BENEFICIATION OF COAL USING SUPERCRITICAL WATER AND CARBON DIOXIDE EXTRACTION

This work explores the use of carbon dioxide, water, and their mixtures as solvent for the pre-combustion beneficiation of raw coal without using any toxic mineral acids in the temperature range of 200-400℃. The fluid polarity, ionic constant, and supercritical point can be adjusted by H2O/CO2 ratio and temperature. Adding carbon dioxide to hydrothermal fluid also increases the ionization by forming carbonic acid. Extractions with supercritical fluids have several benefits including enhanced mass transport, ease of separation and recycle, wide range of extractive capability and tunability, better inherent safety, and in the case of carbon dioxide and water – low cost. A semi-continuous extraction system was designed and built in which pressure, temperature and the relative flow rates of CO2 and H2O can be controlled. Coal powder is kept in a packed bed and the extraction is carried out at 143 bar pressure. Using sulfur as a model heteroatom, extractive efficiency is examined as a function of the temperature, fluid composition, fluid flow, and extraction time. Results indicated that carbon dioxide, water, and supercritical water-carbon dioxide (ScWC) all can effectively extract about 50% of total sulfur from bituminous coal in one hour. Extraction above 350℃ decreased effectiveness, and extraction above the supercritical point of pure water caused polymerization presumably due to hydrothermal carbonization. Elimination of organic sulfur may play a role in the polymerization. The carbonized coal that was obtained from extraction above 350℃ gives an interesting product that is clean, porous, and partly graphitic in nature. The material could have exciting applications to replace metallurgical coke in metal refining and anode carbon in energy storage applications. Some carbonization occurred in pure carbon dioxide around 350℃ as well. Additionally, ScWC extraction may provide necessary control to prevent organic dissolution while removing sulfur. While neither carbon dioxide nor water seemed to affect the ash content, ScWC extraction decreased the ash content to 3.77%, a 45% reduction in ash. The extraction process was further developed to introduce ultrasound energy to enhance mass transfer from solid coal particles to the fluid phase. At the high temperature and pressure conditions as noted above, the introduction of ultrasound was successful and tested for coal extraction. The degree of mass transfer enhancement can be controlled by the intensity of the ultrasound. Such an enhancement, opens up possibility of relaxing the requirement on the fine particle size of the coal. We found that the conversion of pyrite was nearly complete for the best extracted samples with organic sulfur mostly untouched, indicating that the mass transport even without ultrasound was fairly good. In the base design of the extractor, the fluid entry and exit points are both on the top cover plate of the vessel. Here scWC fluid enters at the top and then leaves from the top after extraction, so it is possible that not all the coal solids are efficiently contacted with the fresh fluid coming in. To overcome this possible channeling effect, we have further enhanced the extractor design. The apparatus is designed to allow for the fluid to enter at the top, go through the pack bed of coal, and then exit from the bottom carrying extracted components. The design was tested successfully

Heterogeneity in Surface Sensing Suggests a Division of Labor in Pseudomonas aeruginosa Populations

The second messenger signaling molecule cyclic diguanylate monophosphate (c-di-GMP) drives the transition between planktonic and biofilm growth in many bacterial species. Pseudomonas aeruginosa has two surface sensing systems that produce c-di-GMP in response to surface adherence. Current thinking in the field is that once cells attach to a surface, they uniformly respond by producing c-di-GMP. Here, we describe how the Wsp system generates heterogeneity in surface sensing, resulting in two physiologically distinct subpopulations of cells. One subpopulation has elevated c-di-GMP and produces biofilm matrix, serving as the founders of initial microcolonies. The other subpopulation has low c-di-GMP and engages in surface motility, allowing for exploration of the surface. We also show that this heterogeneity strongly correlates to surface behavior for descendent cells. Together, our results suggest that after surface attachment, P. aeruginosa engages in a division of labor that persists across generations, accelerating early biofilm formation and surface exploration

Fate of the Josephson effect in thin-film superconductors

The dc Josephson effect refers to the dissipationless electrical current -- the supercurrent -- that can be sustained across a weak link connecting two bulk superconductors. This effect is a probe of the fundamental nature of the superconducting state. Here, we analyze the case of two superconducting thin films connected by a point contact. Remarkably, the Josephson effect is absent at nonzero temperature, and the resistance across the contact is nonzero. Moreover, the point contact resistance is found to vary with temperature in a nearly activated fashion, with a UNIVERSAL energy barrier determined only by the superfluid stiffness characterizing the films, an angle characterizing the geometry, and whether or not the Coulomb interaction between Cooper pairs is screened. This behavior reflects the subtle nature of the superconductivity in two-dimensional thin films, and should be testable in detail by future experiments.Comment: 16 + 8 pages. 1 figure, 1 tabl

Discovery and Validation of a New Class of Small Molecule Toll-Like Receptor 4 (TLR4) Inhibitors

Many inflammatory diseases may be linked to pathologically elevated signaling via the receptor for lipopolysaccharide (LPS), toll-like receptor 4 (TLR4). There has thus been great interest in the discovery of TLR4 inhibitors as potential anti-inflammatory agents. Recently, the structure of TLR4 bound to the inhibitor E5564 was solved, raising the possibility that novel TLR4 inhibitors that target the E5564-binding domain could be designed. We utilized a similarity search algorithm in conjunction with a limited screening approach of small molecule libraries to identify compounds that bind to the E5564 site and inhibit TLR4. Our lead compound, C34, is a 2-acetamidopyranoside (MW 389) with the formula C17H27NO9, which inhibited TLR4 in enterocytes and macrophages in vitro, and reduced systemic inflammation in mouse models of endotoxemia and necrotizing enterocolitis. Molecular docking of C34 to the hydrophobic internal pocket of the TLR4 co-receptor MD-2 demonstrated a tight fit, embedding the pyran ring deep inside the pocket. Strikingly, C34 inhibited LPS signaling ex-vivo in human ileum that was resected from infants with necrotizing enterocolitis. These findings identify C34 and the β-anomeric cyclohexyl analog C35 as novel leads for small molecule TLR4 inhibitors that have potential therapeutic benefit for TLR4-mediated inflammatory diseases. © 2013 Neal et al

Sensing remote nuclear spins

Sensing single nuclear spins is a central challenge in magnetic resonance based imaging techniques. Although different methods and especially diamond defect based sensing and imaging techniques in principle have shown sufficient sensitivity, signals from single nuclear spins are usually too weak to be distinguished from background noise. Here, we present the detection and identification of remote single C-13 nuclear spins embedded in nuclear spin baths surrounding a single electron spins of a nitrogen-vacancy centre in diamond. With dynamical decoupling control of the centre electron spin, the weak magnetic field ~10 nT from a single nuclear spin located ~3 nm from the centre with hyperfine coupling as weak as ~500 Hz is amplified and detected. The quantum nature of the coupling is confirmed and precise position and the vector components of the nuclear field are determined. Given the distance over which nuclear magnetic fields can be detected the technique marks a firm step towards imaging, detecting and controlling nuclear spin species external to the diamond sensor

The effect of intervertebral cartilage on neutral posture and range of motion in the necks of sauropod dinosaurs

The necks of sauropod dinosaurs were a key factor in their evolution. The habitual posture and range of motion of these necks has been controversial, and computer-aided studies have argued for an obligatory sub-horizontal pose. However, such studies are compromised by their failure to take into account the important role of intervertebral cartilage. This cartilage takes very different forms in different animals. Mammals and crocodilians have intervertebral discs, while birds have synovial joints in their necks. The form and thickness of cartilage varies significantly even among closely related taxa. We cannot yet tell whether the neck joints of sauropods more closely resembled those of birds or mammals. Inspection of CT scans showed cartilage:bone ratios of 4.5% for Sauroposeidon and about 20% and 15% for two juvenile Apatosaurus individuals. In extant animals, this ratio varied from 2.59% for the rhea to 24% for a juvenile giraffe. It is not yet possible to disentangle ontogenetic and taxonomic signals, but mammal cartilage is generally three times as thick as that of birds. Our most detailed work, on a turkey, yielded a cartilage:bone ratio of 4.56%. Articular cartilage also added 11% to the length of the turkey's zygapophyseal facets. Simple image manipulation suggests that incorporating 4.56% of neck cartilage into an intervertebral joint of a turkey raises neutral posture by 15°. If this were also true of sauropods, the true neutral pose of the neck would be much higher than has been depicted. An additional 11% of zygapophyseal facet length translates to 11% more range of motion at each joint. More precise quantitative results must await detailed modelling. In summary, including cartilage in our models of sauropod necks shows that they were longer, more elevated and more flexible than previously recognised

Coupling models of cattle and farms with models of badgers for predicting the dynamics of bovine tuberculosis (TB)

Bovine TB is a major problem for the agricultural industry in several countries. TB can be contracted and spread by species other than cattle and this can cause a problem for disease control. In the UK and Ireland, badgers are a recognised reservoir of infection and there has been substantial discussion about potential control strategies. We present a coupling of individual based models of bovine TB in badgers and cattle, which aims to capture the key details of the natural history of the disease and of both species at approximately county scale. The model is spatially explicit it follows a very large number of cattle and badgers on a different grid size for each species and includes also winter housing. We show that the model can replicate the reported dynamics of both cattle and badger populations as well as the increasing prevalence of the disease in cattle. Parameter space used as input in simulations was swept out using Latin hypercube sampling and sensitivity analysis to model outputs was conducted using mixed effect models. By exploring a large and computationally intensive parameter space we show that of the available control strategies it is the frequency of TB testing and whether or not winter housing is practised that have the most significant effects on the number of infected cattle, with the effect of winter housing becoming stronger as farm size increases. Whether badgers were culled or not explained about 5%, while the accuracy of the test employed to detect infected cattle explained less than 3% of the variance in the number of infected cattle

Study protocol: evaluation of a parenting and stress management programme: a randomised controlled trial of Triple P discussion groups and stress control

<br>Background: Children displaying psychosocial problems are at an increased risk of negative developmental outcomes. Parenting practices are closely linked with child development and behaviour, and parenting programmes have been recommended in the treatment of child psychosocial problems. However, parental mental health also needs to be addressed when delivering parenting programmes as it is linked with parenting practices, child outcomes, and treatment outcomes of parenting programmes. This paper describes the protocol of a study examining the effects of a combined intervention of a parenting programme and a cognitive behavioural intervention for mental health problems.</br> <br>Methods: The effects of a combined intervention of Triple P Discussion Groups and Stress Control will be examined using a randomised controlled trial design. Parents with a child aged 3?8?years will be recruited to take part in the study. After obtaining informed consent and pre-intervention measures, participants will be randomly assigned to either an intervention or a waitlist condition. The two primary outcomes for this study are change in dysfunctional/ineffective parenting practices and change in symptoms of depression, anxiety, and stress. Secondary outcomes are child behaviour problems, parenting experiences, parental self-efficacy, family relationships, and positive parental mental health. Demographic information, participant satisfaction with the intervention, and treatment fidelity data will also be collected. Data will be collected at pre-intervention, mid-intervention, post-intervention, and 3-month follow-up.</br> <br>Discussion: The aim of this paper is to describe the study protocol of a randomised controlled trial evaluating the effects of a combined intervention of Triple P Discussion Groups and Stress Control in comparison to a waitlist condition. This study is important because it will provide evidence about the effects of this combined intervention for parents with 3?8?year old children. The results of the study could be used to inform policy about parenting support and support for parents with mental health problems. Trial registration ClinicalTrial.gov: NCT01777724, UTN: U1111-1137-1053.</br&gt

Identifying metabolites by integrating metabolome databases with mass spectrometry cheminformatics.

Novel metabolites distinct from canonical pathways can be identified through the integration of three cheminformatics tools: BinVestigate, which queries the BinBase gas chromatography-mass spectrometry (GC-MS) metabolome database to match unknowns with biological metadata across over 110,000 samples; MS-DIAL 2.0, a software tool for chromatographic deconvolution of high-resolution GC-MS or liquid chromatography-mass spectrometry (LC-MS); and MS-FINDER 2.0, a structure-elucidation program that uses a combination of 14 metabolome databases in addition to an enzyme promiscuity library. We showcase our workflow by annotating N-methyl-uridine monophosphate (UMP), lysomonogalactosyl-monopalmitin, N-methylalanine, and two propofol derivatives