Investigation of theoretical maximum water yield and efficiency-optimized temperature for cyclopentane hydrate-based desalination.

Hydrate-based desalination (HBD) shows promise as a freshwater production technology for saline water. Liquid-phase hydrate formers, with their ability to facilitate hydrate formation at atmospheric pressure, have gained attention for their high energy efficiency in HBD. This study explored cyclopentane (CP) HBD by experimentally measuring the thermodynamic properties of CP hydrate in saline solutions and developing a theoretical framework to estimate the water yield of CP HBD under various operating conditions. The measured dissociation enthalpy of CP hydrate was found to be 12 % and 22 % lower compared to those of propane and R134a hydrates, respectively. The equilibrium dissociation temperatures of CP hydrate at different NaCl concentrations under atmospheric pressure were experimentally measured and then predicted using the Hu-Lee-Sum correlation. The theoretically achievable maximum salinity and water yield for CP HBD were calculated in the temperature range of 268-280 K and the initial salinity range of 0-8 wt.%. Additionally, the concept of HBD heat efficiency, representing the maximum amount of pure water producible per unit of heat, was introduced to identify an optimal operating condition for the HBD process. Efficiency-maximized temperatures, where the HBD heat efficiency reached its peaks, were determined for various initial salinities in the process, for example, 273.4 K for NaCl 3.5 wt.% solution. This novel approach provides invaluable guidance for determining the most energy-efficient operating conditions in the HBD process and establishes a solid foundation for further advancements in this field.

Application of Silver Nanofluids on Kinetics of Sulfur Hexafluoride Gas Hydrate Formation.

Gas hydrates are nonstoichiometric nano-structured crystalline compounds which are stabilized by gas molecules incorporated in the cages made of hydrogen bonding of water molecules at suitable thermodynamic conditions. The gas hydrate as a technology has been successful for several potential applications in various engineering fields, such as, gas separation, carbon dioxide sequestration, gas storage and transportation, desalination of salt water and wastewater treatment. Recently, metal-based nanofluids are considered as interesting kinetic promoter candidates for accelerating formation of gas hydrates. Although organic-based kinetic promoters are widely studied for the rapid formation of gas hydrates, research of a new material system is still a challenge. In this study, Silver (Ag) nanofluids as kinetic promoter of sulfur hexafluoride (SF6) hydrate were prepared by electrical explosion of pure metal wire in deionized water. The kinetics of SF6 gas hydrates were evaluated with different concentration of Ag nanofluids at condition of 276 K and 0.7 MPa, respectively. The Ag nanofluids, as kinetic nano-prompter, showed excellent effect on the formation of SF6 hydrates.

Preparation and Characterization of Poly Methyl Methacrylate/Clay Nanocomposite Powders by Microwave-Assisted In-Situ Suspension Polymerization.

The PMMA (poly methyl methacrylate)/clay nanocomposite powders were synthesized by In-Situ suspension polymerizations using microwave heating. The PMMA/clay nanocomposites were also sampled using injection moulding to make specimens for material characterization. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) indicated the formation of a highly intercalated clay layer in the nanocomposites. It was found that the microstructure of PMMA/clay nanocomposites was strongly dependent of content of clay. Thermo gravimetric analysis (TGA) indicated an improvement in the thermal stability of nanocomposites compared to that of the pure PMMA. Differential scanning calorimetry (DSC) showed that the nanocomposites had a higher glass transition (Tg) temperature than the PMMA. Fourier-transform infrared (FT-IR) spectroscopy indicated an interaction between the carbonyl group of PMMA and hydroxyl group of the clay. Therefore, a possible reason in enhanced material properties of nanocomposites is that the chemical interaction and nanostructure of PMMA polymer and intercalated inorganic silicate layer has increased the thermal stability of the PMMA/clay nanocomposites.

Identification of proteins suppressing the functions of oncogenic phosphatase of regenerating liver 1 and 3.

The phosphatase of regenerating liver (PRL) family, including PRL-1, PRL-2, and PRL-3, comprises protein tyrosine phosphatases whose deregulation is associated with the tumorigenesis and metastasis of many types of cancer. However, the underlying mechanism is poorly understood. In this study, aiming to increase understanding of the molecular mechanisms underlying the functions of PRL-1 and PRL-3, a yeast two-hybrid system was employed to screen for their interacting proteins. Alignment with the NCBI BLAST database revealed 12 interactive proteins: Synaptic nuclear envelope protein 2, emerin, mannose 6-phosphate receptor-binding protein 1, low-density lipoprotein receptor-related protein 10, Rab acceptor 1, tumor protein D52-like 2, selectin P ligand (SELPLG), guanylate binding protein 1, transmembrane and ubiquitin-like domain-containing 2, NADH:ubiquinone oxidoreductase subunit B8, syndecan 4 and FK506-binding protein 8 (FKBP8). These proteins are associated with cell proliferation, apoptosis, immune response, cell fate specification and metabolic process in biological process categories, and involved in various signaling pathways, including Alzheimer's disease, Parkinson's disease, Huntington's disease, hypertrophic cardiomyopathy and cell adhesion molecules. Interactions of PRL-1 with the prey proteins SELPLG and FKBP8 were confirmed by immunoprecipitation or immunostaining. Furthermore, SELPLG and FKBP8 suppressed PRL-1- or PRL-3-mediated p53 activity. Identification of the proteins interacting with PRL family proteins may provide valuable information to better understand the mechanism of PRL-mediated signal transduction in cancer and other diverse diseases.

Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids.

Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.

Long and short range order structural analysis of In-situ formed biphasic calcium phosphates.

BACKGROUND: Biphasic calcium phosphates (BCP) have attracted considerable attention as a bone graft substitute. In this study, BCP were prepared by aqueous co-precipitation and calcination method. The crystal phases of in-situ formed BCP consisting of hydroxyapatite (HAp) and ß-tricalcium phosphate (ß-TCP) were controlled by the degree of calcium deficiency of precursors. The long and short range order structures of biphasic mixtures was investigated using Rietveld refinement technique and high resolution Raman spectroscopy. The refined structural parameters of in-situ formed BCP confirmed that all the investigated structures have crystallized in the corresponding hexagonal (space group P63/m) and rhombohedral (space group R3c) structures. RESULTS: The crystal phases, Ca/P molar ratio, and lattice parameters of in-situ formed BCP consisting of HAp and ß-TCP were controlled by the degree of calcium deficiency of calcium phosphate precursors. The significant short range order structural change of BCP was determined by Raman analysis. CONCLUSIONS: The long and short range order structural changes of in-situ formed BCP might be due to the coexistence of ß-TCP and HAp crystal phases.

Synergistic hydrate inhibition of monoethylene glycol with poly(vinylcaprolactam) in thermodynamically underinhibited system.

This study investigates the hydrate inhibition performance of monoethylene glycol (MEG) with poly(vinylcaprolactam) (PVCap) for retarding the hydrate onset as well as preventing the agglomeration of hydrate particles. A high-pressure autoclave was used to determine the hydrate onset time, subcooling temperature, hydrate fraction in the liquid phase, and torque changes during hydrate formation in pure water, 0.2 wt % PVCap solution, and 20 and 30 wt % MEG solutions. In comparison to water with no inhibitors, the addition of PVCap delays the hydrate onset time but cannot reduce the hydrate fraction, leading to a sharp increase in torque. The 20 and 30 wt % MEG solutions also delay the hydrate onset time slightly and reduce the hydrate fraction to 0.15. The addition of 0.2 wt % PVCap to the 20 wt % MEG solution, however, delays the hydrate onset time substantially, and the hydrate fraction was less than 0.19. The torque changes were negligible during the hydrate formation, suggesting the homogeneous dispersion of hydrate particles in the liquid phase. The well-dispersed hydrate particles do not agglomerate or deposit under stirring. Moreover, when 0.2 wt % PVCap was added to the 30 wt % MEG solution, no hydrate formation was observed for at least 24 h. These results suggest that mixing of MEG with a small amount of PVCap in underinhibited conditions will induce the synergistic inhibition of hydrate by delaying the hydrate onset time as well as preventing the agglomeration and deposition of hydrate particles. Decreasing the hydrate fraction in the liquid phase might be the reason for negligible torque changes during the hydrate formation in the 0.2 wt % PVCap and 20 wt % MEG solution. Simple structure II was confirmed by in situ Raman spectroscopy for the synergistic inhibition system, while coexisting structures I and II are observed in 0.2 wt % PVCap solution.

Thermodynamic and spectroscopic identification of guest gas enclathration in the double tetra-n-butylammonium fluoride semiclathrates.

The precise nature and unique pattern of the double tetra-n-butylammonium fluoride (TBAF) semiclathrates with a guest gas (CH(4) or CO(2)) was closely investigated through thermodynamic and spectroscopic analyses. The three-phase equilibria of semiclathrate (H), liquid water (L(W)), and vapor (V) for the ternary CH(4) + TBAF + water and CO(2) + TBAF + water mixtures with various TBAF concentrations were experimentally measured in order to determine the stability conditions of the double TBAF semiclathrates. The double CH(4) (or CO(2)) + TBAF semiclathrates showed remarkably enhanced thermal stability when compared with pure CH(4) (or CO(2)) hydrate. The highest stabilization effect was observed at the stoichiometric concentration of pure TBAF semiclathrate, which is 3.3 mol %. Gas uptake measurements were undertaken in order to estimate the amount of gas consumed during double semiclathrate formation. CH(4) was found to be a relatively more favorable guest for the 5(12) cages of the double TBAF semiclathrate than CO(2). From the results of the NMR and Raman spectroscopic analyses it was identified that the guest gas molecules (CH(4) or CO(2)) were enclathrated in the 5(12) cages of the double TBAF semiclathrates. The overall results given in this study are useful for understanding the fundamental guest gas enclathration behavior in the double semiclathrates.

The essential role of FKBP38 in regulating phosphatase of regenerating liver 3 (PRL-3) protein stability.

The phosphatase of regenerating liver-3 (PRL-3) is a member of protein tyrosine phosphatases and whose deregulation is implicated in tumorigenesis and metastasis of many cancers. However, the underlying mechanism by which PRL-3 is regulated is not known. In this study, we identified the peptidyl prolyl cis/trans isomerase FK506-binding protein 38 (FKBP38) as an interacting protein of PRL-3 using a yeast two-hybrid system. FKBP38 specifically binds to PRL-3 in vivo, and that the N-terminal region of FKBP38 is crucial for binding with PRL-3. FKBP38 overexpression reduces endogenous PRL-3 expression levels, whereas the depletion of FKBP38 by siRNA increases the level of PRL-3 protein. Moreover, FKBP38 promotes degradation of endogenous PRL-3 protein via protein-proteasome pathway. Furthermore, FKBP38 suppresses PRL-3-mediated p53 activity and cell proliferation. These results demonstrate that FKBP38 is a novel regulator of the oncogenic protein PRL-3 abundance and that alteration in the stability of PRL-3 can have a dramatic impact on cell proliferation. Thus, FKBP38 may play a critical role in tumorigenesis.

Crystallographic and mutational analysis of the CD40-CD154 complex and its implications for receptor activation.

CD40 is a tumor necrosis factor receptor (TNFR) family protein that plays an important role in B cell development. CD154/CD40L is the physiological ligand of CD40. We have determined the crystal structure of the CD40-CD154 complex at 3.5 Å resolution. The binding site of CD40 is located in a crevice formed between two CD154 subunits. Charge complementarity plays a critical role in the CD40-CD154 interaction. Some of the missense mutations found in hereditary hyper-IgM syndrome can be mapped to the CD40-CD154 interface. The CD40 interaction area of one of the CD154 subunits is twice as large as that of the other subunit forming the binding crevice. This is because cysteine-rich domain 3 (CRD3) of CD40 has a disulfide bridge in an unusual position that alters the direction of the ladder-like structure of CD40. The Ser(132) loop of CD154 is not involved in CD40 binding but its substitution significantly reduces p38- and ERK-dependent signaling by CD40, whereas JNK-dependent signaling is not affected. These findings suggest that ligand-induced di- or trimerization is necessary but not sufficient for complete activation of CD40.

Separation of SF6 from gas mixtures using gas hydrate formation.

This study aims to examine the thermodynamic feasibility of separating sulfur hexafluoride (SF(6)), which is widely used in various industrial fields and is one of the most potent greenhouse gases, from gas mixtures using gas hydrate formation. The key process variables of hydrate phase equilibria, pressure-composition diagram, formation kinetics, and structure identification of the mixed gas hydrates, were closely investigated to verify the overall concept of this hydrate-based SF(6) separation process. The three-phase equilibria of hydrate (H), liquid water (L(W)), and vapor (V) for the binary SF(6) + water mixture and for the ternary N(2) + SF(6) + water mixtures with various SF(6) vapor compositions (10, 30, 50, and 70%) were experimentally measured to determine the stability regions and formation conditions of pure and mixed hydrates. The pressure-composition diagram at two different temperatures of 276.15 and 281.15 K was obtained to investigate the actual SF(6) separation efficiency. The vapor phase composition change was monitored during gas hydrate formation to confirm the formation pattern and time needed to reach a state of equilibrium. Furthermore, the structure of the mixed N(2) + SF(6) hydrate was confirmed to be structure II via Raman spectroscopy. Through close examination of the overall experimental results, it was clearly verified that highly concentrated SF(6) can be separated from gas mixtures at mild temperatures and low pressure conditions.

Pure SF6 and SF6-N2 mixture gas hydrates equilibrium and kinetic characteristics.

Sulfur hexafluoride (SF6), whether pure or mixed with inexpensive inert gas, has been widely used in a variety of industrial processes, but it is one of the most potent greenhouse gases. For this reason, it is necessary to separate and/or collect it from waste gas streams. In this study, we investigated the pure SF6 and SF6-N2 mixture gas hydrates formation equilibrium aswell asthe gas separation efficiency in the hydrate process. The equilibrium pressure of SF6-N2 mixture gas was higher than that of pure SF6 gas. Phase equilibrium data of SF6-N2 mixture gas was similar to SF6 rather than N2. The kinetics of SF6-N2 mixture gas was controlled by the amount of SF6 at the initial gas composition as well as N2 gas incorporation into the S-cage of structure-II hydrate preformed by the SF6 gas. Raman analysis confirmed the N2 gas incorporation into the S-cage of structure-II hydrate. The compositions in the hydrate phase were found to be 71, 79, 80, and 81% of SF6 when the feed gas compositions were 40, 65, 70, and 73% of SF6, respectively. The present study provides basic information for the separation and purification of SF6 from mixed SF6 gas containing inert gases.

Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

Surfactant effects on SF6 hydrate formation.

Sulfur hexafluoride (SF(6)) has been widely used in a variety of industrial processes, but it is one of the most potent greenhouse gases. For this reason, it is necessary to separate or collect it from waste gas streams. One separation method is through hydrate crystal formation. In this study, SF(6) hydrate was formed in aqueous surfactant solutions of 0.00, 0.01, 0.05, 0.15 and 0.20 wt% to investigate the effects of surfactants on the hydrate formation rates. Three surfactants, Tween 20 (Tween), sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS), were tested in a semi-batch stirred vessel at the constant temperature and pressures of 276.2 K and 0.78 MPa, respectively. All surfactants showed kinetic promoter behavior for SF(6) hydrate formation. It was also found that SF(6) hydrate formation proceeded in two stages with the second stage being the most rapid. In situ Raman spectroscopy analysis revealed that the increased gas consumption rate with the addition of surfactant was possibly due to the increased gas filling rate in the hydrate cavity.