Systemic oxidative stress is implicated in the pathogenesis of brain edema in rats with chronic liver failure.

Chronic liver failure leads to hyperammonemia, a central component in the pathogenesis of hepatic encephalopathy (HE); however, a correlation between blood ammonia levels and HE severity remains controversial. It is believed oxidative stress plays a role in modulating the effects of hyperammonemia. This study aimed to determine the relationship between chronic hyperammonemia, oxidative stress, and brain edema (BE) in two rat models of HE: portacaval anastomosis (PCA) and bile-duct ligation (BDL). Ammonia and reactive oxygen species (ROS) levels, BE, oxidant and antioxidant enzyme activities, as well as lipid peroxidation were assessed both systemically and centrally in these two different animal models. Then, the effects of allopurinol (xanthine oxidase inhibitor, 100mg/kg for 10days) on ROS and BE and the temporal resolution of ammonia, ROS, and BE were evaluated only in BDL rats. Similar arterial and cerebrospinal fluid ammonia levels were found in PCA and BDL rats, both significantly higher compared to their respective sham-operated controls (p<0.05). BE was detected in BDL rats (p<0.05) but not in PCA rats. Evidence of oxidative stress was found systemically but not centrally in BDL rats: increased levels of ROS, increased activity of xanthine oxidase (oxidant enzyme), enhanced oxidative modifications on lipids, as well as decreased antioxidant defense. In PCA rats, a preserved oxidant/antioxidant balance was demonstrated. Treatment with allopurinol in BDL rats attenuated both ROS and BE, suggesting systemic oxidative stress is implicated in the pathogenesis of BE. Analysis of ROS and ammonia temporal resolution in the plasma of BDL rats suggests systemic oxidative stress might be an important "first hit", which, followed by increases in ammonia, leads to BE in chronic liver failure. In conclusion, chronic hyperammonemia and oxidative stress in combination lead to the onset of BE in rats with chronic liver failure.

The Effect of Glass Additives on the Microwave Dielectric Properties of Ba(Mg 1 /3Ta2/3)03 Ceramics

The effect of glass additives on the densification , phase evolution, microstructure and microwave dielectric properties of Ba(Mg1;3 Ta2i3)03 (BMT) was investigated . Different weight percentages of quenched glass such as B203 , Si02, B203-SiO2, ZnO-B203, 5ZnO-2B2O3, Al203-SiO2, Na20-2B203.10H20, BaO-B203-SiO2, MgO-B203-SiO2, PbO-B203-SiO2 , ZnO-B203-SiO2 and 2MgO-Al203-5SiO2 were added to calcined BMT precursor . The sintering temperature of the glass -added BMT samples were lowered down to 1300 °C compared to solid-state sintering where the temperature was 1650 °C. The formation of high temperature satellite phases such as Ba5Ta4O15 and Ba7Ta6O22 were found to be suppressed by the glass addition . Addition of glass systems such as B203, ZnO-B203, 5ZnO-2B203 and ZnO-B203-SiO2 improved the densification and microwave dielectric properties. Other glasses were found to react with BMT to form low-Q phases which prevented densification . The microwave dielectric properties of undoped BMT with a densification of 93 . 1 % of the theoretical density were Cr = 24 . 8, Tr = 8 ppm/°C and Q„ x f= 80,000 GHz. The BMT doped with 1.0 wt% of B203 has Q„ x f = 124,700GHz, Cr = 24.2, and T f = -1.3 ppm /°C. The unloaded Q factor of 0.2 wt% ZnO-B203-doped BMT was 136,500 GHz while that of 1.0 wt% of 5ZnO-2B203 added ceramic was Q„ x f= 141,800 GHz . The best microwave quality factor was observed for ZnO -B203-SiO2 (ZBS) glass-added ceramics which can act as a perfect liquid-phase medium for the sintering of BMT. The microwave dielectric properties of 0.2wt% ZBS-added BMT dielectric was Q„ x f= 152,800 GHz, F,= 25.5, and Tr = - 1.5 ppm/°C

Photopyroelectric study of thermal properties and phase transitions in selected solids

This thesis presents in detail. the theoretical developments and calculations which are used for the simultaneous determination of thermal parameters, namely thermal diffusivity (a). thermal effusivity (e), thermal conductivity (K) and heat capacity (cr ) employing photopyroelectric technique. In our calculations. we have assumed that the pyroelectric detector is supported on a copper backing. so that there will be sufficient heat exchange between the heated pyroelectric detector and the backing so that the signal fluctuations are reduced to a minimum. Since the PPE signal depends on the properties of the detector that are also temperature dependent. a careful temperature calibration of the system need to be carried out. APPE cell has been fabricated for the measurements that can be used to measure the thermal properties of solid samples from ~ 90 K to ~ 350 K. The cell has been calibrated using standard samples and the accuracy of the technique is found to be of the order of± 1%.In this thesis, we have taken up work n photopyroelectric investigation of thermal parameters of ferroelectric crystals such as Glycine phosphite (NH3CH2COOH3P03), Triglycine sulfate and Thiourea as well as mixed valence perovskites samples such as Lead doped Lanthanum Manganate (Lal_xPb~Mn03) Calcium doped (Lal_xCaxMnOJ) and Nickel doped Lanthanum Stroncium Cobaltate (Lao~Sro5Ni,Col_x03).The three ferroelectric crystals are prepared by the slow evaporation technique and the mixed valence perovskites by solid state reaction technique.Mixed valence perovskites, with the general formula RI_xA~Mn03 (R = La. Nd or Pr and A = Ba, Ca, Sr or Pb) have been materials of intense experimental and theoretical studies over the past few years. These materials show . colossal magneloresis/ance' (CMR) in samples with 0.2 < x < 0.5 in such a doping region, resistivity exhibits a peak at T = T p' the metal - insulator transition temperature. The system exhibits metallic characteristics with d %T > Oabove Tp (wherep is the resistivity) and insulating characteristics with d % T < 0 above T p. Despite intensive investigations on the CMR phenomena and associated electrical properties. not much work has been done on the variation of thermal properties of these samples. We have been quite successful in finding out the nature of anomaly associated with thermal properties when the sample undergoes M-I transition.The ferroelectric crystal showing para-ferroelectric phase transitions - Glycine phosphite. Thiourea and Triglycine sulfate - are studied in detail in order to see how well the PPE technique enables one to measure the thermal parameters during phase transitions. It is seen that the phase transition gets clearly reflected in the variation of thermal parameters. The anisotropy in thermal transport along different crystallographic directions are explained in terms of the elastic anisotropy and lattice contribution to the thermal conductivity. Interesting new results have been obtained on the above samples and are presented in three different chapters of the thesis.In summary. we have carried investigations of the variations of the thermal parameters during phase transitions employing photopyroelectric technique. The results obtained on different systems are important not only in understanding the physics behind the transitions but also in establishing the potentiality of the PPE tool. The full potential of PPE technique for the investigation of optical and thermal properties of materials still remains to be taken advantage of by workers in this field.

Investigations on Structural response of Water Backed Perforated plates

The study envisaged herein contains the numerical investigations on Perforated Plate (PP) as well as numerical and experimental investigations on Perforated Plate with Lining (PPL) which has a variety of applications in underwater engineering especially related to defence applications. Finite element method has been adopted as the tool for analysis of PP and PPL. The commercial software ANSYS has been used for static and free vibration response evaluation, whereas ANSYS LS-DYNA has been used for shock analysis. SHELL63, SHELL93, SOLID45, SOLSH190, BEAM188 and FLUID30 finite elements available in the ANSYS library as well as SHELL193 and SOLID194 available in the ANSYS LS-DYNA library have been made use of. Unit cell of the PP and PPL which is a miniature of the original plate with 16 perforations have been used. Based upon the convergence characteristics, the utility of SHELL63 element for the analysis of PP and PPL, and the required mesh density are brought out. The effect of perforation, geometry and orientation of perforation, boundary conditions and lining plate are investigated for various configurations. Stress concentration and deflection factor are also studied. Based on these investigations, stadium geometry perforation with horizontal orientation is recommended for further analysis.Linear and nonlinear static analysis of PP and PPL subjected to unit normal pressure has been carried out besides the free vibration analysis. Shock analysis has also been carried out on these structural components. The analytical model measures 0.9m x 0.9m with stiffener of 0.3m interval. The influence of finite element, boundary conditions, and lining plate on linear static response has been estimated and presented. Comparison of behavior of PP and PPL in the nonlinear strain regime has been made using geometric nonlinear analysis. Free vibration analysis of the PP and PPL has been carried out ‘in vacuum’ condition and in water backed condition, and the influence of water backed condition and effect of perforation on natural frequency have been investigated.Based upon the studies on the vibration characteristics of NPP, PP and PPL in water backed condition and ‘in vacuum’ condition, the reduction in the natural frequency of the plate in immersed condition has been rightly brought out. The necessity to introduce the effect of water medium in the analysis of water backed underwater structure has been highlighted.Shock analysis of PP and PPL for three explosives viz., PEK, TNT and C4 has been carried out and deflection and stresses on plate as well as free field pressure have been estimated using ANSYS LS-DYNA. The effect of perforations and the effect of lining plate have been predicted. Experimental investigations of the measurement of free field pressure using PPL have been conducted in a shock tank. Free field pressure has been measured and has been validated with finite element analysis results. Besides, an experiment has been carried out on PPL, for the comparison of the static deflection predicted by finite element analysis.The distribution of the free field pressure and the estimation of differential pressure from experimentation and the provision for treating the differential pressure as the resistance, as a part of the design load for PPL, has been brought out.

Horizontal nutrient fluxes and production efficiencies in urban and peri-urban crop and livestock husbandry of Niamey, Niger

Urban and peri-urban agriculture (UPA) increasingly supplies food and non-food values to the rapidly growing West African cities. However, little is known about the resource use efficiencies in West African small-scale UPA crop and livestock production systems, and about the benefits that urban producers and retailers obtain from the cultivation and sale of UPA products. To contribute to filling this gap of knowledge, the studies comprising this doctoral thesis determined nutrient use efficiencies in representative urban crop and livestock production system in Niamey, Niger, and investigated potential health risks for consumers. Also assessed was the economic efficiency of urban farming activities. The field study, which was conducted during November 2005 to January 2008, quantified management-related horizontal nutrient flows in 10 vegetable gardens, 9 millet fields and 13 cattle and small ruminant production units. These farms, selected on the basis of a preceding study, represented the diversity of UPA crop and livestock production systems in Niamey. Based on the management intensity, the market orientation and especially the nutrient input to individual gardens and fields, these were categorized as high or low input systems. In the livestock study, high and low input cattle and small ruminant units were differentiated based on the amounts of total feed dry matter offered daily to the animals at the homestead. Additionally, economic returns to gardeners and market retailers cultivating and selling amaranth, lettuce, cabbage and tomato - four highly appreciated vegetables in Niamey were determined during a 6-months survey in forty gardens and five markets. For vegetable gardens and millet fields, significant differences in partial horizontal nutrient balances were determined for both management intensities. Per hectare, average annual partial balances for carbon (C), nitrogen (N), phosphorus (P) and potassium (K) amounted to 9936 kg C, 1133 kg N, 223 kg P and 312 kg K in high input vegetable gardens as opposed to 9580 kg C, 290 kg N, 125 kg P and 351 kg K in low input gardens. These surpluses were mainly explained by heavy use of mineral fertilizers and animal manure to which irrigation with nutrient rich wastewater added. In high input millet fields, annual surpluses of 259 kg C ha-1, 126 kg N ha-1, 20 kg P ha-1 and 0.4 kg K ha-1 were determined. Surpluses of 12 kg C ha-1, 17 kg N ha-1, and deficits of -3 kg P ha-1 and -3 kg K ha-1 were determined for low input millet fields. Here, carbon and nutrient inputs predominantly originated from livestock manure application through corralling of sheep, goats and cattle. In the livestock enterprises, N, P and K supplied by forages offered at the farm exceeded the animals’ requirements for maintenance and growth in high and low input sheep/goat as well as cattle units. The highest average growth rate determined in high input sheep/goat units was 104 g d-1 during the cool dry season, while a maximum average gain of 70 g d-1 was determined for low input sheep/goat units during the hot dry season. In low as well as in high input cattle units, animals lost weight during the hot dry season, and gained weight during the cool dry season. In all livestock units, conversion efficiencies for feeds offered at the homestead were rather poor, ranging from 13 to 42 kg dry matter (DM) per kg live weight gain (LWG) in cattle and from 16 to 43 kg DM kg-1 LWG in sheep/goats, pointing to a substantial waste of feeds and nutrients. The economic assessment of the production of four high value vegetables pointed to a low efficiency of N and P use in amaranth and lettuce production, causing low economic returns for these crops compared to tomato and cabbage to which inexpensive animal manure was applied. The net profit of market retailers depended on the type of vegetable marketed. In addition it depended on marketplace for amaranth and lettuce, and on season and marketplace for cabbage and tomato. Analysis of faecal pathogens in lettuce irrigated with river water and fertilized with animal manure indicated a substantial contamination by Salmonella spp. with 7.2 x 104 colony forming units (CFU) per 25 g of produce fresh matter, while counts of Escherichia coli averaged 3.9 x 104 CFU g-1. In lettuce irrigated with wastewater, Salmonella counts averaged 9.8 x 104 CFU 25 g-1 and E. coli counts were 0.6 x 104 CFU g-1; these values exceeded the tolerable contamination levels in vegetables of 10 CFU g-1 for E. coli and of 0 CFU 25 g-1 for Salmonella. Taken together, the results of this study indicate that Niamey’s UPA enterprises put environmental safety at risk since excess inputs of N, P and K to crop and livestock production units favour N volatilisation and groundwater pollution by nutrient leaching. However, more detailed studies are needed to corroborate these indications. Farmers’ revenues could be significantly increased if nutrient use efficiency in the different production (sub)systems was improved by better matching nutrient supply through fertilizers and feeds with the actual nutrient demands of plants and animals.

Effects of tillage intensity on soil C, N, and P pools with different stability

Es ist bekannt, dass die Umsatzdynamik der organischen Substanz von der Bodenbearbeitungsintensität abhängt. Bis jetzt sind nur wenige Daten zum Einfluss der Bearbeitungsintensität und des Zwischenfruchtanbaus auf C-, N-, und P-Dynamik im Ober- (0-5 cm Tiefe) und Unterboden (5-25 cm Tiefe) von Lössböden verfügbar. Hauptziele dieser Arbeit waren die (i) Quantifizierung des Einflusses von verschiedenen langzeitig durchgeführten Bearbeitungssystemen auf labile, intermediäre, und passive C- und N-Pools; (ii) Quantifizierung des Einflusses dieser Systeme auf P-Fraktionen mit unterschiedlicher Verfügbarkeit für die Pflanzenaufnahme; (iii) Quantifizierung des Einflusses des Zwischenfruchtanbaus in Verbindung mit einer unterschiedlichen Einarbeitungstiefe der der Zwischenfrüchte auf mineralisierbares C und N. Die Ergebnisse des 1. und 2. Teilexperiments basieren auf Untersuchungen von 4 Langzeitfeldexperimenten (LFE) in Ost- und Süddeutschland, die zwischen 1990 und 1997 durch das Institut für Zuckerrübenforschung angelegt wurden. Jedes LFE umfasst 3 Bearbeitungssysteme: konventionelle Bearbeitung (CT), reduzierte Bearbeitung (RT) und Direktsaat (NT). Die Ergebnisse des 3. Teilexperiments basieren auf einem Inkubationsexperiment. Entsprechend den Hauptfragestellungen wurden folgende Untersuchungsergebnisse beschrieben: (i) Im Oberboden von NT wurden höhere labile C-Vorräte gefunden (C: 1.76 t ha-1, N: 166 kg ha-1), verglichen mit CT (C: 0.44 t ha-1, N: 52 kg ha-1). Im Gegensatz dazu waren die labile- C-Vorräte höher im Unterboden von CT mit 2.68 t ha-1 verglichen zu NT mit 2 t ha-1 und RT mit 1.87 t ha-1. Die intermediären C-Vorräte betrugen 73-85% der gesamten organischen C-Vorräte, intermediäre N-Vorräte betrugen 70-95% des Gesamt-N im Ober- und Unterboden und waren vielfach größer als die labilen und passiven C- und N-Vorräte. Nur im Oberboden konnte ein Effekt der Bearbeitungsintensität auf die intermediären N-Pools mit höheren Vorräten unter NT als CT festgestellt werden. Die passiven C- und N-Pools waren eng mit den mineralischen Bodeneigenschaften verbunden und unabhängig vom Bearbeitungssystem. Insgesamt hat sich gezeigt, dass 14 bis 22 Jahre durchgängige Direktsaatverfahren nur im Oberboden zu höheren labilen C- und N-Vorräten führen, verglichen zu konventionellen Systemen. Dies lässt eine tiefenabhängige Stärke der Dynamik der organischen Bodensubstanz vermuten. (ii) Die Konzentration des Gesamt-P (Pt) im Oberboden war höher in NT (792 mg kg-1) und ~15% höher als die Pt-Konzentration in CT (691 mg kg 1). Die Abnahme der Pt-Konzentration mit zunehmender Bodentiefe war höher in NT als in CT. Dies gilt auch für die einzelnen P-Fraktionen, ausgenommen der stabilsten P-Fraktion (residual-P). Generell hatte das Bearbeitungssystem nur einen kleinen Einfluss auf die P-Konzentration mit höheren Pt-Konzentrationen in Böden unter NT als CT. Dies resultiert vermutlich aus der flacheren Einarbeitung der Pflanzenreste als in CT. (iii) Im Zwischenfruchtexperiment war der Biomassezuwachs von Senf am höchsten und nimmt in der Reihenfolge ab (oberirdischer Ertrag in t / ha): Senf (7.0 t ha-1) > Phacelia (5.7 t ha-1) > Ölrettich (4.4 t ha-1). Damit war potentiell mineralisierbares C und N am höchsten in Böden mit Senfbewuchs. Kumulative CO2- und N2O-Emissionen während der Inkubation unterschieden sich nicht signifikant zwischen den Zwischenfruchtvarianten und waren unabhängig von der Verteilung der Pflanzenreste im Boden. Die kumulativen ausgewaschenen mineralisierten N (Nmin)-Vorräte waren in den brachliegenden Böden am höchsten. Die Nmin-Vorräte waren 51-72% niedriger in den Varianten mit Zwischenfrucht und Einarbeitung verglichen zur Brache. In den Varianten ohne Einarbeitung waren die Nmin-Vorräte 36-55% niedriger verglichen zur Brache. Dies weißt auf einen deutlichen Beitrag von Zwischenfrüchten zur Reduzierung von Nitrat-Auswaschung zwischen Winter und Frühjahr hin. Insgesamt führte reduzierte Bearbeitung zu einer Sequestrierung von C und N im Boden und der Zwischenfruchtanbau führte zu reduzierten N-Verlusten. Die P-Verfügbarkeit war höher unter Direktsaat verglichen zur konventionellen Bearbeitung. Diese Ergebnisse resultieren aus den höheren Konzentrationen der OS in den reduzierten, als in den konventionellen Systemen. Die Ergebnisse zeigen deutlich das Potential von reduzierter Bearbeitung zur Sequestrierung von intermediärem C und N zur Reduzierung von klimarelevanten Treibhausgasen. Gleichzeitig steigen die Konzentrationen an pflanzenverfügaren P-Gehalten. Zwischenfrüchte führen auch zu einem Anstieg der C- und N-Vorräte im Boden, offensichtlich unabhängig von der Zwischenfruchtart.

Seguimiento de áreas cruentas cubiertas con queratinocitos autólogos cultivados en suero autólogo: Estudio multicéntrico en Bogotá

En 2009 se presento la estandarización de cultivos de queratinocitos autólogos cultivados en suero autólogo. En este estudio los autores describen la efectividad de estos parches de regeneración de piel, para la cobertura de áreas cruentas con indicación de injerto de piel parcial. El porcentaje de epitelización del área cruenta fue el punto principal. Métodos: 47 pacientes fueron incluidos consecutivamente, equivalentes a 78 áreas cruentas. Las áreas fueron estratificadas según la profundidad: grupo 1:IIA (n=8) grupo 2: IIB (n=39); grupo 3,III (n=24) y grupo 4, etiología diferente: Otras (n=7). Todas las áreas fueron tratadas con injertos de queratinocitos autólogos cultivados en suero autólogo y se realizo registro fotográfico y del porcentaje de epitelización al día 5, 7, 15 y 30. Resultados: La efectividad de los injertos de queratinocitos autólogos es de 53.16% ± 46.46%. El porcentaje de epitelización es mayor para el grupo 1 (100%) y grupo 2 (62.79%) que para el grupo 3 (27.57%) y el grupo 4 (33.86%). Se encontró relación entre la interacción de las medianas del porcentaje de epitelización entre área corporal y grado de quemadura (p<0.001 KW) siendo mayor para el grupo 1 en todas las áreas, grupo 2 en cara, grupo 3 en tronco y grupo 4 en cara; y el menor porcentaje de epitelización en el grupo 3 y grupo 4 de las áreas ubicadas tronco. Conclusión: Los injertos de queratinocitos autólogos cultivados en suero autólogo son un método de cobertura eficaz para áreas cruentas producidas por quemaduras IIA y IIB independientemente del tamaño y la localización , y para las áreas cruentas pequeñas (<9cm2) de etiología diferente o grado III de profundidad. Palabras Clave: Cultivo queratinocitos, cobertura áreas cruentas, efectividad.

Selenium persistency and speciation in the tissues of lambs following the withdrawal of dietary high-dose selenium-enriched yeast

The objective was to determine the concentration of total selenium (Se) and the proportion of total Se comprised as selenomethionine (SeMet) and selenocysteine (SeCys) in post mortem tissues of lambs in the six weeks period following the withdrawal of a diet containing high dose selenized yeast (SY), derived from a specific strain of Saccharomyces cerevisae CNCM (Collection Nationale de Culture de Micro-organism) I-3060. Thirty Texel x Suffolk lambs used in this study had previously received diets (91 days) containing either high dose SY (HSY; 6.30 mg Se/kg DM) or an unsupplemented control (C; 0.13 mg Se/kg DM). Following the period of supplementation all lambs were then offered a complete pelleted diet, without additional Se (0.15 mg Se/kg DM), for 42 days. At enrollment and 21 and 42 days later, five lambs from each treatment were blood sampled, euthanased and samples of heart, liver, kidney and skeletal muscle (Longissimus Dorsi and Psoas Major) tissue were retained. Total Se concentration in whole blood and tissues was significantly (P < 0.001) higher in HSY lambs at all time points that had previously received long term exposure to high dietary concentrations of SY. The distribution of total Se and the proportions of total Se comprised as SeMet and SeCys differed between tissues, treatment and time points. Total Se was greatest in HSY liver and kidney (22.64 and 18.96 mg Se/kg DM, respectively) and SeCys comprised the greatest proportion of total Se. Conversely, cardiac and skeletal muscle (Longissimus Dorsi and Psoas Major) tissues had lower total Se concentration (10.80, 7.02 and 7.82 mg Se/kg DM, respectively) and SeMet was the predominant selenized amino acid. Rates of Se clearance in HSY liver (307 µg Se/day) and kidney (238 µg Se/day) were higher compared with HSY cardiac tissue (120 µg Se/day) and skeletal muscle (20 µg Se/day). In conclusion differences in Se clearance rates were different between tissue types, reflecting the relative metabolic activity of each tissue, and appear to be dependant upon the proportions of total Se comprised as either SeMet or SeCys.

Unification of the probe and singular sources methods for the inverse boundary value problem by the no-response test

In this article, we use the no-response test idea, introduced in Luke and Potthast (2003) and Potthast (Preprint) and the inverse obstacle problem, to identify the interface of the discontinuity of the coefficient gamma of the equation del (.) gamma(x)del + c(x) with piecewise regular gamma and bounded function c(x). We use infinitely many Cauchy data as measurement and give a reconstructive method to localize the interface. We will base this multiwave version of the no-response test on two different proofs. The first one contains a pointwise estimate as used by the singular sources method. The second one is built on an energy (or an integral) estimate which is the basis of the probe method. As a conclusion of this, the probe and the singular sources methods are equivalent regarding their convergence and the no-response test can be seen as a unified framework for these methods. As a further contribution, we provide a formula to reconstruct the values of the jump of gamma(x), x is an element of partial derivative D at the boundary. A second consequence of this formula is that the blow-up rate of the indicator functions of the probe and singular sources methods at the interface is given by the order of the singularity of the fundamental solution.

Control of framework stoichiometry in MeGaPO laumontites using 1-methylimidazole as structure-directing agent

A series of heterometal substituted gallium phosphates, (N2C4H7)(0.5+x)[Me0.5+xGa2.5-x(PO4)(3)] (Me = Mn, Fe, Co and Zn, x approximate to 0.25), has been synthesised under solvothermal conditions at 433 K in ethylene glycol using I-methylimidazole as a templating agent and their structures determined at 150 K using single-crystal X-ray diffraction. The compounds are isostructural, crystallising in the monoclinic space group C 2/c, with lattice parameters ca. 15 x 13 x 15 angstrom and beta = 112 degrees, and adopt the laumontite framework type (LAU). The incorporation of 1-methylimidazole cations into the one-dimensional pore systems of these materials is about three quarters the uptake value obtained previously for the less-bulky amine cations of imidazole and pyridine in other MeGaPO laumontites, which have the formula (TH)[MeGa2(PO4)(3)] (Me = Mn, Fe, Co and Zn; T = C5H5N and C3N2H4). The size, shape and charge of the amine clearly influence both the metal-phosphate framework stoichiometry (i.e. Me2+:Ga3+ ratio) and the framework charge. (C) 2007 Elsevier Inc. All rights reserved.

Higher oxides of chlorine: absorption cross-sections of Cl2O6 and Cl2O4, the decomposition of Cl2O6, and the reactions of OClO with O and O-3

The absorption cross-sections of Cl2O6 and Cl2O4 have been obtained using a fast flow reactor with a diode array spectrometer (DAS) detection system. The absorption cross-sections at the wavelengths of maximum absorption (lambda(max)) determined in this study are those of Cl2O6: (1.47 +/- 0.15) x 10(-17) cm(2) molecule(-1), at lambda(max) = 276 nm and T = 298 K; and Cl2O4: (9.0 +/- 2.0) x 10(-19) cm(2) molecule(-1), at lambda(max) = 234 nm and T = 298 K. Errors quoted are two standard deviations together with estimates of the systematic error. The shapes of the absorption spectra were obtained over the wavelength range 200-450 nm for Cl2O6 and 200-350 nm for Cl2O4, and were normalized to the absolute cross-sections obtained at lambda(max) for each oxide, and are presented at 1 nm intervals. These data are discussed in relation to previous measurements. The reaction of O with OCIO has been investigated with the objective of observing transient spectroscopic absorptions. A transient absorption was seen, and the possibility is explored of identifying the species with the elusive sym-ClO3 or ClO4, both of which have been characterized in matrices, but not in the gas-phase. The photolysis of OCIO was also re-examined, with emphasis being placed on the products of reaction. UV absorptions attributable to one of the isomers of the ClO dimer, chloryl chloride (ClClO2) were observed; some Cl2O4 was also found at long photolysis times, when much of the ClClO2 had itself been photolysed. We suggest that reports of Cl2O6 formation in previous studies could be a consequence of a mistaken identification. At low temperatures, the photolysis of OCIO leads to the formation of Cl2O3 as a result of the addition of the ClO primary product to OCIO. ClClO2 also appears to be one product of the reaction between O-3 and OCIO, especially when the reaction occurs under explosive conditions. We studied the kinetics of the non-explosive process using a stopped-flow technique, and suggest a value for the room-temperature rate coefficient of (4.6 +/- 0.9) x 10(-19) cm(3) molecule(-1) s(-1) (limit quoted is 2sigma random errors). The photochemical and thermal decomposition of Cl2O6 is described in this paper. For photolysis at k = 254 nm, the removal of Cl2O6 is not accompanied by the build up of any other strong absorber. The implications of the results are either that the photolysis of Cl2O6 produces Cl-2 directly, or that the initial photofragments are converted rapidly to Cl-2. In the thermal decomposition of Cl2O6, Cl2O4 was shown to be a product of reaction, although not necessarily the major one. The kinetics of decomposition were investigated using the stopped-flow technique. At relatively high [OCIO] present in the system, the decay kinetics obeyed a first-order law, with a limiting first-order rate coefficient of 0.002 s(-1). (C) 2004 Elsevier B.V. All rights reserved.

Oxidation of oleic acid at the air-water interface and its potential effects on cloud critical supersaturations

The oxidation of organic films on cloud condensation nuclei has the potential to affect climate and precipitation events. In this work we present a study of the oxidation of a monolayer of deuterated oleic acid (cis-9-octadecenoic acid) at the air-water interface by ozone to determine if oxidation removes the organic film or replaces it with a product film. A range of different aqueous sub-phases were studied. The surface excess of deuterated material was followed by neutron reflection whilst the surface pressure was followed using a Wilhelmy plate. The neutron reflection data reveal that approximately half the organic material remains at the air-water interface following the oxidation of oleic acid by ozone, thus cleavage of the double bond by ozone creates one surface active species and one species that partitions to the bulk (or gas) phase. The most probable products, produced with a yield of similar to(87 +/- 14)%, are nonanoic acid, which remains at the interface, and azelaic acid (nonanedioic acid), which dissolves into the bulk solution. We also report a surface bimolecular rate constant for the reaction between ozone and oleic acid of (7.3 +/- 0.9) x 10(-11) cm(2) molecule s(-1). The rate constant and product yield are not affected by the solution sub-phase. An uptake coefficient of ozone on the oleic acid monolayer of similar to 4 x 10(-6) is estimated from our results. A simple Kohler analysis demonstrates that the oxidation of oleic acid by ozone on an atmospheric aerosol will lower the critical supersaturation needed for cloud droplet formation. We calculate an atmospheric chemical lifetime of oleic acid of 1.3 hours, significantly longer than laboratory studies on pure oleic acid particles suggest, but more consistent with field studies reporting oleic acid present in aged atmospheric aerosol.

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.

Global attractivity in a recursive sequence

In this paper, we Study the invariant intervals, the globally attractivity of the two equilibrium points, and the oscillatory behavior of tile solutions of the difference equation x(n =) ax(n-1) - bx(n-2)/c + x(n-2), n = 1,2,......, where a, b. c > 0. (C) 2003 Elsevier Inc. All rights reserved.

Gas-phase reactions of NO3 and N2O5 with (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol

The night-time atmospheric chemistry of the biogenic volatile organic compounds (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these stress-induced plant emissions were measured using the discharge-flow technique. We employed off-axis continuous-wave cavity-enhanced absorption spectroscopy (CEAS) for the detection of NO3, which enabled us to work in excess of the hexenol compounds over NO3. The rate coefficients determined were (2.93 +/- 0.58) x 10(-13) cm(3) molecule(-1) s(-1), (2.67 +/- 0.42) x 10(-13) cm(3) molecule(-1) s(-1), (4.43 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1), (1.56 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1), and (1.30 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1) for (Z)-hex-4-en-1-ol, (Z)-hex-3en-1-ol, (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol. The rate coefficient for the reaction of NO3 with (Z)-hex-3-en-1-ol agrees with the single published determination of the rate coefficient using a relative method. The other rate coefficients have not been measured before and are compared to estimated values. Relative-rate studies were also performed, but required modification of the standard technique because N2O5 (used as the source of NO3) itself reacts with the hexenols. We used varying excesses of NO2 to determine simultaneously rate coefficients for reactions of NO3 and N2O5 with (E)-hex-3-en-1-ol of (5.2 +/- 1.8) x 10(-13) cm(3) molecule(-1) s(-1) and (3.1 +/- 2.3) x 10(-18) cm(3) molecule(-1) s(-1). Our new determinations suggest atmospheric lifetimes with respect to NO3-initiated oxidation of roughly 1-4 h for the hexenols, comparable with lifetimes estimated for the atmospheric degradation by OH and shorter lifetimes than for attack by O-3. Recent measurements of [N2O5] suggest that the gas-phase reactions of N2O5 with unsaturated alcohols will not be of importance under usual atmospheric conditions, but they certainly can be in laboratory systems when determining rate coefficients.