modifications and their concentrations in bioselective membranes.     

Investigation of characteristics of urea and butyrylcholine chloride biosensors based on ion-selective field-effect transistors modified by the incorporation of heat-treated zeolite Beta crystals

Urea and butyrylcholine chloride (BuChCl) biosensors were prepared by adsorption of urease and butyrylcholinesterase (BuChE) on heat-treated zeolite Beta crystals, which were incorporated into membranes deposited on ion-selective field-effect transistor (ISFET) surfaces. The responses, stabilities, and use for inhibition analysis of these biosensors were investigated. Different heat treatment procedures changed the amount of Brønsted acid sites without affecting the size, morphology, overall Si/Al ratio, external specific surface area, and the amount of terminal silanol groups in zeolite crystals. Upon zeolite incorporation the enzymatic responses of biosensors towards urea and BuChCl increased up to ~ 2 and ~ 5 times, respectively; and correlated with the amount of Brønsted acid sites. All biosensors demonstrated high signal reproducibility and stability for both urease and BuChE. The inhibition characteristics of urease and BuChE were also related to the Brønsted acidity. The pore volume and pore size increases measured for the heat-treated samples are very unlikely causes for the improvements observed in biosensors' performance, because urease and BuChE are approximately one order of magnitude larger than the resulting zeolite Beta pores. Overall, these results suggest that the zeolites incorporated into the biologically active membrane with enhanced Brønsted acidity can improve the performance of ISFET-based biosensors.