VLE MEASUREMENTS FOR ASYMMETRIC MIXTURES OF FISCHER-TROPSCH HYDROCARBONS

The ability to model the thermodynamic phase behavior of long-chain and short-chain alkane mixtures is of considerable industrial and theoretical interest. However, attempts to accurately describe the phase behavior of what we call asymmetric mixtures of hydrocarbons (AMoHs) have met with only limited success. Vapor-liquid equilibrium (VLE) data are surprisingly scarce, and the limited data that are available suggest that cubic equations of state may not be capable of fitting (much less predicting) the phase behavior of AMoHs. The following tasks, which address the problems described above, were accomplished during the one-year period of this Phase I UCR grant: (1) A continuous-flow apparatus was modified for the measurement of AMoHs and used to measure VLE for propane + hexadecane mixtures at temperatures from 473 to 626 K and pressures up to the mixture critical pressures of about 100 bar. (2) The extent to which cubic vs. modern, statistical mechanics-based equations of state (EoS) are applicable to AMoHs was evaluated. Peng-Robinson (PR) was found to be a surprisingly accurate equation for fitting AMoHs, but only if its pure component parameters were regressed to liquid densities and vapor pressures. However, even this form of PR was still not a predictive equation, as there was a significant variation of kij with temperature. In spite of its deficiencies in terms of vapor-phase predictions and modeling of the critical region, PC-SAFT was found to be the most appropriate EoS for truly predicting the phase behavior of highly asymmetric mixtures of alkanes. (3) Finally, a dense-gas extraction (DGE) apparatus was designed and constructed for the fractionation of F-T waxes into cuts of pure oligomers. Such oligomers are needed in g-sized quantities to perform VLE measurements with long-chain alkanes with carbon numbers greater than 40. The dense gas and the solute mixture to be extracted are contacted in a packed column that has a separation power significantly greater than what can be achieved in one equilibrium stage. Thus, wax oligomer purities are expected to be much better than what can be obtained by conventional supercritical extraction processes

Solvent and recovery process for lignin

Methods for obtaining purified lignin and the lignin that can be obtained by the methods are described. Methods include processing pretreated lignocellulosic biomass feedstock to recover the lignin and provide a lignin composition with a very low level of impurities such as metals and ash. In addition, the lignin recovered from the process can have a narrow molecular weight distribution and, depending upon the specific stages utilized in the process, can have a predetermined molecular weight. The process includes one or more separation stages in which a lignin-containing feedstock is mixed with a solvent solution. The mixture fractionates to form a solvent-rich liquid phase and a lignin-rich liquid phase, the lignin being partitioned across the phases according to the molecular weight of the lignin. Furthermore, the metal salts of the pretreated lignocellulosic biomass feedstock also partition across the phases

Supercritical fluid explosion process to aid fractionation of lipids from biomass

Disclosed are processes for development and recovery of lipids from biomass. A plant or microorganism-based biomass can be developed to encourage a desired lipid profile. Following development, ecologically friendly normally gaseous fluids such as carbon dioxide can be pressurized to a supercritical state followed by rapid expansion. The fluid is first contacted with a biomass source including oil-containing microorganisms and/or agricultural products. For instance, fungi or algae can be bioconverted from another biomass sources such as canola seed or corn syrup and then contacted with the high pressure fluid. During a contact period, the fluid can diffuse into the biomass, and in particular through the cell walls of the biomass. The fluid undergoes rapid release of pressure and opens the cell structure for improved release of oil. The fluid can optionally be utilized for extraction following the explosion process. For instance, the fluid can be re-pressurized in the same vessel for extraction processes

The Sulfur-Iodine Cycle: Process Analysis and Design Using Comprehensive Phase Equilibrium Measurements and Modeling

Of the 100+ thermochemical hydrogen cycles that have been proposed, the Sulfur-Iodine (S-I) Cycle is a primary target of international interest for the centralized production of hydrogen from nuclear power. However, the cycle involves complex and highly nonideal phase behavior at extreme conditions that is only beginning to be understood and modeled for process simulation. The consequence is that current designs and efficiency projections have large uncertainties, as they are based on incomplete data that must be extrapolated from property models. This situation prevents reliable assessment of the potential viability of the system and, even more, a basis for efficient process design. The goal of this NERI award (05-006) was to generate phase-equilibrium data, property models, and comprehensive process simulations so that an accurate evaluation of the S-I Cycle could be made. Our focus was on Section III of the Cycle, where the hydrogen is produced by decomposition of hydroiodic acid (HI) in the presence of water and iodine (I2) in a reactive distillation (RD) column. The results of this project were to be transferred to the nuclear hydrogen community in the form of reliable flowsheet models for the S-I process. Many of the project objectives were achieved. At Clemson University, a unique, tantalum-based, phase-equilibrium apparatus incorporating a view cell was designed and constructed for measuring fluid-phase equilibria for mixtures of iodine, HI, and water (known as HIx) at temperatures to 350 °C and pressures to 100 bar. Such measurements were of particular interest for developing a working understanding of the expected operation of the RD column in Section III. The view cell allowed for the IR observation and discernment of vapor-liquid (VL), liquid-liquid, and liquid-liquid-vapor (LLVE) equilibria for HIx systems. For the I2-H2O system, liquid-liquid equilibrium (LLE) was discovered to exist at temperatures up to 310-315 °C, in contrast to the models and predictions of earlier workers. For the I2-HI-H2O ternary, LLE and LLVE were all observed for the first time at temperatures of 160 and 200 °C. Three LLE tie-lines were measured at 160 °C, and preliminary indications are that the underlying phase behavior could result in further improvements in the performance of the S-I Cycle. Unfortunately, these new results were obtained too late in the project to be incorporated into the modeling and simulation work described below. At the University of Virginia, a uniquely complete and reliable model was developed for the thermodynamic properties of HIx, covering the range of conditions expected for the separation of product hydrogen and recycled iodine in the RD column located in Section III. The model was validated with all available property spectroscopy data. The results provide major advances over prior understanding of the chemical speciation involved. The model was implemented in process simulation studies of the S-I Cycle, which showed improvement in energy efficiency to 42%, as well as significantly smaller capital requirements due to lower pressure operation and much smaller equipment sizes. The result is that the S-I Cycle may be much more economically feasible than was previously thought. If both the experimental and modeling work described above were to be continued to ultimate process optimization, both the American public and the global community would benefit from this alternative energy source that does not produce carbon emissions

Low-dose vitamin D3 supplementation does not affect natural regulatory T cell population but attenuates seasonal changes in T cell-produced IFN-γ: Results from the D-SIRe2 randomised controlled trial

Background: Seasonal variations have been reported for immune markers. However, the relative contributions of sunlight and vitamin D variability on such seasonal changes are unknown. Objective: This double-blind, randomized, placebo-controlled trial tested whether daily 400 IU vitamin D3 supplementation affected short-term (12 weeks) and long-term (43 weeks) natural regulatory T cell (nTreg) populations in healthy participants. Design: 62 subjects were randomized equally to vitamin D versus placebo in March and assessed at baseline, April (4w), June (12w), September (25w) and January (43w). Circulating nTregs, ex vivo proliferation, IL-10 and IFN-γ productions were measured. Vitamin D metabolites and sunlight exposure were also assessed. Results: Mean serum 25-hydroxyvitamin D (25(OH)D) increased from 35.8(SD 3.0) to 65.3(2.6) nmol/L in April and remained above 70 nmol/L with vitamin D supplementation, whereas it increased from 36.4(3.2) to 49.8(3.5) nmol/L in June to fall back to 39.6(3.5) nmol/L in January with placebo. Immune markers varied similarly between groups according to the season, but independently of 25(OH)D. For nTregs, the mean (%CD3+CD4+CD127lo cells (SEM)) nadir observed in March (2.9(0.1)%) peaked in September at 4.0(0.2)%. Mean T cell proliferation peaked in June (33156(1813) CPM) returning to the nadir in January (17965 (978) CPM), while IL-10 peaked in June and reached its nadir in September (median (IQR) of 262(283) to (121(194) pg/ml, respectively). Vitamin D attenuated the seasonal increase in IFN-γ by ~28% with mean ng/ml (SEM) for placebo vs vitamin D, respectively, for April 12.5(1.4) vs 10.0(1.2) (p=0.02); June 13.9(1.3) vs 10.2(1.7) (p=0.02) and January 7.4(1.1) vs 6.0(1.1) (p=0.04). Conclusions: Daily low dose Vitamin D intake did not affect the nTregs population. There were seasonal variation in nTregs, proliferative response and cytokines, suggesting that environmental changes influence immune response, but the mechanism seems independent of vitamin D status. Vitamin D attenuated the seasonal change in T cell-produced IFN-γ, suggesting a decrease in effector response which could be associated with inflammation. Clinical trial identifier: ISRCTN 73114576 (https://www.isrctn.com

Different paths to the modern state in Europe: the interaction between domestic political economy and interstate competition

Theoretical work on state formation and capacity has focused mostly on early modern Europe and on the experience of western European states during this period. While a number of European states monopolized domestic tax collection and achieved gains in state capacity during the early modern era, for others revenues stagnated or even declined, and these variations motivated alternative hypotheses for determinants of fiscal and state capacity. In this study we test the basic hypotheses in the existing literature making use of the large date set we have compiled for all of the leading states across the continent. We find strong empirical support for two prevailing threads in the literature, arguing respectively that interstate wars and changes in economic structure towards an urbanized economy had positive fiscal impact. Regarding the main point of contention in the theoretical literature, whether it was representative or authoritarian political regimes that facilitated the gains in fiscal capacity, we do not find conclusive evidence that one performed better than the other. Instead, the empirical evidence we have gathered lends supports to the hypothesis that when under pressure of war, the fiscal performance of representative regimes was better in the more urbanized-commercial economies and the fiscal performance of authoritarian regimes was better in rural-agrarian economie

The Genomic Analysis of Lactic Acidosis and Acidosis Response in Human Cancers

The tumor microenvironment has a significant impact on tumor development. Two important determinants in this environment are hypoxia and lactic acidosis. Although lactic acidosis has long been recognized as an important factor in cancer, relatively little is known about how cells respond to lactic acidosis and how that response relates to cancer phenotypes. We develop genome-scale gene expression studies to dissect transcriptional responses of primary human mammary epithelial cells to lactic acidosis and hypoxia in vitro and to explore how they are linked to clinical tumor phenotypes in vivo. The resulting experimental signatures of responses to lactic acidosis and hypoxia are evaluated in a heterogeneous set of breast cancer datasets. A strong lactic acidosis response signature identifies a subgroup of low-risk breast cancer patients having distinct metabolic profiles suggestive of a preference for aerobic respiration. The association of lactic acidosis response with good survival outcomes may relate to the role of lactic acidosis in directing energy generation toward aerobic respiration and utilization of other energy sources via inhibition of glycolysis. This “inhibition of glycolysis” phenotype in tumors is likely caused by the repression of glycolysis gene expression and Akt inhibition. Our study presents a genomic evaluation of the prognostic information of a lactic acidosis response independent of the hypoxic response. Our results identify causal roles of lactic acidosis in metabolic reprogramming, and the direct functional consequence of lactic acidosis pathway activity on cellular responses and tumor development. The study also demonstrates the utility of genomic analysis that maps expression-based findings from in vitro experiments to human samples to assess links to in vivo clinical phenotypes

Rivastigmine Lowers Aβ and Increases sAPPα Levels, Which Parallel Elevated Synaptic Markers and Metabolic Activity in Degenerating Primary Rat Neurons

Overproduction of amyloid-β (Aβ) protein in the brain has been hypothesized as the primary toxic insult that, via numerous mechanisms, produces cognitive deficits in Alzheimer's disease (AD). Cholinesterase inhibition is a primary strategy for treatment of AD, and specific compounds of this class have previously been demonstrated to influence Aβ precursor protein (APP) processing and Aβ production. However, little information is available on the effects of rivastigmine, a dual acetylcholinesterase and butyrylcholinesterase inhibitor, on APP processing. As this drug is currently used to treat AD, characterization of its various activities is important to optimize its clinical utility. We have previously shown that rivastigmine can preserve or enhance neuronal and synaptic terminal markers in degenerating primary embryonic cerebrocortical cultures. Given previous reports on the effects of APP and Aβ on synapses, regulation of APP processing represents a plausible mechanism for the synaptic effects of rivastigmine. To test this hypothesis, we treated degenerating primary cultures with rivastigmine and measured secreted APP (sAPP) and Aβ. Rivastigmine treatment increased metabolic activity in these cultured cells, and elevated APP secretion. Analysis of the two major forms of APP secreted by these cultures, attributed to neurons or glia based on molecular weight showed that rivastigmine treatment significantly increased neuronal relative to glial secreted APP. Furthermore, rivastigmine treatment increased α-secretase cleaved sAPPα and decreased Aβ secretion, suggesting a therapeutic mechanism wherein rivastigmine alters the relative activities of the secretase pathways. Assessment of sAPP levels in rodent CSF following once daily rivastigmine administration for 21 days confirmed that elevated levels of APP in cell culture translated in vivo. Taken together, rivastigmine treatment enhances neuronal sAPP and shifts APP processing toward the α-secretase pathway in degenerating neuronal cultures, which mirrors the trend of synaptic proteins, and metabolic activity