CO2 Desorbs Water from K-MER Zeolite under Equilibrium Control.

Competitive adsorption by water in zeolites is so strongly prevalent that established gravimetric techniques for quantification have assumed that humid CO2 has no effect on preadsorbed water at the same relative humidity. Here, we demonstrate sites in small-pore zeolite K-MER, in which CO2 adsorption causes 20% of preabsorbed water to desorb under equilibrium control at 30 °C and 5% relative humidity. Diffuse reflectance IR spectroscopic data demonstrate that dimeric water species that are coordinated to cationic sites in K-MER zeolite are selectively displaced by CO2 under these humid conditions. Though Cs-RHO contains more weakly bound water than K-MER, we observe a lack of dimeric water species and no evidence of CO2 outcompeting water in Cs-RHO. We conclude that the desorption of water by CO2 in K-MER is driven by a highly desired site for CO2 adsorption as opposed to an intrinsically weak binding of water to the zeolite. Our demonstration that CO2 can outcompete water in a zeolite under wet conditions introduces new opportunities for the design of selective sites for humid CO2 adsorption and stresses the importance of independently characterizing adsorbed water and CO2 in these systems.

In situ spectroscopic studies of the effect of water on the redox cycle of Cu ions in Cu-SSZ-13 during selective catalytic reduction of NOx.

The effect of water on the NH3-assisted selective catalytic reduction of NOx (NH3-SCR) has been largely neglected, despite the inevitable presence of water vapor in real emissions produced by fuel combustion. In this work, we investigated the role of water in the behavior of active Cu2+ ions in Cu-SSZ-13 in the NH3-SCR reaction. The addition of water to the reactant feed leads to significantly increased NOx reduction over the catalyst. By combining in situ DRIFTS and XANES analyses during the NH3-SCR reaction, we found that the redox cycle of Cu ions is promoted by the presence of water.

Mobility of Cu Ions in Cu-SSZ-13 Determines the Reactivity of Selective Catalytic Reduction of NOx with NH3.

Selective catalytic reduction of NOx with NH3 (NH3-SCR) in Cu-SSZ-13 has been proposed to have a unique homogeneous-like mechanism governed by the spatial proximity of mobile Cu ions. Among factors that determine the proximity, the effect of ion density on the SCR reaction is well established; however, it has not been verified how the different mobility of the Cu ion influences the SCR reaction. Herein, we try to reveal the mobility-dependent SCR reaction by controlling the Cu species with different ion mobilities in Cu-SSZ-13. Since the reaction kinetics is governed by the diffusion of Cu ions, the Cu ion mobility determines the reactivity of the Cu-SSZ-13. In terms of this correlation, enhanced ion mobility leads to improved NH3-SCR activity. These findings help understand the behavior of Cu ions in Cu-SSZ-13 under a catalytic reaction and provide insights to design rational catalysts by tuning the ion mobility.

Enhanced activity of vanadia supported on microporous titania for the selective catalytic reduction of NO with NH3: Effect of promoters.

Vanadium oxide-based catalysts are considered a promising catalyst for selective catalytic reduction (SCR) of NO with NH3, which is an effective NOx removal technology. As environmental issues have garnered more attention, however, improvements to vanadium-based SCR catalysts are strongly required. In a previous study, we found that vanadium oxide on microporous titania as a support (V/MPTiO2) has certain advantages, such as improved thermal stability and more suppressed N2O formation, over the use of conventional nanoparticle titania (DT-51) as a support. In this study, widely used promoters, such as W, Sb, and Mo, were added to V/MPTiO2 to investigate whether they have promoting effects on V/MPTiO2 as well. Among these promoters added catalysts, the W and Mo were found to have significant promoting effects on the enhancement of deNOx activities at low temperatures, while the addition of Sb to V/MPTiO2 tended to have a negative effect on the SCR activity. Based on the characterizations, including laser Raman, H2-temperature programmed reduction (H2-TPR), and in situ diffuse reflectance infrared Fourier transform (in situ DRIFT) analysis, we found that the addition of W and Mo increased the degree of polymerization in V/MPTiO2, which generated more reactive vanadia species. Hence, such changes, resulting from the addition of W and Mo promoters to V/MPTiO2, yielded enhanced catalytic activity at low temperatures.

Simple physical mixing of zeolite prevents sulfur deactivation of vanadia catalysts for NOx removal.

NOx abatement has been an indispensable part of environmental catalysis for decades. Selective catalytic reduction with ammonia using V2O5/TiO2 is an important technology for removing NOx emitted from industrial facilities. However, it has been a huge challenge for the catalyst to operate at low temperatures, because ammonium bisulfate (ABS) forms and causes deactivation by blocking the pores of the catalyst. Here, we report that physically mixed H-Y zeolite effectively protects vanadium active sites by trapping ABS in micropores. The mixed catalysts operate stably at a low temperature of 220 °C, which is below the dew point of ABS. The sulfur resistance of this system is fully maintained during repeated aging/regeneration cycles because the trapped ABS easily decomposes at 350 °C. Further investigations reveal that the pore structure and the amount of framework Al determined the trapping ability of various zeolites.

Time-resolved observation of V2O5/TiO2 in NH3-SCR reveals the equivalence of Brønsted and Lewis acid sites.

The involvement of Lewis and Brønsted acid sites on V2O5/TiO2 catalyst in the selective catalytic reduction of NO with NH3 (NH3-SCR) is under debate. Here, a Li doping strategy is applied to selectively block Brønsted sites, which aims to prepare model catalysts with the same V loading but different ratios of the two acid sites. Time-resolved in situ DRIFTS observation demonstrates that the surface ammonia species pre-adsorbed on Lewis and Brønsted sites can participate equally in the reaction. Consideration of site redistribution in the early stages of the transient reaction is key to accurate measurement of the ammonia consumption rate.

Mycobacterium tuberculosis Rv3463 induces mycobactericidal activity in macrophages by enhancing phagolysosomal fusion and exhibits therapeutic potential.

Macrophages are responsible for innate and adaptive immune response activation necessary for eliminating infections. Optimal activation of macrophages to phagocytize Mycobacterium tuberculosis is critical in anti-mycobacterial defense. Here, we identified a novel Rv3463 hypothetical protein that induces macrophage activation in Mtb culture filtrate. Recombinant Rv3463 activated mouse bone marrow-derived macrophages to induce the expression of surface molecules and secrete pro-inflammatory cytokines via the TLR2 and TLR4 pathways. Mitogen activated protein kinase, phospatidylinositol-4,5-bisphosphate 3-kinases, and the NF-κB signaling pathways are involved in Rv3463-mediated macrophage activation. Furthermore, Rv3463 induced bactericidal effects in Mtb-infected macrophages through phagosome maturation and phagolysosomal fusion enhanced by phospatidylinositol-4,5-bisphosphate 3-kinases and Ca2+ signaling pathways and exhibited therapeutic effects in a short-term Mtb-infection mouse model. Overexpression of Rv3463 in M. smegmatis caused rapid clearance of bacteria in macrophages and mice. Our study suggests that Rv3463 is a promising target for the development of post-exposure tuberculosis vaccines or adjunct immune-therapy.

Observation of Restored Topological Surface States in Magnetically Doped Topological Insulator.

The introduction of ferromagnetic order in topological insulators in general breaks the time-reversal symmetry and a gap is opened in topological surface bands. Various studies have focused on gap-opened magnetic topological insulators, because such modified band structures provide a promising platform for observing exotic quantum physics. However, the role of antiferromagnetic order in topological insulators is still controversial. In this report, we demonstrate that it is possible to restore the topological surface states by effectively reducing the antiferromagnetic ordering in Gd-substituted Bi2Te3. We successfully control the magnetic impurities via thermal treatments in ultra-high vacuum condition and observe apparent restoration of topological surface band dispersions. The microscopic mechanism of atomic rearrangements and the restoration process of topological surface states are unraveled by the combination of scanning tunneling microscopy measurements and density functional theory calculations. This work provides an effective way to control the magnetic impurities which is strongly correlated with topological surface states.

Rotation-Assisted Hydrothermal Synthesis of Thermally Stable Multiwalled Titanate Nanotubes and Their Application to Selective Catalytic Reduction of NO with NH3.

Titanate nanotubes are widely applied in various fields, including photocatalysts and electronic devices, but their weak thermal stability limits their application for catalyst support. Here, we found that titanate nanotubes with a thick multiwalled structure of 15 layers or more can be prepared by using rotation-assisted hydrothermal synthesis. The porous structure of conventional nanotubes synthesized without rotation collapsed easily after thermal treatment, whereas the nanotubes having a thick multiwalled structure retained their pore structure and the specific surface area (∼300 m2/g) even after calcination at 400 °C in air. Systematic variation of rotation speed suggested that rotation in the synthesis process accelerated the stacking of layered titanate nanosheets, which are known to be intermediates of nanotubes. Thus, the rapid assembly of titanate nanosheets facilitated by rotation led to the formation of nanotubes with a multiwalled structure. Overly fast rotation, however, caused excessive stacking and created a thicker structure that cannot be easily wrapped into nanotubes. Therefore, it is essential to maintain the optimum rotation speed to obtain both the nanotube morphology and the thick multiwalled structure. Vanadium-tungsten-oxide catalyst supported on the multiwalled titanate nanotubes was used in NH3-selective catalytic reduction, which showed stable NO x reduction performance with high selectivity to N2, which may originate from the suppressed sintering of VO x on multiwalled nanotubes. This study demonstrates that the morphology of nanotubes can be tuned by controlling the degree of interaction supplied by external forces.

Origin of first-order-type electronic and structural transitions in IrTe2.

We have explored the origin of unusual first-order-type electronic and structural transitions in IrTe2, based on the first-principles total energy density functional theory analysis. We have clarified that the structural transition occurs through the interplay among the charge density wavelike lattice modulation with q1/5=(1/5,0,1/5), in-plane dimer ordering, and the uniform lattice deformation. The Ir-Ir dimer formation via a molecular-orbital version of the Jahn-Teller distortion in the Ir-Ir zigzag stripe is found to play the most important role in producing the charge disproportionation state. Angle-resolved photoemission spectroscopy reveals the characteristic features of structural transition, which are in good agreement with the density functional theory bands obtained by the band-unfolding technique.

hKv1.5 channels play a pivotal role in the functions of human alveolar macrophages.

We examined the pharmacological properties, the molecular identity, and the functional roles of hKv1.5 channel in human alveolar macrophage. Some of outward K(+) current was inhibited by 4-aminopyridine and antisense oligodeoxynucleotides against hKv1.5 mRNA. Consistently, the protein and mRNA expressions of hKv1.5 channel were detected. Furthermore, the phagocytosis and migration of human alveolar macrophages were significantly suppressed when the protein expression of hKv1.5 channel was lowered by the antisense hKv1.5 oligodeoxynucleotides. These results suggest that hKv1.5 channel is expressed in human alveolar macrophages and it plays a role in phagocytosis and migration of the human alveolar macrophage.

A novel fluorometric assay for ADP-ribose pyrophosphatase activity.

ADP-ribose pyrophosphatase (ADPRase) hydrolyzes ADP-ribose to ribose-5-phosphate and AMP. The ADPRase activity have been assessed by coupling the reaction to alkaline phosphatase and colorimetrically measuring the amount of inorganic phosphate released from AMP that is one of the products of ADPRase. Another but less sensitive colorimetric method has been employed: the reaction mixture was treated with charcoal to adsorb the adenine-containing compounds such as AMP and ADPR and subsequently remaining ribose-5-phosphate was measured colorimetrically. However, the measurement of inorganic phosphate cannot be feasible to assay ADPRase in phosphate-containing samples and the determination of ribose-5-phosphate also is less sensitive. Here we develop a fluorescent assay for ADPRase that utilizes 1, N(6)-etheno ADP-ribose, a fluorescent analogue of ADP-ribose. This method measures fluorescent 1, N(6)-etheno adenosine that is produced by coupling the hydrolysis of 1, N(6)-etheno ADP-ribose to dephosphorylation with alkaline phosphatase. The fluorometric assay is comparable in sensitivity and useful for ADPRase assay in phosphate-containing samples.

Mechanism of phagolysosome biogenesis block by viable Mycobacterium tuberculosis.

Live Mycobacterium tuberculosis persists in macrophage phagosomes by interfering with phagolysosome biogenesis. Here, using four-dimensional microscopy and in vitro assays, we report the principal difference between phagosomes containing live and dead mycobacteria. Phosphatidylinositol 3-phosphate (PI3P), a membrane trafficking regulatory lipid essential for phagosomal acquisition of lysosomal constituents, is retained on phagosomes harboring dead mycobacteria but is continuously eliminated from phagosomes with live bacilli. We show that the exclusion of PI3P from live mycobacterial phagosomes can be only transiently reversed by Ca2+ fluxes, and that live M. tuberculosis secretes a lipid phosphatase, SapM, that hydrolyzes PI3P, inhibits phagosome-late endosome fusion in vitro, and contributes to inhibition of phagosomal maturation.

Development of a solid-phase binding assay and identification of nonpeptide ligands for the FynB Src homology 2 domain.

The nonreceptor tyrosine kinase FynB is known to be required in the induction of long-term potentiation (LTP), a cellular mechanism for learning and memory. Ligands of the FynB SH2 domain as a possible FynB activator are, thus, of great interest. In this study, a solid-phase ligand binding assay was established to meet the screening requirement of high-throughput and ease of use, and in an attempt to find the specific ligands for the FynB SH2 domain. This assay measures the competitive inhibition of the binding of the biotinylated phosphopeptide (GGSETDDY*AEIID), derived from a binding sequence in human focal adhesion kinase, to the SH2 domain of FynB precoated as a glutathione S-transferase fusion protein on a solid-phase. Using this high-throughput screening method for SH2 ligands, a modest size of chemical library was screened, and two non-peptide compounds, 4-acetamidobenzene sulfinic acid and 1-allylpyridinium 3-sulfonate, were identified by their strong binding affinity to the FynB SH2 domain. This result demonstrates the feasibility of the developed assay in high-throughput screening. Further studies on the molecular structures of the identified SH2-binding ligands will allow presentation of specific models for ligand-domain complexes for improving the ligands and will help to develop a potential lead compound for improving LTP.