Formation and surface exchange of nitrous acid

Die salpetrige Säure (HONO) ist eine der reaktiven Stickstoffkomponenten der Atmosphäre und Pedosphäre. Die genauen Bildungswege von HONO, sowie der gegenseitige Austausch von HONO zwischen Atmosphäre und Pedosphäre sind noch nicht vollständig aufgedeckt. Bei der HONO-Photolyse entsteht das Hydroxylradikal (OH) und Stickstoffmonooxid (NO), was die Bedeutsamkeit von HONO für die atmosphärische Photochemie widerspiegelt.rnUm die genannte Bildung von HONO im Boden und dessen anschließenden Austausch mit der Atmosphäre zu untersuchen, wurden Messungen von Bodenproben mit dynamischen Kammern durchgeführt. Im Labor gemessene Emissionsflüsse von Wasser, NO und HONO zeigen, dass die Emission von HONO in vergleichbarem Umfang und im gleichen Bodenfeuchtebereich wie die für NO (von 6.5 bis 56.0 % WHC) stattfindet. Die Höhe der HONO-Emissionsflüsse bei neutralen bis basischen pH-Werten und die Aktivierungsenergie der HONO-Emissionsflüsse führen zu der Annahme, dass die mikrobielle Nitrifikation die Hauptquelle für die HONO-Emission darstellt. Inhibierungsexperimente mit einer Bodenprobe und die Messung einer Reinkultur von Nitrosomonas europaea bestärkten diese Theorie. Als Schlussfolgerung wurde das konzeptionelle Model der Bodenemission verschiedener Stickstoffkomponenten in Abhängigkeit von dem Wasserhaushalt des Bodens für HONO erweitert.rnIn einem weiteren Versuch wurde zum Spülen der dynamischen Kammer Luft mit erhöhtem Mischungsverhältnis von HONO verwendet. Die Messung einer hervorragend charakterisierten Bodenprobe zeigte bidirektionale Flüsse von HONO. Somit können Böden nicht nur als HONO-Quelle, sondern auch je nach Bedingungen als effektive Senke dienen. rnAußerdem konnte gezeigt werden, dass das Verhältnis von HONO- zu NO-Emissionen mit dem pH-Wert des Bodens korreliert. Grund könnte die erhöhte Reaktivität von HONO bei niedrigem pH-Wert und die längere Aufenthaltsdauer von HONO verursacht durch reduzierte Gasdiffusion im Bodenporenraum sein, da ein niedriger pH-Wert mit erhöhter Bodenfeuchte am Maximum der Emission einhergeht. Es konnte gezeigt werden, dass die effektive Diffusion von Gasen im Bodenporenraum und die effektive Diffusion von Ionen in der Bodenlösung die HONO-Produktion und den Austausch von HONO mit der Atmosphäre begrenzen. rnErgänzend zu den Messungen im Labor wurde HONO während der Messkampagne HUMPPA-COPEC 2010 im borealen Nadelwald simultan in der Höhe von 1 m über dem Boden und 2 bis 3 m über dem Blätterdach gemessen. Die Budgetberechnungen für HONO zeigen, dass für HONO sämtliche bekannte Quellen und Senken in Bezug auf die übermächtige HONO-Photolyserate tagsüber vernachlässigbar sind (< 20%). Weder Bodenemissionen von HONO, noch die Photolyse von an Oberflächen adsorbierter Salpetersäure können die fehlende Quelle erklären. Die lichtinduzierte Reduktion von Stickstoffdioxid (NO2) an Oberflächen konnte nicht ausgeschlossen werden. Es zeigte sich jedoch, dass die fehlende Quelle stärker mit der HONO-Photolyserate korreliert als mit der entsprechenden Photolysefrequenz, die proportional zur Photolysefrequenz von NO2 ist. Somit lässt sich schlussfolgern, dass entweder die Photolyserate von HONO überschätzt wird oder dass immer noch eine unbekannte, HONO-Quelle existiert, die mit der Photolyserate sehr stark korreliert. rn rn

Galactic fountain flows in high-resolution hydrodynamical simulations of galaxy disks

Feedback from the most massive components of a young stellar cluster deeply affects the surrounding ISM driving an expanding over-pressured hot gas cavity in it. In spiral galaxies these structures may have sufficient energy to break the disk and eject large amount of material into the halo. The cycling of this gas, which eventually will fall back onto the disk, is known as galactic fountains. We aim at better understanding the dynamics of such fountain flow in a Galactic context, frame the problem in a more dynamic environment possibly learning about its connection and regulation to the local driving mechanism and understand its role as a metal diffusion channel. The interaction of the fountain with a hot corona is hereby analyzed, trying to understand the properties and evolution of the extraplanar material. We perform high resolution hydrodynamical simulations with the moving-mesh code AREPO to model the multi-phase ISM of a Milky Way type galaxy. A non-equilibrium chemical network is included to self consistently follow the evolution of the main coolants of the ISM. Spiral arm perturbations in the potential are considered so that large molecular gas structures are able to dynamically form here, self shielded from the interstellar radiation field. We model the effect of SN feedback from a new-born stellar cluster inside such a giant molecular cloud, as the driving force of the fountain. Passive Lagrangian tracer particles are used in conjunction to the SN energy deposition to model and study diffusion of freshly synthesized metals. We find that both interactions with hot coronal gas and local ISM properties and motions are equally important in shaping the fountain. We notice a bimodal morphology where most of the ejected gas is in a cold $10^4$ K clumpy state while the majority of the affected volume is occupied by a hot diffuse medium. While only about 20\% of the produced metals stay local, most of them quickly diffuse through this hot regime to great scales.

Mobile goes global: The effect of cell phones on economic growth and development

This study investigates the effect of cell phones on economic development and growth by performing an econometric analysis using data from the International Telecommunications Union and the Penn World Table. It discusses the various ways cell phones can make markets more efficient and how the diffusion of information andknowledge plays into development. Several approaches (OLS, Fixed Effects, 2SLS) were used to test over 20 econometric models. Overall, the mobile cellular subscriptions rate was found to have a positive and significant impact on countries’ level of real per capitaGDP and GDP growth rate. Furthermore, the study provides policy implications for the use of technology to promote global growth.

Au@Hg nanoalloy formation through direct amalgamation: Structural, spectroscopic, and computational evidence for slow nanoscale diffusion

Dynamic core-shell nanoparticles have received increasing attention in recent years. This paper presents a detailed study of Au-Hg nanoalloys, whose composing elements show a large difference in cohesive energy. A simple method to prepare Au@Hg particles with precise control over the composition up to 15 atom% mercury is introduced, based on reacting a citrate stabilized gold sol with elemental mercury. Transmission electron microscopy shows an increase of particle size with increasing mercury content and, together with X-ray powder diffraction, points towards the presence of a core-shell structure with a gold core surrounded by an Au-Hg solid solution layer. The amalgamation process is described by pseudo-zero-order reaction kinetics, which indicates slow dissolution of mercury in water as the rate determining step, followed by fast scavenging by nanoparticles in solution. Once adsorbed at the surface, slow diffusion of Hg into the particle lattice occurs, to a depth of ca. 3 nm, independent of Hg concentration. Discrete dipole approximation calculations relate the UV-vis spectra to the microscopic details of the nanoalloy structure. Segregation energies and metal distribution in the nanoalloys were modeled by density functional theory calculations. The results indicate slow metal interdiffusion at the nanoscale, which has important implications for synthetic methods aimed at core-shell particles.

Contrast media enhancement of intracranial lesions in magnetic resonance imaging does not reflect histopathologic findings consistently

Certain magnetic resonance (MR) enhancement patterns are often considered to be associated with a specific diagnosis but experience shows that this association is not always consistent. Therefore, it is not clear how reliably contrast enhancement patterns correlate with specific tissue changes. We investigated the detailed histomorphologic findings of intracranial lesions in relation to Gadodiamide contrast enhancement in 55 lesions from 55 patients, nine cats, and 46 dogs. Lesions were divided into areas according to their contrast enhancement; therefore 81 areas resulted from the 55 lesions which were directly compared with histopathology. In 40 of 55 lesions (73%), the histomorphologic features explained the contrast enhancement pattern. In particular, vascular proliferation and dilated vessels occurred significantly more often in areas with enhancement than in areas without enhancement (P = 0.044). In 15 lesions, there was no association between MR images and histologic findings. In particular, contrast enhancement was found within necrotic areas (10 areas) and ring enhancement was seen in lesions without central necrosis (five lesions). These findings imply that necrosis cannot be differentiated reliably from viable tissue based on postcontrast images. Diffusion of contrast medium within lesions and time delays after contrast medium administration probably play important roles in the presence and patterns of contrast enhancement. Thus, histologic features of lesions cannot be predicted solely by contrast enhancement patterns.

High interstitial fluid pressure is associated with low tumour penetration of diagnostic monoclonal antibodies applied for molecular imaging purposes

The human epithelial cell adhesion molecule (EpCAM) is highly expressed in a variety of clinical tumour entities. Although an antibody against EpCAM has successfully been used as an adjuvant therapy in colon cancer, this therapy has never gained wide-spread use. We have therefore investigated the possibilities and limitations for EpCAM as possible molecular imaging target using a panel of preclinical cancer models. Twelve human cancer cell lines representing six tumour entities were tested for their EpCAM expression by qPCR, flow cytometry analysis and immunocytochemistry. In addition, EpCAM expression was analyzed in vivo in xenograft models for tumours derived from these cells. Except for melanoma, all cell lines expressed EpCAM mRNA and protein when grown in vitro. Although they exhibited different mRNA levels, all cell lines showed similar EpCAM protein levels upon detection with monoclonal antibodies. When grown in vivo, the EpCAM expression was unaffected compared to in vitro except for the pancreatic carcinoma cell line 5072 which lost its EpCAM expression in vivo. Intravenously applied radio-labelled anti EpCAM MOC31 antibody was enriched in HT29 primary tumour xenografts indicating that EpCAM binding sites are accessible in vivo. However, bound antibody could only be immunohistochemically detected in the vicinity of perfused blood vessels. Investigation of the fine structure of the HT29 tumour blood vessels showed that they were immature and prone for higher fluid flux into the interstitial space. Consistent with this hypothesis, a higher interstitial fluid pressure of about 12 mbar was measured in the HT29 primary tumour via "wick-in-needle" technique which could explain the limited diffusion of the antibody into the tumour observed by immunohistochemistry.

Distribution of radiodense contrast medium after perineural injection of the palmar and palmar metacarpal nerves (low 4-point nerve block): an in vivo and ex vivo study in horses

REASONS FOR PERFORMING STUDY: Evidence-based information is limited on distribution of local anaesthetic solution following perineural analgesia of the palmar (Pa) and palmar metacarpal (PaM) nerves in the distal aspect of the metacarpal (Mc) region ('low 4-point nerve block'). OBJECTIVES: To demonstrate the potential distribution of local anaesthetic solution after a low 4-point nerve block using a radiographic contrast model. METHODS: A radiodense contrast medium was injected subcutaneously over the medial or the lateral Pa nerve at the junction of the proximal three-quarters and distal quarter of the Mc region (Pa injection) and over the ipsilateral PaM nerve immediately distal to the distal aspect of the second or fourth Mc bones (PaM injection) in both forelimbs of 10 mature horses free from lameness. Radiographs were obtained 0, 10 and 20 min after injection and analysed subjectively and objectively. Methylene blue and a radiodense contrast medium were injected in 20 cadaver limbs using the same techniques. Radiographs were obtained and the limbs dissected. RESULTS: After 31/40 (77.5%) Pa injections, the pattern of the contrast medium suggested distribution in the neurovascular bundle. There was significant proximal diffusion with time, but the main contrast medium patch never progressed proximal to the mid-Mc region. The radiological appearance of 2 limbs suggested that contrast medium was present in the digital flexor tendon sheath (DFTS). After PaM injections, the contrast medium was distributed diffusely around the injection site in the majority of the limbs. In cadaver limbs, after Pa injections, the contrast medium and the dye were distributed in the neurovascular bundle in 8/20 (40%) limbs and in the DFTS in 6/20 (30%) of limbs. After PaM injections, the contrast and dye were distributed diffusely around the injection site in 9/20 (45%) limbs and showed diffuse and tubular distribution in 11/20 (55%) limbs. CONCLUSIONS AND POTENTIAL RELEVANCE: Proximal diffusion of local anaesthetic solution after a low 4-point nerve block is unlikely to be responsible for decreasing lameness caused by pain in the proximal Mc region. The DFTS may be penetrated inadvertently when performing a low 4-point nerve block.

Continuous Formation and Separation of Calcium-Alginate Capsules Containing Viable Mammalian Cells in Microfluidic Devices

Microfluidic devices can be used for many applications, including the formation of well-controlled emulsions. In this study, the capability to continuously create monodisperse droplets in a microfluidic device was used to form calcium-alginate capsules.Calcium-alginate capsules have many potential uses, such as immunoisolation of cells and microencapsulation of active drug ingredients or bitter agents in food or beverage products. The gelation of calcium-alginate capsules is achieved by crosslinking sodiumalginate with calcium ions. Calcium ions dissociated from calcium carbonate due to diffusion of acetic acid from a sunflower oil phase into an aqueous droplet containing sodium-alginate and calcium carbonate. After gelation, the capsules were separated from the continuous oil phase into an aqueous solution for use in biological applications. Typically, capsules are separated bycentrifugation, which can damage both the capsules and the encapsulated material. A passive method achieves separation without exposing the encapsulated material or the capsules to large mechanical forces, thereby preventing damage. To achieve passiveseparation, the use of a microfluidic device with opposing channel wa hydrophobicity was used to stabilize co-laminar flow of im of hydrophobicity is accomplished by defining one length of the channel with a hydrogel. The chosen hydrogel was poly (ethylene glycol) diacrylate, which adheres to the glass surface through the use of self-assembled monolayer of 3-(trichlorosilyl)-propyl methacrylate. Due to the difference in surface energy within the channel, the aqueous stream is stabilized near a hydrogel and the oil stream is stabilized near the thiolene based optical adhesive defining the opposing length of the channel. Passive separation with co-laminar flow has shown success in continuously separating calcium-alginatecapsules from an oil phase into an aqueous phase. In addition to successful formation and separation of calcium alginate capsules,encapsulation of Latex micro-beads and viable mammalian cells has been achieved. The viability of encapsulated mammalian cells was determined using a live/dead stain. The co-laminar flow device has also been demonstrated as a means of separating liquid-liquidemulsions.

A MICROFLUIDIC METHOD TO MEASURE DIFFUSION IN HYDROGELS

A novel microfluidic method is proposed for studying diffusion of small molecules in a hydrogel. Microfluidic devices were prepared with semi-permeable microchannels defined by crosslinked poly(ethylene glycol) (PEG). Uptake of dye molecules from aqueous solutions flowing through the microchannels was observedoptically and diffusion of the dye into the hydrogel was quantified. To complement the diffusion measurements from the microfluidic studies, nuclear magnetic resonance(NMR) characterization of the diffusion of dye in the PEG hydrogels was performed. The diffusion of small molecules in a hydrogel is relevant to applications such asdrug delivery and modeling transport for tissue-engineering applications. The diffusion of small molecules in a hydrogel is dependent on the extent of crosslinking within the gel, gel structure, and interactions between the diffusive species and the hydrogel network. These effects were studied in a model environment (semi-infinite slab) at the hydrogelfluid boundary in a microfluidic device. The microfluidic devices containing PEG microchannels were fabricated using photolithography. The unsteady diffusion of small molecules (dyes) within the microfluidic device was monitored and recorded using a digital microscope. The information was analyzed with techniques drawn from digital microscopy and image analysis to obtain concentration profiles with time. Using a diffusion model to fit this concentration vs. position data, a diffusion coefficient was obtained. This diffusion coefficient was compared to those from complementary NMR analysis. A pulsed field gradient (PFG) method was used to investigate and quantify small molecule diffusion in gradient (PFG) method was used to investigate and quantify small molecule diffusion in hydrogels. There is good agreement between the diffusion coefficients obtained from the microfluidic methods and those found from the NMR studies. The microfluidic approachused in this research enables the study of diffusion at length scales that approach those of vasculature, facilitating models for studying drug elution from hydrogels in blood-contacting applications.

A Microfluidic Method to Measure Small Molecule Diffusion in Hydrogels

Drug release from a fluid-contacting biomaterial is simulated using a microfluidic device with a channel defined by solute-loaded hydrogel; as water is pumped through the channel, solute transfers from the hydrogel into the water. Optical analysis of in-situ hydrogels, characterization of the microfluidic device effluent, and NMR methods were used to find diffusion coefficients of several dyes (model drugs) in poly( ethylene glycol) diacrylate (PEG-DA) hydrogels. Diffusion coefficients for methylene blue and sulforhodamine 101 in PEG-DA calculated using the three methods are in good agreement; both dyes are mobile in the hydrogel and elute from the hydrogel at the aqueous channel interface. However, the dye acid blue 22 deviates from typical diffusion behavior and does not release as expected from the hydrogel. Importantly, only the microfluidic method is capable of detecting this behavior. Characterizing solute diffusion with a combination of NMR, optical and effluent methods offer greater insight into molecular diffusion in hydrogels than employing each technique individually. The NMR method made precise measurements for solute diffusion in all cases. The microfluidic optical method was effective for visualizing diffusion of the optically active solutes. The optical and effluent methods show potential to be used to screen solutes to determine if they elute from a hydrogel in contact with flowing fluid. Our data suggest that when designing a drug delivery device, analyzing the diffusion from the molecular level to the device level is important to establish a complete picture of drug elution, and microfluidic methods to study such diffusion can play a key role. (C) 2013 Elsevier B.V. All rights reserved.

Structural and functional diversity of connexin genes in the mouse and human genome

Gap junctions are clustered channels between contacting cells through which direct intercellular communication via diffusion of ions and metabolites can occur. Two hemichannels, each built up of six connexin protein subunits in the plasma membrane of adjacent cells, can dock to each other to form conduits between cells. We have recently screened mouse and human genomic data bases and have found 19 connexin (Cx) genes in the mouse genome and 20 connexin genes in the human genome. One mouse connexin gene and two human connexin genes do not appear to have orthologs in the other genome. With three exceptions, the characterized connexin genes comprise two exons whereby the complete reading frame is located on the second exon. Targeted ablation of eleven mouse connexin genes revealed basic insights into the functional diversity of the connexin gene family. In addition, the phenotypes of human genetic disorders caused by mutated connexin genes further complement our understanding of connexin functions in the human organism. In this review we compare currently identified connexin genes in both the mouse and human genome and discuss the functions of gap junctions deduced from targeted mouse mutants and human genetic disorders.

Effects of carbonation on the mineral composition of cement kiln dust

Due to their relatively high calcium oxide content, industrial mineral oxide wastes are potential candidates for mineral sequestration of carbon dioxide (CO2). Cement kiln dust (CKD), a byproduct of cement manufacturing contains 20-60% CaO making it a possible candidate for CO2 sequestration. In this study, three types of CKD are characterized, before and after carbonation, using environmental scanning electron microscopy and energy dispersive x-ray microanalysis to determine the mineralogical and morphological changes occurring due to carbonation. The reactants, products, and precipitation mechanisms were investigated to enhance understanding of the governing processes and allow better utilization of CKD for CO2 sequestration. The results of multiple independent analyses confirmed the formation of CaCO3 during carbonation. Examinations of the reaction pathways found that CaO and calcium hydroxide (Ca(OH)2) were the major reactants. Three types of CaCO3 precipitation mechanisms were observed: (1) diffusion of CO2 into Ca(OH)2 particles causing precipitation in the pores of the particle and the growth of a CaCO3 ring from the outside inward, (2) precipitation onto existing particles, and (3) precipitation from aqueous solution. The growth of a CaCO3 ring on the outside of a particle may slow further diffusion of CO2 into a particle slowing iv the overall sequestration rate. Additionally, changes caused by carbonation in the solubility of trace metals were studied by mixing pre- and post-carbonated CKD with water and analyzing the solution using inductively coupled plasma mass spectrometry. Decreases in the leaching of chromium, lead, and copper were observed, and is an incentive for use of CKD for CO2 sequestration. Equilibrium modeling using PHREEQC confirmed that CaO and Ca(OH)2 would carbonate readily and form CaCO3.

UNDERSTANDING PEOPLE'S ADOPTION OF INDIVIDUAL-USE RENEWABLE ENERGY TECHNOLOGY

This thesis attempts to understand why people adopt or reject individual-use renewable energy technologies (IURET). I used factors from Everett Rogers' Diffusion of Innovation Theory to understand how people's perceptions towards the characteristics of a given IURET (such as price, compatibility, complexity, etc.), the characteristics of the individual adopter (such as innovativeness and environmental awareness), and the communication network (inter-personal communications and mass media) can influence adoption. An online questionnaire was sent to 101randomly selected Michigan households (using random digit dialing) to ask people whether or not they had adopted at least one IURET and to assess the above-mentioned factors from Rogers' theory. Data analysis was then conducted in SPSS using Chi-squared and binary logistic regression to determine the relationship between adoption behaviors (the dependent variable) and the factors from Rogers' theory (the independent variables) while controlling for education. The results show that Rogers' factors of price and observability and the control variable of education were all significant in explaining adoption but the other factors of Rogers' theory were not. For example, if individuals perceive the price of IURET to be reasonable or if they observe their neighbors using these technologies, then they are more likely to adopt. These results indicate that, if we want to promote greater adoption of IURET, we should focus our efforts on making the price of IURET more affordable through incentives and other mechanisms. Adopters should also be given some form of reward if they provide free demonstrations of their IURET in use to their neighbors to take advantage of the observability effects.

Some Preliminary Investiagtions of the Magnetic Permeabilities of Alloys of the Ferromagnetic Metals

The problem presented for this thesis was an investigation of the magnetic properties of the alloys produced by the methods of powder metallurgy. The question behind this was the correlation of the magnetic properties with the bonding properties and with the diffusion of the constituents.

Not for Designers: On the Inadequacies of EU Design Law and How to Fix It

Design rights represent an interesting example of how the EU legislature has successfully regulated an otherwise heterogeneous field of law. Yet this type of protection is not for all. The tools created by EU intervention have been drafted paying much more attention to the industry sector rather than to designers themselves. In particular, modern, digitally based, individual or small-sized, 3D printing, open designers and their needs are largely neglected by such legislation. There is obviously nothing wrong in drafting legal tools around the needs of an industrial sector with an important role in the EU economy, on the contrary, this is a legitimate and good decision of industrial policy. However, good legislation should be fair, balanced, and (technologically) neutral in order to offer suitable solutions to all the players in the market, and all the citizens in the society, without discriminating the smallest or the newest: the cost would be to stifle innovation. The use of printing machinery to manufacture physical objects created digitally thanks to computer programs such as Computer-Aided Design (CAD) software has been in place for quite a few years, and it is actually the standard in many industrial fields, from aeronautics to home furniture. The change in recent years that has the potential to be a paradigm-shifting factor is a combination between the opularization of such technologies (price, size, usability, quality) and the diffusion of a culture based on access to and reuse of knowledge. We will call this blend Open Design. It is probably still too early, however, to say whether 3D printing will be used in the future to refer to a major event in human history, or instead will be relegated to a lonely Wikipedia entry similarly to ³Betamax² (copyright scholars are familiar with it for other reasons). It is not too early, however, to develop a legal analysis that will hopefully contribute to clarifying the major issues found in current EU design law structure, why many modern open designers will probably find better protection in copyright, and whether they can successfully rely on open licenses to achieve their goals. With regard to the latter point, we will use Creative Commons (CC) licenses to test our hypothesis due to their unique characteristic to be modular, i.e. to have different license elements (clauses) that licensors can choose in order to adapt the license to their own needs.”