生物－热催化过渡带沉积成岩演化及其成烃作用研究

The biothermocatalytic transitional zone gas is a new type of natural gas genetic theory, and also an clean, effective and high quality energy with shallow burial depth, wide distribution and few investment. Meanwhile, this puts biothermocatalytic transitional zone gas in important position to the energy resource and it is a challenging front study project. This paper introduces the concept, the present situation of study and developmental trend about biothermocatalytic transitional zone gas in detail. Then by using heat simulating of source rocks and catalysis mechanism analysis in the laboratory and studying structural evolution, sedimentation, diagenesis and the conditions of accumulation formation and so on, this paper also discusses catalytic mechanism and evolutionary model of the biothermocatalytic transitional zone gas formation, and establishes the methods of appraisal parameter and resources prediction about the biothermocatalytic transitional zone gas. At last, it shows that geochemical characteristics and differentiated mark of the biothermocatalytic transitional zone gas, and perfect natural gas genetic theory, and points out the conditions of accumulation formation, distribution characteristics and potential distribution region on the biothermocatalytic transitional zone gas m China. The paper mainly focuses on the formation mechanism and the resources potential about the biothermocatalytic transitional zone gas. Based on filed work, it is attached importance to a combination of macroscopic and microcosmic analysis, and the firsthand data are obtained to build up framework and model of the study by applying geologic theory. Based on sedimentary structure, it is expounded that structural actions have an effect on filling space and developmental cource of sediments and evolution of source rocks. Carried out sedimentary environment, sequence stratigraphy, sedimentary system and diagenesis and so on, it is concluded that diagenesis influences developmental evolution of source rocks, and basic geologic conditions of the biothermocatalytic transitional zone gas. Applying experiment simulating and catalytic simulating as well as chemical analysis, catalytic mechanism of clay minerals is discussed. Combined diagenecic dynamics with isotope fractionation dynamics, it is established that basis and method of resource appraisal about the biothermocatalytic transitional zone gas. All these results effectively assess and predict oil&gas resources about the biothermocatalytic transitional zone gas-bearing typical basin in China. I read more than 170 volumes on the biothermocatalytic transitional zone gas and complete the dissertation' summary with some 2.4 ten thousand words, draw up study contents in some detail and set up feasible experimental method and technologic course. 160 pieces of samples are obtained in oilfield such as Liaohe, Shengli, Dagang and Subei and so on, some 86 natural gas samples and more than 30 crude oil samples. Core profiles about 12 wells were observed and some 300 geologic photos were taken. Six papers were published in the center academic journal at home and abroad. Collected samples were analysised more than 1000 times, at last I complete this dissertation with more than 8 ten thousand words, and with 40 figures and 4 plates. According to these studies, it is concluded the following results and understandings. 1. The study indicates structural evolution and action of sedimentary basin influence and control the formation and accumulation the biothermocatalytic transitional zone gas. Then, the structural action can not only control accommodation space of sediments and the origin, migration and accumulation of hydrocarbon matters, but also can supply the origin of energy for hygrocarbon matters foramtion. 2. Sedimentary environments of the biothermocatalytic transitional zone gas are lake, river and swamp delta- alluvial fan sedimentary systems, having a warm, hot and humid climate. Fluctuation of lake level is from low to high., frequency, and piling rate of sedimentary center is high, which reflect a stable depression and rapidly filling sedimentary course, then resulting in source rocks with organic matter. 3. The paper perfects the natural gas genetic theory which is compound and continuous. It expounds the biothermocatalytic transitional zone gas is a special gas formation stage in continuous evolutionary sequence of organic matter, whose exogenic force is temperture and catalysis of clay minerals, at the same time, having decarbxylation, deamination and so on. 4. The methodology is established which is a combination of SEM, TEM and Engery spectrum analysis to identify microstructure of crystal morphology about clay minerals. Using differential thermal-chromatographic analysis, it can understand that hydrocarbon formation potential of different typies kerogens and catalytic method of all kinds of mineral matrix, and improve the surface acidity technology of clay minerals measured by the pyridine analytic method. 5. The experiments confirm catalysis of clay minerals to organic matter hygrocarbon formation. At low temperature (<300 ℃), there is mainly catalysis of montmorillonite, which can improve 2-3 times about produced gas of organic matters and the pyrolyzed temperature decreased 50 ℃; while at the high temperature, there is mainly catalysis of illite which can improve more than 2 times about produced gas of organic matters. 6. It is established the function relationship between organic matter (reactant) concentration and temperature, pressure, time, water and so on, that is C=f (D, t). Using Rali isotope fractionation effect to get methane isotope fractionation formula. According to the relationship between isotope fractionation of diagenesis and depth, and combined with sedimentary rate of the region, it is estimated that relict gas of the biothermocatalytic transitional zone gas in the representative basin. 7. It is revealed that hydrocarbon formation mechanism of the biothermocatalytic transitional zone gas is mainly from montmorillonite to mixed minerals during diagenesis. In interlayer, a lot of Al~(3+) substitute for Si~(4+), resulting in a imbalance between surface charge and interlayer charge of clay minerals and the occurrence of the Lewis and Bronsted acid sites, which promote to form the carbon cation. The cation can form alkene or small carbon cation. 8. It is addressed the comprehensive identification mark of the biothermo - catalytic transitional zone gas. In the temproal-spatial' distribution, its source rocks is mainly Palaeogene, secondly Cretaceous and Jurassic of Mesozoic, Triassic, having mudy rocks and coal-rich, their organic carbon being 0.2% and 0.4% respectively. The vitrinite reflection factor in source rocks Ro is 0.3-0.65%, a few up to 0.2%. The burial depth is 1000-3000m, being characterized by emerge of itself, reservoir of itself, shallow burial depth. In the transitional zone, from shallow to deep, contents of montmorillonites are progressively reduced while contents of illites increasing. Under SEM, it is observed that montmorillonites change into illite.s, firstly being mixed illite/ montmorillonite with burr-like, then itlite with silk-like. Carbon isotope of methane in the biothermocatatytic transitional zone gas , namely δ~(13)C_1-45‰- -60 ‰. 9. From the evolutionary sequence of time, distribution of the biothermocatalytic transitional zone gas is mainly oil&gas bearing basin in the Mesozoic-Neozoic Era. From the distribution region, it is mainly eastern stuctural active region and three large depressions in Bohaiwang basin. But most of them are located in evolutionary stage of the transitional zone, having the better relationship between produced, reservoir and seal layers, which is favorable about forming the biothermocatalytic transitional zone gas reservoir, and finding large gas (oil) field.

大城市内部商业环境满意度评价与消费区位决策研究-以北京市西城区和海淀区为例

Since 1990s, commercial conditions in China including commercial environment, retail types, scale of retail enterprises, spatial structure of retail and shopping decision making factors have changed. In order to keep up with these changes, commercial geography should set up new perspectives, theories and methods to analyze its internal mechanism and changing rules, and thus provide reasonable and practical scientific basis to commercial planning, location decision of retail enterprises and commercial environment construction. Taking Xicheng and Haidian District of Beijing as research case, which is a sector region from city center to rural region, this paper selects 12 commercial centers as most important study objects of this sector. This paper mainly makes use of the methods of Modeling, Pearson Bivaiiate Correlations Analysis, Factor Analysis and Logit model. Based on 1300 questionnaires and fieldwork, this paper focuses on modeling of Consumer Satisfaction of Commercial Environment (CSCE), evaluation of commercial environment and driving factors of consumers' shopping location decision. Firstly, this paper discusses the development of commercial geography and commercial environment evaluation, the new characteristics and trends of commercial development in Beijing and physical commercial environment of Xicheng and Haidian District of Beijing from chapter 1 to chapter 4. Secondly, this paper summarizes characteristics of residents' shopping behavior in chapter 5. Thirdly, this paper sets up an evaluative model of CSCE, and analyzes consumer satisfaction indexes of commercial environment and their spatial features in chapter 6. Fourthly, this paper infers how residents' attributes and shopping behaviors affect their preferences of shopping location and what are residents' shopping location decisions and their influencing factors in chapter 7. Fifthly, this paper constructs a significant index model and a pyramidal framework of CSCE, and further analyzes the diversity and competitive advantage of commercial environment in chapter 8. Finally, some conclusions are drawn as follows: 1. Characteristics of residents' shopping behavior mostly embody residents' time distance preference, commodity consumption preference, shopping time distribution and shopping activity characteristics. The important factors that influence shopping location choice of residents are distance, transportation, commodity price, commodity types and commodity quality. However, the important factors, which influence shopping location re-choice of residents, are commodity price, commodity quality, commodity types and transportation. 2. CSCE indexes of 12 commercial centers show us significant spatial characteristics, such as spatial differences of "Center-fringe region", spatial characteristics of axes, spatial diversity of ring roads and so on. 3. Influencing factors including factor endowments, relative establishment factor and location and transportation factor of commercial environment are of importance for CSCE. 4. Logit model 1 indicates that shopping behavior of residents is significantly and positively related to working in high-tech companies, high income and by car and positively related to high school diploma, by bus and subway. 5. Logit model 2 indicates that residents' shopping location decision is significantly and positively related to leisure establishment and relative restaurant and entertainment establishment and negatively related to commercial location, commodity price, service quality, parking site. 6. The significant index model and the pyramidal framework of CSCE indicate competitive advantages are crucial to attractive capability of commercial center, and competitive weakness limits development of commercial centers, in particular the weakness of service quality and parking site now is the chief factors restricting development of commercial centers

Novos sistemas terapêuticos para administração nasal de fármacos

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

An Information Theoretic Framework for Field Monitoring Using Autonomously Mobile Sensors

We consider a mobile sensor network monitoring a spatio-temporal field. Given limited cache sizes at the sensor nodes, the goal is to develop a distributed cache management algorithm to efficiently answer queries with a known probability distribution over the spatial dimension. First, we propose a novel distributed information theoretic approach in which the nodes locally update their caches based on full knowledge of the space-time distribution of the monitored phenomenon. At each time instant, local decisions are made at the mobile nodes concerning which samples to keep and whether or not a new sample should be acquired at the current location. These decisions account for minimizing an entropic utility function that captures the average amount of uncertainty in queries given the probability distribution of query locations. Second, we propose a different correlation-based technique, which only requires knowledge of the second-order statistics, thus relaxing the stringent constraint of having a priori knowledge of the query distribution, while significantly reducing the computational overhead. It is shown that the proposed approaches considerably improve the average field estimation error by maintaining efficient cache content. It is further shown that the correlation-based technique is robust to model mismatch in case of imperfect knowledge of the underlying generative correlation structure.

Antisense Gene Silencing and Bacteriophages as Novel Disinfection Processes for Engineered Systems

The growth and proliferation of invasive bacteria in engineered systems is an ongoing problem. While there are a variety of physical and chemical processes to remove and inactivate bacterial pathogens, there are many situations in which these tools are no longer effective or appropriate for the treatment of a microbial target. For example, certain strains of bacteria are becoming resistant to commonly used disinfectants, such as chlorine and UV. Additionally, the overuse of antibiotics has contributed to the spread of antibiotic resistance, and there is concern that wastewater treatment processes are contributing to the spread of antibiotic resistant bacteria.

Due to the continually evolving nature of bacteria, it is difficult to develop methods for universal bacterial control in a wide range of engineered systems, as many of our treatment processes are static in nature. Still, invasive bacteria are present in many natural and engineered systems, where the application of broad acting disinfectants is impractical, because their use may inhibit the original desired bioprocesses. Therefore, to better control the growth of treatment resistant bacteria and to address limitations with the current disinfection processes, novel tools that are both specific and adaptable need to be developed and characterized.

In this dissertation, two possible biological disinfection processes were investigated for use in controlling invasive bacteria in engineered systems. First, antisense gene silencing, which is the specific use of oligonucleotides to silence gene expression, was investigated. This work was followed by the investigation of bacteriophages (phages), which are viruses that are specific to bacteria, in engineered systems.


For the antisense gene silencing work, a computational approach was used to quantify the number of off-targets and to determine the effects of off-targets in prokaryotic organisms. For the organisms of Escherichia coli K-12 MG1655 and Mycobacterium tuberculosis H37Rv the mean number of off-targets was found to be 15.0 + 13.2 and 38.2 + 61.4, respectively, which results in a reduction of greater than 90% of the effective oligonucleotide concentration. It was also demonstrated that there was a high variability in the number of off-targets over the length of a gene, but that on average, there was no general gene location that could be targeted to reduce off-targets. Therefore, this analysis needs to be performed for each gene in question. It was also demonstrated that the thermodynamic binding energy between the oligonucleotide and the mRNA accounted for 83% of the variation in the silencing efficiency, compared to the number of off-targets, which explained 43% of the variance of the silencing efficiency. This suggests that optimizing thermodynamic parameters must be prioritized over minimizing the number of off-targets. In conclusion for the antisense work, these results suggest that off-target hybrids can account for a greater than 90% reduction in the concentration of the silencing oligonucleotides, and that the effective concentration can be increased through the rational design of silencing targets by minimizing off-target hybrids.

Regarding the work with phages, the disinfection rates of bacteria in the presence of phages was determined. The disinfection rates of E. coli K12 MG1655 in the presence of coliphage Ec2 ranged up to 2 h-1, and were dependent on both the initial phage and bacterial concentrations. Increasing initial phage concentrations resulted in increasing disinfection rates, and generally, increasing initial bacterial concentrations resulted in increasing disinfection rates. However, disinfection rates were found to plateau at higher bacterial and phage concentrations. A multiple linear regression model was used to predict the disinfection rates as a function of the initial phage and bacterial concentrations, and this model was able to explain 93% of the variance in the disinfection rates. The disinfection rates were also modeled with a particle aggregation model. The results from these model simulations suggested that at lower phage and bacterial concentrations there are not enough collisions to support active disinfection rates, which therefore, limits the conditions and systems where phage based bacterial disinfection is possible. Additionally, the particle aggregation model over predicted the disinfection rates at higher phage and bacterial concentrations of 108 PFU/mL and 108 CFU/mL, suggesting other interactions were occurring at these higher concentrations. Overall, this work highlights the need for the development of alternative models to more accurately describe the dynamics of this system at a variety of phage and bacterial concentrations. Finally, the minimum required hydraulic residence time was calculated for a continuous stirred-tank reactor and a plug flow reactor (PFR) as a function of both the initial phage and bacterial concentrations, which suggested that phage treatment in a PFR is theoretically possible.

In addition to determining disinfection rates, the long-term bacterial growth inhibition potential was determined for a variety of phages with both Gram-negative and Gram-positive bacteria. It was determined, that on average, phages can be used to inhibit bacterial growth for up to 24 h, and that this effect was concentration dependent for various phages at specific time points. Additionally, it was found that a phage cocktail was no more effective at inhibiting bacterial growth over the long-term than the best performing phage in isolation.

Finally, for an industrial application, the use of phages to inhibit invasive Lactobacilli in ethanol fermentations was investigated. It was demonstrated that phage 8014-B2 can achieve a greater than 3-log inactivation of Lactobacillus plantarum during a 48 h fermentation. Additionally, it was shown that phages can be used to protect final product yields and maintain yeast viability. Through modeling the fermentation system with differential equations it was determined that there was a 10 h window in the beginning of the fermentation run, where the addition of phages can be used to protect final product yields, and after 20 h no additional benefit of the phage addition was observed.

In conclusion, this dissertation improved the current methods for designing antisense gene silencing targets for prokaryotic organisms, and characterized phages from an engineering perspective. First, the current design strategy for antisense targets in prokaryotic organisms was improved through the development of an algorithm that minimized the number of off-targets. For the phage work, a framework was developed to predict the disinfection rates in terms of the initial phage and bacterial concentrations. In addition, the long-term bacterial growth inhibition potential of multiple phages was determined for several bacteria. In regard to the phage application, phages were shown to protect both final product yields and yeast concentrations during fermentation. Taken together, this work suggests that the rational design of phage treatment is possible and further work is needed to expand on this foundation.

Decadal changes in climate and ecosystems in the North Atlantic Ocean and adjacent seas

Climate change is unambiguous and its effects are clearly detected in all functional units of the Earth system. This study presents new analyses of sea-surface temperature changes and show that climate change is affecting ecosystems of the North Atlantic. Changes are seen from phytoplankton to zooplankton to fish and are modifying the dominance of species and the structure, the diversity and the functioning of marine ecosystems. Changes also range from phenological to biogeographical shifts and have involved in some regions of the Atlantic abrupt ecosystem shifts. These alterations reflect a response of pelagic ecosystems to a warmer temperature regime. Mechanisms are complex because they are nonlinear exhibiting tipping points and varying in space and time. Sensitivity of organisms to temperature changes is high, implicating that a small temperature modification can have sustained ecosystem effects. Implications of these changes for biogeochemical cycles are discussed. Two observed changes detected in the North Sea that could have opposite effects on carbon cycle are discussed. Increase in phytoplankton, as inferred from the phytoplankton colour index derived from the Continuous Plankton Recorder (CPR) survey, has been detected in the North Sea. This pattern has been accompanied by a reduction in the abundance of the herbivorous species Calanus finmarchicus. This might have reduced the grazing pressure and increase diatomaceous ‘fluff’, therefore carbon export in the North Sea. Therefore, it could be argued that the biological carbon pump might increase in this region with sea warming. In the meantime, however, the mean size of organisms (calanoid copepods) has dropped. Such changes have implications for the turnover time of biogenic carbon in plankton organisms and the mean residence time of particulate carbon they produce. The system characterising the warmer period is more based on recycling and less on export. The increase in the minimum turnover time indicates an increase in the ecosystem metabolism, which can be considered as a response of the pelagic ecosystems to climate warming. This phenomenon could reduce carbon export. These two opposite patterns of change are examples of the diversity of mechanisms and pathways the ecosystems may exhibit with climate change. Oversimplification of current biogeochemical models, often due to lack of data and biological understanding, could lead to wrong projection on the direction ecosystems and therefore some biogeochemical cycles might take in a warmer world.

Mesoscale fronts as foraging habitats: composite front mapping reveals oceanographic drivers of habitat use for a pelagic seabird

The oceanographic drivers of marine vertebrate habitat use are poorly understood yet fundamental to our knowledge of marine ecosystem functioning. Here, we use composite front mapping and high-resolution GPS tracking to determine the significance of mesoscale oceanographic fronts as physical drivers of foraging habitat selection in northern gannets Morus bassanus. We tracked 66 breeding gannets from a Celtic Sea colony over 2 years and used residence time to identify area-restricted search (ARS) behaviour. Composite front maps identified thermal and chlorophyll-a mesoscale fronts at two different temporal scales—(i) contemporaneous fronts and (ii) seasonally persistent frontal zones. Using generalized additive models (GAMs), with generalized estimating equations (GEE-GAMs) to account for serial autocorrelation in tracking data, we found that gannets do not adjust their behaviour in response to contemporaneous fronts. However, ARS was more likely to occur within spatially predictable, seasonally persistent frontal zones (GAMs). Our results provide proof of concept that composite front mapping is a useful tool for studying the influence of oceanographic features on animal movements. Moreover, we highlight that frontal persistence is a crucial element of the formation of pelagic foraging hotspots for mobile marine vertebrates.

Freeze-dried, mucoadhesive system for vaginal delivery of the HIV microbicide, dapivirine: Optimisation by an artificial neural network

Dapivirine mucoadhesive gels and freeze-dried tablets were prepared using a 3 x 3 x 2 factorial design. An artificial neural network (ANN) with multi-layer perception was used to investigate the effect of hydroxypropyl-methylcellulose (HPMC): polyvinylpyrrolidone (PVP) ratio (XI), mucoadhesive concentration (X2) and delivery system (gel or freeze-dried mucoadhesive tablet, X3) on response variables; cumulative release of dapivirine at 24 h (Q(24)), mucoadhesive force (F-max) and zero-rate viscosity. Optimisation was performed by minimising the error between the experimental and predicted values of responses by ANN. The method was validated using check point analysis by preparing six formulations of gels and their corresponding freeze-dried tablets randomly selected from within the design space of contour plots. Experimental and predicted values of response variables were not significantly different (p > 0.05, two-sided paired t-test). For gels, Q(24) values were higher than their corresponding freeze-dried tablets. F-max values for freeze-dried tablets were significantly different (2-4 times greater, p > 0.05, two-sided paired t-test) compared to equivalent gets. Freeze-dried tablets having lower values for X1 and higher values for X2 components offered the best compromise between effective dapivirine release, mucoadhesion and viscosity such that increased vaginal residence time was likely to be achieved. (C) 2009 Elsevier B.V. All rights reserved.

Phase-Transfer Catalysis in Segmented Flow in a Microchannel: Fluidic Control of Selectivity and Productivity

Precise control over the interfacial area of aqueous and organic slugs in segmented flow in a microchannel reactor provides an attractive means to optimize the yield and productivity of a phase-transfer-catalyzed reaction. Herein, we report the selective alkylation of phenylacetonitrile to the monoalkylated product in a microchannel of 250-mu m internal diameter operated in a continuous and solvent-free manner in the slug-flow regime. The conversion of phenylacetonitrile increased from 40% to 99% as a result of a 97% larger slug surface-to-volume ratio when the volumetric aqueous-to-organic phase flow ratio was raised from 1.0 to 6.1 at the same residence time. The larger surface-to-volume ratio significantly promoted catalyst phase transfer but decreased selectivity because of the simultaneous increase of the rate of the consecutive reaction to the dialkylated product. There exists all Optimum flow ratio with a maximum productivity. Conversion and selectivity in the microchannel reactor were both found to be significantly larger than in a stirred reactor.

A kinetic study of the liquid-phase hydrogenation of citral on Au/TiO2 and Pt-Sn/TiO2 thin films in capillary microreactors

The kinetics of the liquid-phase hydrogenation of citral (3,7-dimethyl-2,6-octadienal) on Au/TiO2 and Pt-Sn/TiO2 thin films was studied in the temperature range 313-353 K and citral concentrations of 0.25-10.0 mol m(-3). The thin films were deposited onto the inner walls of silica capillaries with internal diameter of 250 mu m. First-order dependence on hydrogen pressure and near zero order dependence on citral concentration were observed for the initial rate of citral hydrogenation over the Pt-Sn/TiO2 and Au/TiO2 thin films. The Au/TiO2 catalyst prevents citronellal formation. The highest yield of unsaturated alcohols was obtained on the Pt-Sn/TiO2 film at a reaction temperature of 343 K, liquid residence time of 30 min and a citral conversion of 99%. (C) 2011 Elsevier B.V. All rights reserved.

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

On the universality of a one-dimensional model of a rice pile

A one-dimensional model of a rice pile is numerically studied for different driving mechanisms and different levels of medium disorder. The universality of the scaling exponents for the transit time distribution and avalanche size distribution is discussed. (C) 1997 Published by Elsevier Science B.V.

Hydrodynamic cavitation in micro channels with channel sizes of 100 and 750 micrometers

Decreasing the constriction size and residence time in hydrodynamic cavitation is predicted to give increased hot spot temperatures at bubble collapse and increased radical formation rate. Cavitation in a 100 x 100 mu m(2) rectangular micro channel and in a circular 750 mu m diameter milli channel has been investigated with computational fluid dynamics software and with imaging and radical production experiments. No radical production has been measured in the micro channel. This is probably because there is no spherically symmetrical collapse of the gas pockets in the channel which yield high hot spot temperatures. The potassium iodide oxidation yield in the presence of chlorohydrocarbons in the milli channel of up to 60 nM min(-1) is comparable to values reported on hydrodynamic cavitation in literature, but lower than values for ultrasonic cavitation. These small constrictions can create high apparent cavitation collapse frequencies.

Using temporal analysis of products and flux response technology to determine diffusion coefficients in catalytic monoliths

The importance of accurately measuring gas diffusivity in porous materials has led to a number of methods being developed. In this study the Temporal Analysis of Products (TAP) reactor and Flux Response Technology (FRT) have been used to examine the diffusivity in the washcoat supported on cordierite monoliths. Herein, the molecular diffusion of propane within four monoliths with differently prepared alumina/CeZrOx washcoats was investigated as a function of temperature. Moment-based analysis of the observed TAP responses led to the calculation of the apparent intermediate gas constant, Kp, that characterises adsorption into the mesoporous network and apparent time delay, tapp, that characterises residence time in the mesoporous network. Additionally, FRT has been successfully adapted as an extensive in situ perturbation technique in measuring intraphase diffusion coefficients in the washcoats of the same four monolith samples. The diffusion coefficients obtained by moment-based analysis of TAP responses are larger than the coefficients determined by zero length column (ZLC) analysis of flux response profiles with measured values of the same monolith samples between 20 and 100 °C ranging from 2–5×10^-9 m² s^-1 to 4–8×10^-10 m² s^-1, respectively. The TAP and FRT data, therefore, provide a range of the lower and upper limits of diffusivity, respectively. The reported activation energies and diffusivities clearly correlate with the difference in the washcoat structure of different monolith samples.

Methylation using dimethylcarbonate catalysed by ionic liquids under continuous flow conditions

The ionic liquid, tributylmethylammonium methylcarbonate, has been employed as a catalytic base for clean N-methylation of indole with dimethylcarbonate. The reaction conditions were optimised under microwave heating to give 100% conversion and 100% selectivity to N-methylindole, and subsequently transferred to a high temperature/high pressure (285 degrees C/150 bar) continuous flow process using a short (3 min) residence time and 2 mol% of the catalyst to efficiently methylate a variety of different amines, phenols, thiophenols and carboxylic acid substrates. The extremely short residence times, versatility, and high selectivity have significant implications for the synthesis of a wide range of pharmaceutical intermediates, as high product throughputs can be obtained via this scalable continuous flow protocol. It has also been shown that the ionic liquid can be generated in situ from tributylamine, which has the net effect of transforming an ineffective stoichiometric base into a highly efficient catalyst for this broad class of reactions.