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We report a unique dynamic morphology transformation of a Ag+-coordinated supramolecular nanostructure accompanying the conversion of complex structures in aqueous solution. In the presence of AgNO3 (1.0 equiv), the achiral bipyridine-based ligand 1G, possessing hydrazine and glycine moieties, preferentially generated a 1D needle-like structure (nanostructure I) based on the 1GAgNO3 complex (1G:Ag+ = 1:1) as a metastable product. Nanostructure I was then transformed into nanostructure II, which was composed of the 1G3Ag2(NO3)2 complex (1G:Ag+ = 3:2) as the thermodynamically stable product. This nanostructure exhibited a 1D helical tubular structure with a uniform diameter via a 2D ribbon as an intermediator, which led to the generation of a circular dichroism (CD) signal with right-handed (P-type) helicity. The observed dynamic transformation was attributed to formation of the thermodynamically favored helical 1G3Ag2(NO3)2 complex. In addition, the helical 1G3Ag2(NO3)2 complex acted as an initiator in the transformation from the 1D needle-like structure to the 1D helical tube via a 2D ribbon. The enhanced ΔG° value of nanostructure II compared to that of nanostructure I confirmed that nanostructure II is thermodynamically stable. More importantly, the transformation of supramolecular nanostructure I to nanostructure II occurred via an "on" pathway, even though the 1GAgNO3 complex was converted to the 1G3Ag2(NO3)2 complex, which did not involve dissociation from nanostructure I into the monomeric 1GAgNO3 complex species. In the kinetic study, the NO3- anion was found to act as an accelerator for the dynamic transformation from nanostructure I to nanostructure II. This result provides the first example of a dynamic transformation of a 1D needle-like structure into a 1D tubular structure via a 2D ribbon structure, accompanied by the conversion of a complex structure and the generation of a large CD signal for the metallo-supramolecular nanostructure. This study may open up new avenues to the understanding of a dynamic morphology transformation process in biological systems.

Metal-coordination polymeric gels are interesting areas as organic/inorganic hybrid supramolecular materials. The bispicolylamine (BPA) based gelator (1) showed excellent gelation with typical fibrillar morphology in acetonitrile. Upon complexing 1 with Zn2+, complexes ([1 + Zn + ACN]2+ and [1 + zinc trifluoromethanesulfonate (ZnOTf )]+) with four coordination numbers were formed, which determine the gel structure significantly. A gel-sol transition was induced, driven by the ratio of the two metal complexes produced. Through nuclear magnetic resonance analysis, the driving forces in the gel formation (i.e., hydrogen-bonding and &pi, &ndash, &pi, stacking) were observed in detail. In the absence and the presence of Zn2+, the intermolecular hydrogen-bonds and &pi, stacking were the primary driving forces in the gel formation, respectively. In addition, the supramolecular gels exhibited a monolayer lamellar structure irrespective of Zn2+. Conclusively, the gels&rsquo, elasticity and viscosity reduced in the presence of Zn2+.

We report on the design and fabrication of a Fe3O4 core-mesoporous silica nanoparticle shell (Fe3O4@MSNs)-based mitochondria-targeting drug nanocarrier. A guanidinium derivative (GA) was conjugated onto the Fe3O4@MSNs as the mitochondria-targeting ligand. The fabrication of the Fe3O4@MSNs and their functionalization with GA were carried out by the sol-gel polymerization of alkoxysilane groups. Doxorubicin (DOX), an anti-cancer drug, was loaded into the pores of a GA-attached Fe3O4@MSNs due to both its anti-cancer properties and to allow for the fluorescent visualization of the nanocarriers. The selective and efficient mitochondria-targeting ability of a DOX-loaded GA-Fe3O4@MSNs (DOX/GA-Fe3O4@MSNs) was demonstrated by a co-localization study, transmission electron microscopy, and a fluorometric analysis on isolated mitochondria. It was found that the DOX/GA-Fe3O4@MSNs selectively accumulated into mitochondria within only five minutes; to the best of our knowledge, this is the shortest accumulation time reported for mitochondria targeting systems. Moreover, 2.6 times higher amount of DOX was accumulated in mitochondria by DOX/GA-Fe3O4@MSNs than by DOX/TPP-Fe3O4@MSNs. A cell viability assay indicated that the DOX/GA-Fe3O4@MSNs have high cytotoxicity to cancer cells, whereas the GA-Fe3O4@MSNs without DOX are non-cytotoxic; this indicates that the DOX/GA-Fe3O4@MSNs have great potential for use as biocompatible and effective mitochondria-targeting nanocarriers for cancer therapy.

Typical supramolecular gels do not exhibit electrical conductivity because of the wide band gaps present in the low-conjugation gelator molecules and the long distances between them, which arise because of the large amount of solvent within gel networks. Consequently, the practical applications of supramolecular gels are largely limited. Herein, a strategy for significantly enhancing the mechanical, electrical, and vibrational isolation properties of supramolecular gels derived from low-molecular-weight building blocks, which involves the incorporation of Cs+ ions, is described. High-elasticity supramolecular gels produced from the hydrazone reaction between calix[4]arene- and 18-crown-6-ether-based building blocks are mechanically strong and can be molded into free-standing objects. By controlling the concentration of Cs+ in the supramolecular gels, their mechanical and electrical properties can be tuned. The supramolecular gels exhibit 34-fold and 62-fold enhanced storage and loss moduli, respectively, upon addition of Cs+ ions. Furthermore, the electrical conductivities of the supramolecular gels proportionally increase with the amount of Cs+ ions in the gel network. These dramatic enhancements are due to the sandwich complex formation between the 18-crown-6 moieties and Cs+ ions. Also, the supramolecular gels reveal effective vibration-isolation abilities. It is believed that this strategy presents new possibilities for developing soft materials with unique functions.

We report on the cyano-OPV (1) possessing a trimethyl-locked quinone group exhibited monomer and aggregate emissions with distinct colors determined by the ratio of tetrahydrofuran/water (THF/H2O), thereby suggesting a strong dependence on the polarity of the solvent. In contrast, cyano-OPV (2) possessing an amine group exhibited a yellow emission in the THF/H2O mixture, regardless of the ratio of solvents used, which is indicative of the formation of a supramolecular aggregate by π-π stacking and intermolecular hydrogen-bonds. This further supports the AFM and DLS observations in which 1 and 2 are shown to be comprised of spherical nanoparticles with mean diameters of ~300 nm. The supramolecular aggregate 2 is generated by a cooperative pathway involving a nucleation-elongation mechanism. More interestingly, 1 was converted to 2 in the presence of NQO1 and NADPH, in a mixture of THF/H2O (20:80 v/v) at 37 °C, which lead to the formation of the supramolecular aggregate with its characteristic yellow emission.

Three different hydrates of LB30870, a new direct thrombin inhibitor, were identified during the screening of solid form, and their interconversion relationship and relative thermodynamic stabilities were investigated. Form I (hexahydrate) changes to Form II (dihydrate) or Form III (tetrahydrate) by dehydration, while Form II becomes Form I by hydration, and both Form II and Form III change to Form I in the aqueous slurry. Single crystals obtained from two different crystallization conditions, wet or air-dried, were found to be isostructural with a difference in the solvent channels, and based on the simulated and experimental powder X-ray diffraction patterns, the air-dried crystals are assigned as Form I and Form III, respectively. In all crystal structures, LB30870 is in a folded conformation forced by the presence of strong hydrogen bonds by two structural water molecules. The solvent channel formed can hold up to six additional hydration water sites per each LB30870, and the one-dimensional solvent c...

We demonstrate the different origins of helical directions in polymeric gels derived from a hydrazone reaction in the absence and presence of Ni2+. The right-handed helicity of polymeric gels without Ni2+ originates from the enantiomeric d-form alanine moiety embedded in the building block. However, the right-handed helicity is inverted to a left-handed helicity upon the addition of Ni2+, indicating that added Ni2+ greatly affects the conformation of the polymeric gel by overcoming the influence of the enantiomer embedded in the building block on the helicity at the supramolecular level. More interestingly, the ratio of the right-toleft-handed helical fibers varies with the concentration of Ni2+, which converts from 100% right-handed helical fiber to 90% left-handed helical fiber. In the presence of Ni2+, both right- and left-handed helical fibers coexist at the supramolecular level. Some fibers also exhibit both right- and left-handed helicities in a single fiber.

The viscoelastic and stiffness properties of azobenzene-based supramolecular gels have been investigated by rheometry and AFM. Interestingly, the viscoelastic properties of cis-isomers were 8–10 fold enhanced in comparison to the trans-isomer, which was a unique phenomenon. More interestingly, Young's modulus of gels increased linearly with time of UV irradiation. The stiffness of gels was finely controlled in the spatial micro-scale environment. The improved mechanical strength was attributed to electrostatic interaction with the production of radicals of the gelators.

The Potassium-based dry sorbent CO2 capture process can selectively capture CO2 from flue gas without toxicity. In this study, the optimization of regeneration condition was investigated to pursue economical CO2 capture process in a circulated fluidized bed reactor as most energy for CO2 capture is consumed in the sorbent regeneration. One important part for CO2 capture process is to produce highly concentrated CO2 during the sorbent regeneration in the conditions of CO2 rich with a presence of H2O, which thermodynamically reduces the sorbent regeneration efficiency at low temperature. This could be overcome by increasing the regeneration temperature although the sorbent regeneration energy increases. The dry sorbent performance in the carbonator was evaluated by changing the temperature, CO2 and H2O concentration in the regenerator, which showed about 88% CO2 removal efficiency and 5.6 wt% dynamic sorption capacity. The dry sorbent was sampled at each operating condition to confirm the dry sorbent performance, evaluated over CO2 concentration. The optimal regeneration condition was obtained by considering CO2 removal efficiency, dynamic sorption capacity and regeneration energy. Finally, the optimal regenerator temperature was determined to be approximately 468 K where the CO2 capture process in the circulated fluidized bed reactor showed 95% for CO2 purity.

Planar chirality inversion of pillar[5]arenes bearing d- or l-alanine substituents on both rims was investigated upon addition of guest molecules having pyridinium or imidazole moieties and long alkyl chains. The d- and l-alanine-substituted pillar[5]arenes exhibited pS and pR planar chirality, respectively. However, this planar chirality was inverted upon inclusion of certain achiral molecules, comprising pyridinium or imidazole moieties and long alkyl chains with terminal hydroxyl or methyl groups.

Chemical looping combustion (CLC) is a promising technology for fossil fuel combustion with inherent CO2 capture and sequestration that is able to mitigate greenhouse gases (GHGs) emission. The CLC process employs metal oxide as an oxygen carrier circulating between fuel reactor, where the fuel is combusted to CO2 and H2O, and air reactor, where the oxygen carrier returned to its oxidized form by aeration. In order to demonstrate and investigate the CLC concept experimentally, several previous studies have been carried out with the aim of improving the performance of oxygen carrier. The performance of the oxygen carrier, which circulate between the air reactor and the fuel reactor to transfer oxygen and heat, is the most important factor that determines the efficiency of the CLC process. In order to evaluate the reactivity of the oxygen carrier, the fuel conversion and CO2 selectivity of oxygen carrier have been investigated using thermogravimetric analyzer, batch type bubbling fluidized bed, etc. However, the hydrodynamic study for the solid circulation of oxygen carrier should be preceded to ensure the steady state operation of CLC process. In this study, the characteristics of solid circulation between the air reactor and the fuel reactor was examined in the bench scale CLC unit made of Plexiglas, and the effects of change of fuel reactor configuration and cyclone on the solid circulation between the two reactors were investigated. Ni based oxygen carrier was used as the bed material and the optimal fluidizing gas flow rate capable of maintaining stable solid circulation were investigated.

>> Reactivity of commercial WGS catalyst(MDC-7) and four new catalysts(RMC-3, PC-73, PC-67SU, PC-59) manufactured with various compositions by Korea Electric Power Research Institute(KEPCO RI) were compared to select suitable WGS catalyst for SEWGS system. Steam/CO ratio, gas velocity, flow rates of syngas,and temperature were considered as operating variables. As a result, MDC-7 catalyst showed the highest CO conversion and RMC-3 catalyst showed also high CO conversion. Therefore, MDC-7 and RMC-3 catalysts were selected as applicable catalysts. However, PC-73 catalyst showed low CO conversion at low temperature(200℃) but showed good reactivity at high temperature(225~250℃), and therefore, PC-73 catalyst was selected as applicablecatalyst for high temperature operation. Continuous operations up to 24 hours for those three catalysts(MDC-7,RMC-3, PC-73) were conducted to check reactivity decay of catalysts. All three catalysts maintained their originalreactivity. Key words

The self-sorting between aromaticcompounds that can serve as electron donors and electronacceptors allows the formation of distinct p- and n-typebundles of fibers that further intermix and generate multiplejunction points for efficient electron transfer and transport ofthe charge carriers. However, a difficulty associated withsimple mixing of such compounds is the possibility of adifferent mode of assembly, i.e., charge-transfer interactionmediated by alternate donor–acceptor stacking. Thus, ex-amples related to self-sorting among donor–acceptor chromo-phores have been limited.

We have synthesized a calix[4]arene derivative (1) containing terpyridine and showed that gelation occurred in the presence of Pt(2+) in DMSO/H2O of varying compositions. Gelation was presumably mediated by the Pt-Pt and π-π stacking interactions. The scanning electron microscopy image of the xerogel showed a spherical structure with diameter of 1.8-2.1 μm. Interestingly, the metallogel showed strong luminescence enhancement, which was dependent on the DMSO/H2O ratio of the solvent. We examined the effects of concentration, temperature, and time resolution on the luminescence emission of both the gel 1-Pt(2+) and the sol 1-Pt(2+). The luminescence lifetimes of the metallogel were particularly long, on the order of several microseconds. The luminescence lifetimes were also strongly dependent on the solvent composition. We also determined the thermodynamic parameters for the self-assembly of the gel by the Birks kinetic scheme. Furthermore, the rheological properties of the metallogels in the presence of more than 4.0 equiv of Pt(2+) were independent of the concentration of Pt(2+) applied.

Structure-based drug design was used to guide the optimization of a series of selective BTK inhibitors as potential treatments for Rheumatoid arthritis. Highlights include the introduction of a benzyl alcohol group and a fluorine substitution, each of which resulted in over 10-fold increase in activity. Concurrent optimization of drug-like properties led to compound 1 (RN486) ( J. Pharmacol. Exp. Ther. 2012 , 341 , 90 ), which was selected for advanced preclinical characterization based on its favorable properties.

This research explores the production of low-moisture, high-rank coal using a batch-type, laboratory-scale, circulating fluidized bed to dry low-rank Indonesian coal with a high moisture content of 35 wt%. The operation was performed using air as a fluidization gas in a riser (a 4-m-tall pipe with an inner diameter of 0.04 m) at a gas velocity ranging from 2.0 to 2.7 m/s and a riser temperature of 80 to 150°C. The electric heaters were installed in the upper part of a downcomer to prevent the condensation of the evaporated moist- ure. The drying rate of the coal was investigated in terms of the inlet gas temperature, the gas velocity, and the drying time in order to determine the optimum operating conditions. Changes in the moist- ure content of the coal, before and after the experiments, were char- acterized by a proximate analysis, an ultimate analysis, the higher heating value (HHV), the lower heating value (LHV), a particle size analysis, and by the equilibrium moisture content. The results show that ...

To develop SEWGS (sorption enhanced water gas shift) system using dry CO2 absorbent for pre-combustion CO2 capture, hydrodynamic characteristics of CO2 absorbents were measured and investigated. The minimum fluidization velocity of CO2 absorbent was measured and the effects of the operating conditions were investigated to operate the system at bubbling fluidized bed condition. The minimum fluidization velocity decreased as pressure and temperature increased. Moreover, the minimum fluidization velocity decreased as column diameter increased. The effects of operating conditions on the solid cir- culation rate were measured and investigated to select appropriate operating conditions for continuous CO2 capture and regenera- tion. The measured solid circulation rates were ranged between 10 and 65 kg/h and increased as the solid injection velocity, gas velocity in the regeneration reactor, and solid height increased.

A number of countries are mixing wood biomass with coal in existing coal-fired power plants according to the implementation of renewable portfolio standard (RPS) and cap-and-trade systems; problems arise due to mixing of the two fuels which have different combustion reactivities. In the previous work, research on glycerol impregnated hybrid fuel (Hybrid Coal by Korea Institute of Energy Research; HCK) was conducted for the diversification of bioliquid and issues to be resolved through further study in the application of glycerol to Hybrid Coal were noted. As a solution, a hydrogel having a small quantity of poly vinyl alcohol (PVA) added to glycerol was applied in the present work. PVA allowed the solidification of glycerol and contributed to the binding energy being stronger among glycerol derivatives and the surface of coal pore; thus, the fuel loss by readsorption of water can be inhibited by setting hydrogel into coal pores.

In the past few years, there have been many advances in the efforts to cure patients with hepatitis C virus (HCV). The ultimate goal of these efforts is to develop a combination therapy consisting of only direct-antiviral agents (DAAs). In this paper, we discuss our efforts that led to the identification of a bicyclic template with potent activity against the NS5B polymerase, a critical enzyme on the life cycle of HCV. In continuation of our exploration to improve the stilbene series, the 3,5,6,8-tetrasubstituted quinoline core was identified as replacement of the stilbene moiety. 6-Methoxy-2(1H)-pyridone was identified among several heterocyclic headgroups to have the best potency. Solubility of the template was improved by replacing a planar aryl linker with a saturated pyrrolidine. Profiling of the most promising compounds led to the identification of quinoline 41 (RG7109), which was selected for advancement to clinical development.

The splicing of pre-mRNA is a critical process in normal cells and is deregulated in cancer. Compounds that modulate this process have recently been shown to target a specific vulnerability in tumors. We have developed a novel cell-based assay that specifically activates luciferase in cells exposed to SF3B1 targeted compounds, such as sudemycin D6. This assay was used to screen a combined collection of approved drugs and bioactive compounds. This screening approach identified several active hits, the most potent of which were CGP-74514A and aminopurvalanol A, both have been reported to be cyclin-dependent kinases (CDKs) inhibitors. We found that these compounds, and their analogs, show significant cdc2-like kinase (CLK) inhibition and clear structure-activity relationships (SAR) at CLKs. We prepared a set of analogs and were able to ‘dial out’ the CDK activity and simultaneously developed CLK inhibitors with low nanomolar activity. Thus, we have demonstrated the utility of our exon-skipping assay and identified new molecules that exhibit potency and selectivity for CLK, as well as some structurally related dual CLK/CDK inhibitors.

New experimental method to measure solid descending velocity in a vertical downcomer was presented and effects of downcomer diameter and particle properties on descending velocities for Geldart group A, B, and D par- ticle have been measured and investigated. The effect of initial solid inventory on solid descending velocity was negli- gible. However, solid flow rate, solid circulation rate and solid descending velocity increased as the downcomer diameter increased. Moreover, solid descending velocity increased linearly as the downcomer diameter increased and showed distinguishable trend for Geldart group D particle from Geldart group A and B particles. Empirical correlations of solid descending velocity for Geldart group D and Geldart group A and B particles have been derived based on the measured values. The correlations could predict well the solid descending velocities.

Learnings from previous Roche p38-selective inhibitors were applied to a new fragment hit, which was optimized to a potent, exquisitely selective preclinical lead with a good pharmacokinetic profile.

LB71350 is an HIV protease inhibitor with poor aqueous solubility and extensive first pass effect. The purpose of the present study was to test the feasibility of solid dosage form of LB71350 with improved bioavailability utilizing solid dispersion. Three different compositions with varying ratio of (LB71350: Gelucire 44/14: Tween 20) were studied. Capsule filling of these solid dispersion compositions was tested using a semi-automatic capsule filling system. Oral bioavailability in dog was tested. Chemical and physical stability at 4, 25 and 40˚C was monitored by HPLC assay, dissolution test, powder XRD and microscopy. The capsule filling system yielded uniform products of drug loading up to 10%. Oral bioavailability in dog was improved compared to the aqueous suspension of crystalline LB71350. Capsules were chemically stable for up to 6 months at 40˚C. However, there were temperature and composition dependent physical changes. Decrease in dissolution rates after storage at 40˚C was due to the polymorphic change. In conclusion, manufacturing process, bioavailability, and physico-chemical stability have been considered to propose a solid dispersion capsule formulation for the HIV protease inhibitor with poor physico-chemical properties. A new less soluble crystalline form identified during the physical stability test warrants further study.

The development of a new series of p38α inhibitors resulted in the identification of two clinical candidates, one of which was advanced into a phase 2 clinical study for rheumatoid arthritis. The original lead, an lck inhibitor that also potently inhibited p38α, was a screening hit from our kinase inhibitor library. This manuscript describes the optimization of the lead to p38-selective examples with good pharmacokinetic properties.

Supramolecular gels comprised of low-molecular-weight gelators are generally regarded as mechanically weak and unable to support formation of free-standing structures, hence, their practical use with applied loads has been limited. Here, we reveal a technique for in situ generation of high tensile strength supramolecular hydrogels derived from low-molecular-weight gelators. By controlling the concentration of hydrochloric acid during hydrazone formation between calix-[4]arene-based gelator precursors, we tune the mechanical and ductile properties of the resulting gel. Organogels formed without hydrochloric acid exhibit impressive tensile strengths, higher than 40 MPa, which is the strongest among self-assembled gels. Hydrogels, prepared by solvent exchange of organogels in water, show 7,000- to 10,000-fold enhanced mechanical properties because of further hydrazone formation. This method of molding also allows the gels to retain shape after processing, and furthermore, we find organogels when prepared as gel electrolytes for lithium battery applications to have good ionic conductivity., The physical properties of gel materials makes them attractive options in various applications, but supramolecular gels typically lack mechanical strength. Here, the authors present a calix[4]arene-based supramoleculer gel tuned to possess high tensile strength.

In this work, chemical vapor deposition in a fluidized bed was employed for the immobilization of a photocatalyst on beads. By introducing carbon (TiOC), nitrogen (TiON) and iron (Fe/TiO 2 ) into TiO 2 matrix, samples were prepared, respectively. The X-ray diffractometer pattern of TiOC revealed a mixture of the anatase and rutile crystalline forms (65% and 34%, respectively) at the reaction temperature of 600 °C. TiOC absorbed in the visible region and showed photocatalytic activity in terms of isopropyl alcohol (IPA) degradation under a fluorescent lamp and blue light-emitting diode. TiON exhibited a shoulder in the absorption near 520 nm and was photocatalytically active under visible light at 460 nm. In the case of the Fe/TiO 2 species, lowering the bubbler temperature, i.e. reducing the amount of doped-iron, caused the rate of CO 2 evolution to increase during IPA degradation. Among studied species, Fe/TiO 2 under the condition of the bubbler temperature at 109 °C with a flow rate of 10 cm 3 /min showed highest photocatalytic activity in IPA degradation.

The splicing of pre-mRNA is a critical process in normal cells and is deregulated in cancer. Compounds that modulate this process have recently been shown to target a specific vulnerability in tumors. We have developed a novel cell-based assay that specifically activates luciferase in cells exposed to SF3B1 targeted compounds, such as sudemycin D6. This assay was used to screen a combined collection of approved drugs and bioactive compounds. This screening approach identified several active hits, the most potent of which were CGP-74514A and aminopurvalanol A, both have been reported to be cyclin-dependent kinases (CDKs) inhibitors. We found that these compounds, and their analogs, show significant cdc2-like kinase (CLK) inhibition and clear structure-activity relationships (SAR) at CLKs. We prepared a set of analogs and were able to ‘dial out’ the CDK activity and simultaneously developed CLK inhibitors with low nanomolar activity. Thus, we have demonstrated the utility of our exon-skipping assay and identified new molecules that exhibit potency and selectivity for CLK, as well as some structurally related dual CLK/CDK inhibitors. Citation Format: Yihui Shi, Jaehyeon Park, Chandraiah Lagisetti, Wei Zhou, Lidia C. Sambucetti, Thomas R. Webb. A triple exon-skipping luciferase reporter assay identifies a new CLK inhibitor scaffold [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2017; 2017 Apr 1-5; Washington, DC. Philadelphia (PA): AACR; Cancer Res 2017;77(13 Suppl):Abstract nr 4193. doi:10.1158/1538-7445.AM2017-4193

Glucokinase (GK) activators represent a class of type 2 diabetes therapeutics actively pursued due to the central role that GK plays in regulating glucose homeostasis. Herein we report a novel C5-alkyl-2-methylurea-substituted pyridine series of GK activators derived from our previously reported thiazolylamino pyridine series. Our efforts in optimizing potency, enzyme kinetic properties, and metabolic stability led to the identification of compound 26 (AM-9514). This analogue showed a favorable combination of in vitro potency, enzyme kinetic properties, acceptable pharmacokinetic profiles in preclinical species, and robust efficacy in a rodent PD model.

The characteristics of emission and heat transfer coefficient in a pressurized fluidized bed combustor are investigated. The pressure of the combustor is fixed at 6 atm. and the combustion temperatures are set to 850, 900, and 950 °C. The gas velocities are 0.9, 1.1, and 1.3 m/s and the excess air ratios are 5, 10, and 20%. The desulfurization experiment is performed with limestone and dolomite and Ca/S mole ratios are 1,2, and 4. The coal used in the experiment is Cumnock coal from Australia. All experiments are executed at 2 m bed height. In this study, the combustion efficiency is higher than 99.8% through the experiments. The heat transfer coefficient affected by gas velocity, bed temperature and coal feed rate is between 550-800 W/m2 °C, which is higher than those of AFBC and CFBC. CO concentration with increasing freeboard temperature decreases from 100 ppm to 20 ppm. NOx concentration in flue gas is in the range of 5-130 ppm and increases with increasing excess air ratio. N2O concentration in flue gas decreases from 90 to 10 ppm when the bed temperature increases from 850 to 950 °C.

Thousands of ppmv of hydrogen sulfide included in coal gas should be reduced to less than a hundred ppmv in the case of IGCC to prevent a gas turbine from being corroded, and few ppmv to prevent the performance of electrodes from declining in the case of MCFC. In the present paper a laboratory scale AEBG (Agitation Fluidized Bed Granulator) is made and improved. The sorbent for the removal of hydrogen sulfide is produced using an agitation fluidized bed granulator (ZnO 1.5 mole+TiO2 l.0mole+bentonite 5.0 wt%). The techniques for fluidizing fine particles, classified in Geldart C group, in a fluidized bed are developed by installing an agitator blade in a fluidized bed granulator. The fine particles are fluidized and granulated successfully by using the techniques. Statistical, spectral and chaos analyses with granulated sorbent (100-300 Μm) are performed to investigate the hydrodynamics of granulates in a fluidized bed. The average absolute deviation, power spectral density functions, phase space trajectories, and Kolmogorov entropy obtained from pressure fluctuation are plotted as a function of fluidizing velocity. It is shown that the Kolmogorov entropy implying the rate of generation of information can be applied to the control of fluidization regimes.

A new technique of thermal fluidized-bed metal-organic chemical vapor deposition (FB-MOCVD) was developed to prepare titania nano-coated silica-gel beads on a large scale (20 kg/batch) at different deposition temperatures of 450, 500, 550, and 600°C. Titanium tetra iso-propoxide (TTIP, Ti[OCH(CH3)2]4, Aldrich Chemical Co.) was used as a precursor of titania. The titania nano-coated silica-gel beads prepared by FB-MOCVD apparatus were hardly breakable compared to other common coating techniques in liquid phase such as sol-gel and dipping method. It was found that, from the FE-SEM/EDXS analysis and XPS results, the surfaces of silica-gel beads were covered with particle forms of titania. The photocatalytic degradation of acetaldehyde into CO2 and H2O was not much affected by deposition temperature.

A special spear-tip semisolid electrode has been used to measure the pH of solid oxide-aqueous slurries at very high solid to liquid ratios. A simple non-Nernstian model of the oxide charging along with the experimental results demonstrate a very strong buffering effect of common oxide surfaces at high oxide content. This provides a simple, accurate measurement of oxide PZC which compares favorably to other common methods for PZC determination. The ramifications of the buffering effect on catalyst preparation are discussed.

MAP4K4, a Ser/Thr kinase, was identified as an important pro-migratory kinase in an siRNA screen, targeting 5,234 human genes for modulators of tumor cell motility. MAP4K4 siRNA potently suppressed cell invasion and migration of multiple cancer cell lines, indicating a broad role in cell motility. There are no drugs in the clinic that are known to specifically target MAP4K4 for cancer therapy. We have successfully developed an orally active, highly effective and selective MAP4K4 inhibitor (SRI-28731) with potent in vitro and in vivo anticancer activity. SRI-28731 is more potent than Paclitaxel (Taxol) against most of the breast cancer cell lines tested. SRI-28731 exhibits more potent activities against triple negative (MDA-MB-231, BT549 and Hs578T) than estrogen-dependent (T47D and MCF-7) breast cancer cell lines, and its potency is positively correlated with MAP4K4 expression in cancer cell lines. SRI-28731 is also more potent than Docetaxel against both androgen-dependent (LNCaP) and -independent (PC-3 and DU-145) prostate cancer cell lines. In vitro mechanistic studies showed that SRI-28731 induced apoptosis and a time-dependent M phase arrest. Treatment with SRI-28731 (12.5, 25 and 50 mg/kg/day) caused a significant dose-dependent growth reduction of PC-3 tumors (30%, 61% and 88% growth inhibition, respectively), while Docetaxel at its MTD (7.5 mg/kg; Q3Dx2) produced only 10-15% growth inhibition. At the end of PC-3 tumor xenograft studies, we conducted an ex vivo invasion assay using PC-3 tumor cells isolated from tumor-bearing mice. SRI-28731 significantly reduced ex vivo tumor cell invasion by ∼80%. Pharmacokinetic studies showed that SRI-28731 could be detected in plasma up to 8 hours after oral dosing, and drug plasma concentrations remained above the IC50 values needed to inhibit prostate or breast cancer proliferation. To quantitatively define the kinase selectivity of SRI-28731, we tested the interaction of SRI-28731 with 456 kinase protein kinases (KINOMEscan), followed by in vitro pharmacology studies. Our data indicated that SRI-28731 is a highly selective Type-II MAP4K4 inhibitor. Type II kinase inhibitors bind to both the ATP site and an adjacent hydrophobic site exposed in the non-activated kinase state. Generally, type II inhibitors show higher selectivity for targets, and act primarily by locking the equilibrium switch between conformational states in a way that prevents kinase activation, rather than directly inhibiting it. Elevated MAP4K4 expression is strongly associated with higher rate of metastasis, and is regarded as an independent predictor of overall survival in cancer patients. Since MAP4K4 is overexpressed in many human cancer cell lines but is undetectable in non-transformed epithelial cells, targeting MAP4K4 may provide effective anti-metastatic therapy with limited side effects on normal tissues. Citation Format: Chih-Tsung Chang, Jaehyeon Park, Wei Zhou, Xiaohe Liu, Barbara Sato, Dominic Dinh, Anna Furimsky, Lucia Beviglia, Lidia Sambucetti, Ling Jong. SRI-28731, a highly potent and selective MAP4K4 (HGK) inhibitor for cancer therapy. [abstract]. In: Proceedings of the 105th Annual Meeting of the American Association for Cancer Research; 2014 Apr 5-9; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2014;74(19 Suppl):Abstract nr 731. doi:10.1158/1538-7445.AM2014-731