Microwave-assisted synthesis and characterization of flower shaped zinc oxide nanostructures

A microwave-assisted solution-phase approach has been applied for the synthesis of zinc oxide nanostructures. The synthesis procedure was carried out by using two reagents: hydrazine hydrate and ammonia. Flower shaped particles were obtained with hydrazine hydrate whereas mainly spherical agglomerated particles were observed with ammonia. The nanostructures were influenced by microwave irradiation time, reagent concentration and molar ratio of the precursors. High crystalline materials were found without the need of a post-synthesis treatment. The average crystalline size of ZnO nanostructures has been analyzed by X-ray Diffraction (XRD) pattern and estimated to be 18 nm. The presence of flower shaped zinc oxide with nanorods arranged has been confirmed from Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) micrographs. The samples were further analyzed by Fourier Transform InfraRed (FT-IR), Thermogravimetric Analysis (TGA) and photoluminescence spectroscopic techniques.     

An Environmentally Assisted Cracking Evaluation of UNS C64200 (Al–Si–Bronze) and UNS C63200 (Ni–Al–Bronze)

A recent failure of a union nut, UNS C64200, made of Al–Si–Bronze (ASB) in a breathing air system of a marine platform has highlighted the need for environmentally assisted cracking (EAC) data for both ASB and Ni–Al–Bronze UNS C63200 (NAB) components in environments relevant to marine use. In addition, the possibility of exposure to ammonia environments via cleaning agents or biological processes warrants consideration because of the known susceptibility of bronze to EAC in ammonia environments. A displacement-controlled, rising step load (RSL) technique was employed on precracked compact tension specimens to quantify and compare the threshold stress intensities for EAC in air, seawater (SW), and SW + ammonia environments for wrought ASB and NAB materials. These results are compared to calculations of the stress intensity in service to determine the probability of EAC initiation. ASB was found to be susceptible to subcritical intergranular EAC initiation in laboratory air, SW, and SW + ammonia environments. NAB was immune to EAC under the conditions tested in laboratory air and SW, but was susceptible to intergranular EAC in SW + ammonia solution. The threshold stress intensity in SW + ammonia was found to be similar for both ASB and NAB; however, the subcritical crack growth rate for NAB was found to be 2–3 times faster than ASB. Calculations of stress intensity indicate that, in the air system applications where the installation torques are higher, the likelihood of subcritical cracking in ammonia environments is high. Stress intensities approach the ASB threshold values for subcritical intergranular cracking in air when the defect depth approaches half the wall thickness of the nut.     

Off-axis cavity enhanced spectroscopy based on a pulsed quantum cascade laser for sensitive detection of ammonia and ethylene

A pulsed, distributed feedback (DFB) quantum cascade (QC) laser centered at 970 cm(-1) was used in combination with an off-axis cavity enhanced absorption (CEA) spectroscopic technique for the detection of ammonia and ethylene. Here, the laser is coupled into a high-finesse cavity with an optical path length of ～76 m. The cavity is installed into a 53 cm long sample cell with a volume of 0.12 L. The laser is excited with short current pulses (5-10 ns), and the pulse amplitude is modulated with an external current ramp, resulting in a ～0.3 cm(-1) frequency scan. A demodulation approach followed by numerical filtering was utilized to improve the signal-to-noise ratio. We demonstrated detection limits of ~15 ppb and ～20 ppb for ammonia and ethylene, respectively, with less than 5 s averaging time.     

Hydrothermal dechlorination of PVC in the presence of ammonia

Poly(vinyl chloride) (PVC) powder and commercial rigid PVC pipe were dechlorinated hydrothermally in the presence of alkalis such as ammonia, sodium hydroxide, and potassium hydroxide in a semi-batch flow reactor, with comparison to dechlorination using water alone. Aqueous ammonia was the most effective among these solvents. Dechlorination with aqueous ammonia proceeded in three stages: initial incubation, major dechlorination, and slow dechlorination. In the initial stage the rates were very slow and scarcely affected by temperature or ammonia concentration. In the second stage extensive dechlorination took place, and the rates were affected by temperature and ammonia concentration. These higher rates were found to be significantly influenced by swelling, not alkalinity, when these various alkalis solvents were compared. In the last stage the rates were slower than in the previous stage, and were not significantly dependent on temperature or ammonia concentration.     

Kinetic analysis on photocatalytic degradation of gaseous acetaldehyde,ammonia and hydrogen sulfide on nanosized porous TiO2 films

The characteristics of the UV illumination-assisted degradation of gaseous acetaldehyde, hydrogen sulfide, and ammonia on highly active nanostructured-anatase and rutile films were investigated. It was found that the anatase film showed a higher photocatalytic activity than the counterpart did, however, the magnitude of difference in the photocatalytic activity of both films decreased in the order ammonia > acetaldehyde > hydrogen sulfide. To elucidate the reasons for the observation, the adsorption characteristics and the kinetics of photocatalytic degradation of the three reactants on both films were analyzed. The adsorption analysis examined using a simple Langmuir isotherm, showed that adsorbability on both films decreased in the order ammonia > acetaldehyde > hydrogen sulfide, which can be explained in terms of the decreasing electron-donor capacity. Acetaldehyde and ammonia adsorbed more strongly and with higher coverage on anatase film (1.2 and 5.6 molecules/nm², respectively) than on rutile (0.6 and 4.7 molecules/nm², respectively). Conversely, hydrogen sulfide molecules adsorbed more strongly on rutile film (0.7 molecules/nm²) than on anatase (0.4 molecules/nm²). Exposure to UV light illumination brought about the photocatalytic oxidation of the three gases in contact with both TiO₂ films, and the decrease in concentration were measured, and their kinetics are analyzed in terms of the Langmuir–Hinshelwood kinetic model. From the kinetic analysis, it was found that the anatase film showed the photocatalytic activities that were factors of ～8 and ～5 higher than the rutile film for the degradation of gaseous ammonia and acetaldehyde, respectively. However, the activity was only a factor of ～1.5 higher for the photodegradation of hydrogen sulfide. These observations are systematically explained by the charge separation efficiency and the adsorption characteristics of each catalyst as well as by the physical and electrochemical properties of each reactant.     

One-step synthesis of magnetically recyclable Au/Co/Fe triple-layered core-shell nanoparticles as highly efficient catalysts for the hydrolytic dehydrogenation of ammonia borane

Magnetically recyclable Au/Co/Fe core-shell nanoparticles (NPs) have been successfully synthesized via a one-step in situ procedure. Transmission electron microscope (TEM), energy dispersive X-ray spectroscopic (EDS), and electron energy-loss spectroscopic (EELS) measurements revealed that the trimetallic Au/Co/Fe NPs have a triple-layered core-shell structure composed of a Au core, a Co-rich inter-layer, and a Fe-rich shell. The Au/Co/Fe core-shell NPs exhibit much higher catalytic activities for hydrolytic dehydrogenation of ammonia borane (NH₃BH₃, AB) than the monometallic (Au, Co, Fe) or bimetallic (AuCo, AuFe, CoFe) counterparts.      

Comparison of organic and inorganic packing materials in the removal of ammonia gas in biofilters

Two organic and two inorganic packing materials were compared with regard to the removal of ammonia gas in a biofilter inoculated with night-soil sludge. By gradually increasing the inlet load of ammonia, the complete removal capacity, which was defined as the inlet load of ammonia that was completely removed, and the maximum removal capacity of ammonia, which was the value when the removal capacity leveled off for each packing material, were estimated. Both values which were based on a unit volume of packing material, were higher for organic packing materials than inorganic ones. By using kinetic analysis, the maximum removal rate of ammonia, V(m), and the saturation constant, K(s), were determined for all packing materials and the values of V(m) for organic packing materials were found to be larger. By using the kinetic parameters, the removal rates for ammonia were compared among the four packing materials, and the organic packing materials showed superior performance for the removal of ammonia in the concentration range of 0-300 ppm as compared to inorganic packing materials.     

Physical Forces Modulate Oxidative Status and Stress Defense Meditated Metabolic Adaptation of Yeast Colonies: Spaceflight and Microgravity Simulations

Baker’s yeast (Saccharomyces cerevisiae) has broad genetic homology to human cells. Although typically grown as 1-2mm diameter colonies under certain conditions yeast can form very large (10 + mm in diameter) or ‘giant’ colonies on agar. Giant yeast colonies have been used to study diverse biomedical processes such as cell survival, aging, and the response to cancer pharmacogenomics. Such colonies evolve dynamically into complex stratified structures that respond differentially to environmental cues. Ammonia production, gravity driven ammonia convection, and shear defense responses are key differentiation signals for cell death and reactive oxygen system pathways in these colonies. The response to these signals can be modulated by experimental interventions such as agar composition, gene deletion and application of pharmaceuticals. In this study we used physical factors including colony rotation and microgravity to modify ammonia convection and shear stress as environmental cues and observed differences in the responses of both ammonia dependent and stress response dependent pathways We found that the effects of random positioning are distinct from rotation. Furthermore, both true and simulated microgravity exacerbated both cellular redox responses and apoptosis. These changes were largely shear-response dependent but each model had a unique response signature as measured by shear stress genes and the promoter set which regulates them These physical techniques permitted a graded manipulation of both convection and ammonia signaling and are primed to substantially contribute to our understanding of the mechanisms of drug action, cell aging, and colony differentiation.     

Effects of end‐stage renal disease and dialysis modalities on blood ammonia level

Introduction: Uremia results in a characteristic breath odor (uremic fetor) which is largely due to its high ammonia content. Earlier studies have shown a strong correlation between breath ammonia and blood urea levels and a 10‐fold reduction in breath ammonia after hemodialysis in patients with chronic kidney disease. Potential sources of breath ammonia include: (i) local ammonia production from hydrolysis of urea in the oropharyngeal and respiratory tracts by bacterial flora, and (ii) release of circulating blood ammonia by the lungs. While the effects of uremia and hemodialysis on breath ammonia are well known their effects on blood ammonia are unknown and were explored here. Methods: Blood samples were obtained from 23 hemodialysis patients (immediately before and after dialysis), 14 peritoneal dialysis patients, and 10 healthy controls. Blood levels of ammonia, creatinine, urea, and electrolytes were measured. Findings: No significant difference was found in baseline blood ammonia between hemodialysis, peritoneal dialysis and control groups. Hemodialysis procedure led to a significant reduction in urea concentration (P < 0.001) which was paradoxically accompanied by a modest but significant (P < 0.05) rise in blood ammonia level in 10 of the 23 patients studied. Change in blood ammonia pre‐ and post‐hemodialysis correlated with change in serum bicarbonate levels (r = 0.61, P < 0.01). On subgroup analysis of patients who had a rise in blood ammonia levels after dialysis, there was a strong correlation with drop in mean arterial pressure (r = 0.88, P < 0.01). The nadir intradialytic systolic blood pressure trended lower in the hemodialysis patients who had a rise in blood ammonia compared to the patients who manifested a fall in blood ammonia (124 ± 8 vs. 136 ± 6 mmHg respectively, P = 0.27). Discussion: Fall in blood urea following hemodialysis in ESRD patients was paradoxically accompanied by a modest rise in blood ammonia levels in 43% of the patients studied, contrasting prior reported effects of hemodialysis on breath ammonia. In this subgroup of patients, changes in blood ammonia during hemodialysis correlated with rise in blood bicarbonate and fall in mean arterial blood pressure.     

Optical properties and switching of a Rose Bengal derivative: A spectroscopic ellipsometry study

Optical properties in terms of the complex-valued dielectric function were determined for spin-coated films of a Rose Bengal derivative using variable angle of incidence spectroscopic ellipsometry in the visible and infrared wavelength regions. In addition, the thickness and roughness of the films were determined and related to the solution concentration of Rose Bengal. Switching between two different oxidation states of the Rose Bengal derivative was investigated. The two states were chemically induced by exposure to vapors of hydrochloric acid and ammonia, respectively. A substantial and reversible change of the optical properties of the films was observed.     

Anaerobic ammonia removal in presence of organic matter: a novel route

This study describes the feasibility of anaerobic ammonia removal process in presence of organic matter. Different sources of biomass collected from diverse eco-systems containing ammonia and organic matter (OM) were screened for potential anaerobic ammonia removal. Sequential batch studies confirmed the possibility of anaerobic ammonia removal in presence of OM, but ammonia was oxidized anoxically to nitrate (at oxidation reduction potential; ORP=-248+/-25 mV) by an unknown mechanism unlike in the reported anammox process. The oxygen required for oxidation of ammonia might have been generated through catalase enzymatic activity of facultative anaerobes in mixed culture. The oxygen generation possibility by catalase enzyme route was demonstrated. Among the inorganic electron acceptors (NO(2)(-), NO(3)(-) and SO(4)(2-)) studied, NO(2)(-) was found to be most effective in total nitrogen removal. Denitrification by the developed culture was much effective and faster compared to ammonia oxidation. The results of this study show that anaerobic ammonia removal is feasible in presence of OM. The novel nitrogen removal route is hypothesized as enzymatic anoxic oxidation of NH(4)(+) to NO(3)(-), followed by denitrification via autotrophic and/or heterotrophic routes. The results of batch study were confirmed in continuous reactor operation.     

Improved understanding of factors contributing to quantification of anhydrate/hydrate powder mixtures

Different spectroscopic approaches have proved to be excellent analytical tools for monitoring process-induced transformations of active pharmaceutical ingredients during pharmaceutical unit operations. In order to use these tools effectively, it is necessary to build calibration models that describe the relationship between the amount of each solid-state form of interest and the spectroscopic signal. In this study, near-infrared (NIR) and Raman spectroscopic methods have been evaluated for the quantification of hydrate and anhydrate forms in pharmaceutical powders. Process type spectrometers were used to collect the data and the role of the sampling procedure was examined. Multivariate regression models were compared with traditional univariate calibrations and special emphasis was placed on data treatment prior to multivariate modeling by partial least squares (PLS). It was found that the measured sample volume greatly affected the performance of the model whereby the calibrations were significantly improved by utilizing a larger sampling area. In addition, multivariate regression did not always improve the predictability of the data compared to univariate analysis. The data treatment prior to multivariate modeling had a significant influence on the quality of predictions with standard normal variate transformation generally proving to be the best preprocessing method. When the appropriate sampling techniques and data analysis methods were utilized, both NIR and Raman spectroscopy were found to be suitable methods for the quantification of anhydrate/hydrate in powder systems, and thus the method of choice will depend on the conditions in the process under investigation.     

Optimizing the dimensions of magnesium ammonium phosphate to maximize its ammonia uptake ability

Magnesium ammonium phosphate (MgNH₄PO₄·6H₂O:MAP) releases approximately 70% of its ammonia at a mild temperature of 378 K. The resultant material (magnesium hydrogen phosphate (MgHPO₄:MHP)-like material), which appears to be an amorphous phase, to remove ammonia from wastewater was investigated. Because the original size of MAP crystals was found to critically affect the kinetics of ammonia uptake by the corresponding MHP-like material, MAP with different sizes were synthesized by changing concentration, pH and temperature of the synthesis solution. The variation in the synthesis concentration was found to change the size of MAP as well as the aspect ratio of the long-axis to the short-axis. The rate of ammonia uptake depends primarily on the dimension of the short-axis of the corresponding MAP crystals. Furthermore, analysis of ammonia uptake using a method similar to the shrinking-core model shows approximately 0.5 μm from the surface is effectively used for ammonia uptake over a period of a realistic process time. Thus, the results suggest it is crucial to synthesize small MAP crystals with the size of short-axis less than 1 μm. Our results also show that small MAP crystals can be used at least four times repeatedly for ammonia uptake.     

Characterization of bidimensional gratings by spectroscopic ellipsometry and angle-resolved Mueller polarimetry

We studied two bidimensional square gratings of square holes formed in photoresist layers deposited on silicon wafers, both by classical spectroscopic ellipsometry (1.5-4.5-eV spectral range) at a constant incidence angle (70.7 degrees) and by angle-resolved Mueller polarimetry at a constant wavelength (532 nm). The grating period was 1 microm in both directions, and the nominal hole sizes were 250 and 500 nm, respectively. The ellipsometric spectra were fitted by rigorous coupled-wave analysis simulations with two adjustable parameters, the resist layer thickness and the hole size. These parameters were found to be in good agreement with independent scanning electron microscopy measurements. The experimental angle-resolved Mueller spectra were remarkably well reproduced by the simulations, showing that angle-resolved Mueller polarimetry has a great potential for grating metrology applications.     

Ammonia vapor sensing properties of polyaniline-titanium(IV)phosphate cation exchange nanocomposite

In this study, the electrically conducting polyaniline-titanium(IV)phosphate (PANI-TiP) cation exchange nanocomposite was synthesized by sol-gel method. The cation exchange nanocomposite based sensor for detection of ammonia vapors was developed at room temperature. It was revealed that the sensor showed good reversible response towards ammonia vapors ranging from 3 to 6%. It was found that the sensor with p-toluene sulphonic acid (p-TSA) doped exhibited higher sensing response than hydrochloric acid doped. This sensor has detection limit ≤1% ammonia. The response of resistivity changes of the cation exchange nanocomposite on exposure to different concentrations of ammonia vapors shows its utility as a sensing material. These studies suggest that the cation exchange nanocomposite could be a good material for ammonia sensor at room temperature.     

Effect of vapor flow on the falling-film heat and mass transfer of the ammonia/water absorber

Falling-film heat and mass transfer in an absorber can be influenced by the motion of the surrounding refrigerant vapor. In this study, the effect of the vapor flow direction on the absorption heat and mass transfer has been investigated for a falling-film helical coil absorber which is frequently used in the ammonia/water absorption refrigerators. The heat and mass transfer performance was measured for both parallel and countercurrent flow. The experiments were carried out for three different solution concentrations (3, 14, and 30%). The vapor in equilibrium with the solution is supplied to the test section. It is found that the falling-film heat and mass transfer is deteriorated in the countercurrent flow if the specific volume of the vapor solution is large. For the countercurrent flow, the high velocity of the vapor due to large specific volume seems to cause the unfavorable distribution of falling-film and reduce the heat and mass transfer performance of the ammonia absorber. The effect of vapor flow direction decreased with increasing concentration of ammonia solution since the specific volume of the ammonia vapor which is in equilibrium with the solution becomes smaller and the vapor velocity becomes lower.     

Behaviors of the "raman spectroscopic signature of life" in single living fission yeast cells under different nutrient, stress, and atmospheric conditions

Time- and space-resolved Raman spectra of mitochondria in single living fission yeast cells have been measured under various nutrient, stress, and atmospheric conditions. A focus is placed on the behavior of the Raman band located at 1602 cm(-1), which sensitively reflects the metabolic activity in mitochondria and which has been called by us the "Raman spectroscopic signature of life". Addition of nutrients increases the intensity of this band by approximately 1.5 times, confirming its correlation with the metabolic activity in mitochondria. The spectra of cells cultured under 100% N(2), 100% O(2), and N(2)/O(2) (V(N2):V(O2) congruent with approximately = 4:1) atmospheres have been measured for both (16)O(2) and (18)O(2). Yeast cells have been found to lose their metabolic activity after the culture under 100% N(2) and 100% O(2) atmospheres. Cells cultured under a N(2)/(16)O(2) ((16)O(2) = 20%) atmosphere show strong "Raman spectroscopic signature of life". No (18)O isotopic shift has been found for the wavenumber 1602 cm(-1), indicating that the origin of this signature is neither O(2) nor an O-containing small molecule. Addition of H(2)O(2) causes a quick decrease of the "Raman spectroscopic signature of life", followed by the cis-trans isomerization in the unsaturated phospholipid chain. The "Raman spectroscopic signature of life" has thus been proved to be a reliable real-time and in vivo indicator for monitoring the metabolic activity in living cells.     

Effects of post-deposition chemical treatment on the formation of mesoporous titania films

Mesoporous titania films have been synthesized by a modified sol–gel method in conjunction with amphiphilic triblock copolymers. The effects of ammonia vapor treatment on the formation of mesoporous structures were investigated. Mesoporous titania films with hexagonal structures were obtained by ammonia vapor treatment. Without ammonia vapor treatment, it was found that the mesoporous structures collapse due to crystallization. The framework of mesoporous titania was found to be amorphous. Mesoporous titania films prepared by ammonia vapor treatment showed thermal stability up to 500 °C. Mesoporous samples showed better photo-catalytic activity than anatase titania films under UV-light irradiation.     

Quantitative analysis of metabolic gases by multichannel Raman spectroscopy: use of a newly designed elliptic-spherical integration type of cell holder

We describe the quantitative analysis of some metabolic gases bymultichannel Raman spectroscopy. Raman spectra were measured forair, acetone, ammonia, carbon dioxide, and mixed gas consisting ofacetone, ammonia, and air. We designed a new elliptic-sphericalintegration type of cell holder to obtain the Raman spectra of gaseswith a high signal-to-noise ratio. Concentrations of acetone, ammonia, and carbon dioxide were determined by the peak intensities ofRaman bands at 2940, 3228, and 1385 cm(-1), respectively. To compensate for the fluctuations of Ramanintensities caused by several factors, such as the fluctuations oflaser power, the peak intensity of a band at 2324 cm(-1) dueto nitrogen gas was used as an internal intensity standard. Thecorrelation coefficient between the corrected Raman intensity at 2940cm(-1) and the concentration of acetone was calculated to be0.984 for a concentration range of 2-12 ppm. The detection limitof acetone gas was found to be 2 ppm.     

Polyphosphate gel/methyl orange supramolecular composites

The aims of this work were to investigate theoretically the optical properties of methyl orange (MO) and the synthesis of new supramolecular composites based on the incorporation of this dye in an aluminum polyphosphate gel network. The theoretical methodology was based in semiempirical (AM1 and INDO/S-CI) and ab initio (3-21G*) methods. Our results reveal the existence of different electronic patterns for the acidic and basic forms of these molecules. Also, we present a theoretical spectroscopic study for the molecules including interactions with water molecules. MO was successfully incorporated in its acidic form within the host matrix, leading to pink–red transparent self-standing films. The dye could be converted to its basic form upon exposure to ammonia vapor. The spectrum of MO basic form within the gel network differs from its behavior in aqueous solution.