Computational Study of the Hydration of Sulfuric Acid Dimers: Implications for Acid Dissociation and Aerosol Formation

We have investigated the thermodynamics of sulfuric acid dimer hydration using ab initio quantum mechanical methods. For (H2SO4)2(H2O)n where n = 0−6, we employed high-level ab initio calculations to locate the most stable minima for each cluster size. The results presented herein yield a detailed understanding of the first deprotonation of sulfuric acid as a function of temperature for a system consisting of two sulfuric acid molecules and up to six waters. At 0 K, a cluster of two sulfuric acid molecules and one water remains undissociated. Addition of a second water begins the deprotonation of the first sulfuric acid leading to the di-ionic species (the bisulfate anion HSO4−, the hydronium cation H3O+, an undissociated sulfuric acid molecule, and a water). Upon the addition of a third water molecule, the second sulfuric acid molecule begins to dissociate. For the (H2SO4)2(H2O)3 cluster, the di-ionic cluster is a few kcal mol−1 more stable than the neutral cluster, which is just slightly more stable than the tetra-ionic cluster (two bisulfate anions, two hydronium cations, and one water). With four water molecules, the tetra-ionic cluster, (HSO4−)2(H3O+)2(H2O)2, becomes as favorable as the di-ionic cluster H2SO4(HSO4−)(H3O+)(H2O)3 at 0 K. Increasing the temperature favors the undissociated clusters, and at room temperature we predict that the di-ionic species is slightly more favorable than the neutral cluster once three waters have been added to the cluster. The tetra-ionic species competes with the di-ionic species once five waters have been added to the cluster. The thermodynamics of stepwise hydration of sulfuric acid dimer is similar to that of the monomer; it is favorable up to n = 4−5 at 298 K. A much more thermodynamically favorable pathway forming sulfuric acid dimer hydrates is through the combination of sulfuric acid monomer hydrates, but the low concentration of sulfuric acid relative to water vapor at ambient conditions limits that process.

Provenance signature of a forearc basin modified by spreading ridge subduction: Detrital zircon geochronology and detrital modes from the Paleogene Arkose Ridge Formation, southern Alaska

Upper Paleocene–Eocene boulder conglomerate, cross-stratified sandstone, and laminated carbonaceous mudstone of the Arkose Ridge Formation exposed in the southern Talkeetna Mountains record fluvial-lacustrine deposition proximal to the volcanic arc in a forearc basin modified by Paleogene spreading ridge subduction beneath southern Alaska. U-Pb ages of detrital zircon grains and modal analyses were obtained from stratigraphic sections spanning the 2,000 m thick Arkose Ridge Formation in order to constrain the lithology, age, and location of sediment sources that provided detritus. Detrital modes from 24 conglomerate beds and 54 sandstone thin sections aredominated by plutonic and volcanic clasts and plagioclase feldspar with minor quartz, schist, hornblende, argillite, and metabasalt. Westernmost sandstone and conglomerate strata contain <5% volcanic clasts whereas easternmost sandstone and conglomerate strata contain 40 to >80% volcanic clasts. Temporally, eastern sandstones andconglomerates exhibit an upsection increase in volcanic detritus from <40 to >80% volcanic clasts. U-Pb ages from >1400 detrital zircons in 15 sandstone samples reveal three main populations: late Paleocene–Eocene (60-48 Ma; 16% of all grains), Late Cretaceous–early Paleocene (85–60 Ma; 62%) and Jurassic–Early Cretaceous (200–100 Ma; 12%). A plot of U/Th vs U-Pb ages shows that >97% of zircons are <200 Ma and>99% of zircons have <10 U/Th ratios, consistent with mainly igneous source terranes. Strata show increased enrichment in late Paleocene–Eocene detrital zircons from <2% in the west to >25% in the east. In eastern sections, this younger age population increases temporally from 0% in the lower 50 m of the section to >40% in samples collected >740 m above the base. Integration of the compositional and detrital geochronologic data suggests: (1) Detritus was eroded mainly from igneous sources exposed directly north of the Arkose Ridge Formation strata, mainly Jurassic–Paleocene plutons and Paleocene–Eocenevolcanic centers. Subordinate metamorphic detritus was eroded from western Mesozoic low-grade metamorphic sources. Subordinate sedimentary detritus was eroded from eastern Mesozoic sedimentary sources. (2) Eastern deposystems received higher proportions of juvenile volcanic detritus through time, consistent with construction of adjacent slab-window volcanic centers during Arkose Ridge Formation deposition. (3)Western deposystems transported detritus from Jurassic–Paleocene arc plutons that flank the northwestern basin margin. (4) Metasedimentary strata of the Chugach accretionaryprism, exposed 20-50 km south of the Arkose Ridge Formation, did not contribute abundant detritus. Conventional provenance models predict reduced input of volcanic detritus to forearc basins during exhumation of the volcanic edifice and increasing exposure ofsubvolcanic plutons (Dickinson, 1995; Ingersoll and Eastmond, 2007). In the forearc strata of these conventional models, sandstone modal analyses record progressive increases upsection in quartz and feldspar concomitant with decreases in lithic grains, mainly volcanic lithics. Additionally, as the arc massif denudes through time, theyoungest detrital U-Pb zircon age populations become significantly older than the age of forearc deposition as the arc migrates inboard or ceases magmatism. Westernmost strata of the Arkose Ridge Formation are consistent with this conventional model. However, easternmost strata of the Arkose Ridge Formation contain sandstone modes that record an upsection increase in lithic grains accompanied by a decrease in quartz and feldspar, and detrital zircon age populations that closely match the age of deposition. This deviation from the conventional model is due to the proximity of the easternmost strata to adjacent juvenile volcanic rocks emplaced by slab-window volcanic processes. Provenance data from the Arkose Ridge Formation show that forearc basins modified by spreading ridge subduction may record upsection increases in non-arc, syndepositional volcanic detritusdue to contemporaneous accumulation of thick volcanic sequences at slab-window volcanic centers. This change may occur locally at the same time that other regions of the forearc continue to receive increasing amounts of plutonic detritus as the remnant arc denudes, resulting in complex lateral variations in forearc basin petrofacies and chronofacies.

Maximizing Product Formation and Minimizing Degradation: A Look at Buffering Conditions and Post-Reaction Degradation for the In-Line Jaffe Reaction with Capillary Electrophoresis

Creatinine levels in blood serum are typically used to assess renal function. Clinical determination of creatinine is often based on the Jaffe reaction, in which creatinine in the serum reacts with sodium picrate, resulting in a spectrophotometrically quantifiable product. Previous work from our lab has introduced an electrophoretically mediated initiation of this reaction, in which nanoliter plugs of individual reagent solutions can be added to the capillary and then mixed and reacted. Following electrophoretic separation of the product from excess reactant(s), the product can be directly determined on column. This work aims to gain a detailed understanding of the in-capillary reagent mixing dynamics, in-line reaction yield, and product degradation during electrophoresis, with an overall goal of improving assay sensitivity. One set of experiments focuses on maximizing product formation through manipulation of various conditions such as pH, voltage applied, and timing of the applied voltage, in addition to manipulations in the identity, concentration, and pH of the background electrolyte. Through this work, it was determined that dramatic changes in local voltage fields within the various reagent zones lead to ineffective reagent overlapping. Use of the software simulation program Simul 5 enabled visualization of the reaction dynamics within the capillary, specifically the wide variance between the electric field intensities within the creatinine and picrate zones. Because of this simulation work, the experimental method was modified to increase the ionic strength of the creatinine reagent zone to lower the local voltage field, thus producing more predictable and effective overlap conditions for the reagents and allowing the formation of more Jaffe product. As second set of experiments focuses on controlling the post-reaction product degradation. In that vein, we have systematically explored the importance of the identity, concentration, and pH of the background electrolyte on the post-reaction degradation rate of the product. Although prior work with borate background electrolytes indicated that product degradation was probably a function of the ionic strength of the background electrolyte, this work with a glycine background electrolyte demonstrates that degradation is in fact not a function of ionic strength of the background electrolyte. As the concentration and pH of the glycine background increased, the rate of degradation of product did not change dramatically, whereas in borate-buffered systems, the rate of Jaffe product degradation increased linearly with background electrolyte concentration above 100.0 mM borate. Similarly, increasing pH of the glycine background electrolyte did not result in a corresponding increase in product degradation, as it had with the borate background electrolyte. Other general trends that were observed include: increasing background electrolyte concentration increases peak efficiency and higher pH favors product formation; thus, it appears that use of a background electrolyte other than borate, such as glycine, the rate of degradation of the Jaffe product can be slowed, increasing the sensitivity of this in-line assay.

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.

Efficient Liquid Liquid Extraction By Emulsion Formation and Separation in Robust Milli-Fluidic Devices

Conventional liquid liquid extraction (LLE) methods require large volumes of fluids to achieve the desired mass transfer of a solute, which is unsuitable for systems dealing with a low volume or high value product. An alternative to these methods is to scale down the process. Millifluidic devices share many of the benefits of microfluidic systems, including low fluid volumes, increased interfacial area-to-volume ratio, and predictability. A robust millifluidic device was created from acrylic, glass, and aluminum. The channel is lined with a hydrogel cured in the bottom half of the device channel. This hydrogel stabilizes co-current laminar flow of immiscible organic and aqueous phases. Mass transfer of the solute occurs across the interface of these contacting phases. Using a y-junction, an aqueous emulsion is created in an organic phase. The emulsion travels through a length of tubing and then enters the co-current laminar flow device, where the emulsion is broken and each phase can be collected separately. The inclusion of this emulsion formation and separation increases the contact area between the organic and aqueous phases, therefore increasing the area over which mass transfer can occur. Using this design, 95% extraction efficiency was obtained, where 100% is represented by equilibrium. By continuing to explore this LLE process, the process can be optimized and with better understanding may be more accurately modeled. This system has the potential to scale up to the industrial level and provide the efficient extraction required with low fluid volumes and a well-behaved system.

Where Is "Home"? Value Conflicts, Identity Crises and the Formation of Cosmopolitan Identity in Myanmar Students Studying in the United States

Fully engaging in a new culture means translating oneself into a different set of cultural values, and many of the values can be foreign to the individual. The individual may face conflicting tensions between the psychological need to be a part of the new society and feelings of guilt or betrayal towards the former society, culture or self. Many international students from Myanmar, most of whom have little international experience, undergo this value and cultural translation during their time in American colleges. It is commonly assumed that something will be lost in the process of translation and that the students become more Westernized or never fit into both Myanmar and US cultures. However, the study of the narratives of the Myanmar students studying in the US reveals a more complex reality. Because individuals have multifaceted identities and many cultures and subcultures are fluctuating and intertwined with one another, the students¿ cross-cultural interactions can also help them acquire new ways of seeing things. Through their struggle to engage in the US college culture, many students display the theory of ¿cosmopolitanism¿ in their transformative identity formation process and thus, define and identify themselves beyond one set of cultural norms.