Plasma-Enabled Dry Methane Reforming

Plasma-enabled dry methane reforming is a promising technology for biogas upgrade and shows multiple benefits to provide additional energy and material conversion pathways. This chapter first presents the role of nonthermal plasma as a potential energy supply pathway in the low-temperature methane conversion: an appropriated combination of electrical energy provided by plasma (ΔG) and the low-temperature thermal energy (TΔS) satisfies the overall reaction enthalpy (ΔH) with higher energy conversion efficiency. Moreover, plasma-enabled dry methane reforming could be operated at much lower temperature than thermal catalysis with sufficient material conversion. Three kinds of typical packed-bed plasma reactor were introduced to give a better understanding of the application of plasma and catalyst hybrid system. Subsequently, plasma-enabled dry methane reforming was diagnosed by pulsed reaction spectrometry compared with thermal catalysis, presenting a clear overview of gas component changes and significant promotion in reactant conversion and product yield. The interaction between plasma and catalyst was summarized based on two aspects: catalyst affects plasma, and plasma affects catalyst. We discussed the coke formation behavior of Ni/Al2O3 catalyst in the plasma-enabled and thermal dry methane reforming, followed by the oxidation behavior. The interaction between plasma and catalyst pellets was discussed toward deeper insight into the mechanism

Simultaneous Improvements in Performance and Durability of an Octahedral PtNix/C Electrocatalyst for Next-Generation Fuel Cells by Continuous, Compressive, and Concave Pt Skin Layers

Simultaneous improvements in oxygen reduction reaction (ORR) activity and long-term durability of Pt-based cathode catalysts are indispensable for the development of next-generation polymer electrolyte fuel cells but are still a major dilemma. We present a robust octahedral core–shell PtNix/C electrocatalyst with high ORR performance (mass activity and surface specific activity 6.8–16.9 and 20.3–24.0 times larger than those of Pt/C, respectively) and durability (negligible loss after 10000 accelerated durability test (ADT) cycles). The key factors of the robust octahedral nanostructure (core–shell Pt73Ni27/C) responsible for the remarkable activity and durability were found to be three continuous Pt skin layers with 2.0–3.6% compressive strain, concave facet arrangements (concave defects and high coordination), a symmetric Pt/Ni distribution, and a Pt67Ni33 intermetallic core, as found by STEM-EDS, in situ XAFS, XPS, etc. The robust core–shell Pt73Ni27/C was produced by the partial release of the stress, Pt/Ni rearrangement, and dimension reduction of an as-synthesized octahedral Pt50Ni50/C with 3.6–6.7% compressive Pt skin layers by Ni leaching during the activation process. The present results on the tailored synthesis of the PtNix structure and composition and the better control of the robust catalytic architecture renew the current knowledge and viewpoint for instability of octahedral PtNix/C samples to provide a new insight into the development of next-generation PEFC cathode catalysts

Antioxidant Activity and Oxidation Products of 1,2,3,4- Tetrahydroquinoxalines in Peroxyl Radical Scavenging Reactions, Part I

This paper studies the antioxidant activity of 1,2,3,4-tetrahydroquinolines, 3,4-dihydro-2H-benzo[1,4]thiazines and 1,2,3,4-tetrahydroquinoxalines in the inhibition of the peroxidation of tetralin induced by an azo initiator. Neither 1,2,3,4- tetrahydroquinoline nor 3,4-dihydro-2H-benzo[1,4]thiazine alone acted as an antioxidant, but when they have an electron-donating group at the para position to the NH group, they act as potent antioxidants. On the other hand, 1,2,3,4- tetrahydroquinoxaline on its own showed good antioxidant activity. However, 1,2,3,4-tetrahydroquinoxalines with methyl and methoxy groups in the phenyl ring have reactivities similar to or less than that of unsubstituted 1,2,3,4-tetrahydroquinoxaline. The induction periods of 1,2,3,4-tetrahydroquinoxalines with an alkyl group or phenyl group at the 2-position were all longer than the value for the unsubstituted 1,2,3,4-tetrahydroquinoxaline, except for a compound with a t-butyl group. The oxidation of 1,2,3,4-tetrahydroquinoxalines by peroxyl radicals generated from an azo initiator in tetralin or benzene yields quinoxalines and a dimer product of quinoxalines, 6-(1,2,3,4-tetrahydroquinoxalin-1-yl)-quinoxaline

Cystic Artery Variations and Associated Vascular Complications in Laparoscopic Cholecystectomy

Substantial knowledge of the arterial supply and its anatomical variations of the gall bladder and liver are important in all the hepatobiliary surgical procedures. The arterial supply of gallbladder called cystic artery (CA) is a vital structure required to get ligated or clipped in the path of laparoscopic cholecystectomy. The possible concerns like intra-operative bleeding or adjoining accidental injuries will almost always be focused on the research consisting of dissection and clipping with cystic artery. Pseudoaneurysm of the cystic artery has additionally been belonging to the presence of acute cholecystitis or pancreatitis. An original supply of CA is usually assessed depending on the existence of hepatic artery variants. Laparoscopic cholecystectomy is really a recent and arduous noninvasive procedure and might even result in substantial unintended effects possibly iatrogenic or in the form of post-procedural complications. The perfect knowledge of anatomy in addition to feasible variation of cystic artery is mandatory. An efficient operative strategy and consciousness are probably the key components with all the results and marginal likelihood of complications, which often can be ultimately attainable. Within this chapter, we have attempted to explore some variations of cystic artery, complications and management

TONS504-PHOTODYNAMIC THERAPY INDUCES CYTOTOXIC EFFECTS IN EMT6 CELLS

In the present study, TONS504 (C51H58N8O5I2; molecular weight, 1,116.9), a novel cationic hydrophilic photosensitizer, was synthesized from protoporphyrin IX dimethyl ester through a five‑step process according to a patented method for use in photodynamic therapy (PDT). The subcellular localization of TONS504 and the cytotoxic effects of TONS504‑mediated PDT in the mouse mammary tumor EMT6 cell line were investigated. TONS504 was localized primarily in the lysosomes and partially in the mitochondria. The cytotoxic effects of TONS504‑mediated PDT in the mouse mammary tumor EMT6 cell line were investigated using a WST8 assay and an Oxidative Stress kit. The cell viability values following treatment with 10 µg/ml TONS504 at light energies of 0, 1, 5 and 10 J/cm2 were 92.5, 101.8, 27.7 and 1.8%, respectively. The percentages of reactive oxygen species (ROS)(+) cells following the same treatment were 8.6, 8.5, 29.2 and 70.1%, respectively, whereas the percentages of apoptotic cells were 7.1, 5.6, 24.8 and 48.7%, respectively. The percentages of ROS(+) and apoptotic cells in the group subjected to TONS504‑mediated PDT increased in a manner dependent on the TONS504 concentration and light energy. Further studies are required to evaluate the in vivo pharmacokinetics, tissue distribution and photodynamic effects of TONS504

Key Structural Transformations and Kinetics of Pt Nanoparticles in PEFC Pt/C Electrocatalysts by a Simultaneous Operando Time-Resolved QXAFS–XRD Technique

This account article treats with the key structural transformations and kinetics of Pt nanoparticles in Pt/C cathode catalysts under transient voltage operations (0.4 VRHE→1.4 VRHE→0.4 VRHE) by simultaneous operando time-resolved QXAFS–XRD measurements, summarizing and analyzing our previous kinetic data in more detail and discussing on the key reaction steps and rate constants for the performance and durability of polymer electrolyte fuel cells (PEFC). The time-resolved QXAFS–XRD measurements were conducted at each acquisition time of 20 ms, while measuring the current/charge of the PEFC. The rate constants for the transient responses of Pt valence, CN(Pt–O) (CN: coordination number), CN(Pt–Pt), and Pt metallic-phase core size under the transient voltage operations were determined by the combined time-resolved QXAFS‒XRD technique. The relationship of the structural kinetics with the performance and durability of the PEFC Pt/C was also documented as key issues for the development of next-generation PEFCs. The present account emphasizes the time-resolved QXAFS and XRD techniques to be a powerful technique to analyze directly the structural and electronic change of metal nanoparticles inside PEFC under the operating conditions

Observation of Degradation of Pt and Carbon Support in Polymer Electrolyte Fuel Cell Using Combined Nano-X-ray Absorption Fine Structure and Transmission Electron Microscopy Techniques

It is hard to directly visualize spectroscopic and atomic–nanoscopic information on the degraded Pt/C cathode layer inside polymer electrolyte fuel cell (PEFC). However, it is mandatory to understand the preferential area, sequence, and relationship of the degradations of Pt nanoparticles and carbon support in the Pt/C cathode layer by directly observing the Pt/C cathode catalyst for the development of next-generation PEFC cathode catalysts. Here, the spectroscopic, chemical, and morphological visualization of the degradation of Pt/C cathode electrocatalysts in PEFC was performed successfully by a same-view combination technique of nano-X-ray absorption fine structure (XAFS) and transmission electron microscopy (TEM)/scanning TEM–energy-dispersive spectrometry (EDS) under a humid N2 atmosphere. The same-view nano-XAFS and TEM/STEM–EDS imaging of the Pt/C cathode of PEFC after triangular-wave 1.0–1.5 VRHE (startup/shutdown) accelerated durability test (tri-ADT) cycles elucidated the site-selective area, sequence, and relationship of the degradations of Pt nanoparticles and carbon support in the Pt/C cathode layer. The 10 tri-ADT cycles caused a carbon corrosion to reduce the carbon size preferentially in the boundary regions of the cathode layer with both electrolyte and holes/cracks, accompanied with detachment of Pt nanoparticles from the degraded carbon. After the decrease in the carbon size to less than 8 nm by the 20 tri-ADT cycles, Pt nanoparticles around the extremely corroded carbon areas were found to transform and dissolve into oxidized Pt2+–O4 species

An Al-doped SrTiO3 photocatalyst maintaining sunlight-driven overall water splitting activity for over 1000 h of constant illumination

Photocatalytic water splitting is a viable approach to the large-scale production of renewable solar hydrogen. The apparent quantum yield for this reaction has been improved, but the lifespan of photocatalysts functioning under sunlight at ambient pressure have rarely been examined, despite the critical importance of this factor in practical applications. Herein, we show that Al-doped SrTiO3 (SrTiO3: Al) loaded with a RhCrOx (rhodium chromium oxide) cocatalyst splits water with an apparent quantum yield greater than 50% at 365 nm. Moreover, following the photodeposition of CoOOH and TiO2, this material maintains 80% of its initial activity and a solar-to-hydrogen energy conversion efficiency greater than or equal to 0.3% over a span of 1300 h under constant illumination by simulated sunlight at ambient pressure. This result is attributed to reduced dissolution of Cr in the cocatalyst following the oxidative photodeposition of CoOOH. The photodeposition of TiO2 further improves the durability of this photocatalyst. This work demonstrates a concept that could allow the design of longterm, large-scale photocatalyst systems for practical sunlight-driven water splitting.ArticleCHEMICAL SCIENCE.10(11):3196-3201(2019)journal articl

Zinc is a novel intracellular second messenger

Zinc is an essential trace element required for enzymatic activity and for maintaining the conformation of many transcription factors; thus, zinc homeostasis is tightly regulated. Although zinc affects several signaling molecules and may act as a neurotransmitter, it remains unknown whether zinc acts as an intracellular second messenger capable of transducing extracellular stimuli into intracellular signaling events. In this study, we report that the cross-linking of the high affinity immunoglobin E receptor (Fcɛ receptor I [FcɛRI]) induced a release of free zinc from the perinuclear area, including the endoplasmic reticulum in mast cells, a phenomenon we call the zinc wave. The zinc wave was dependent on calcium influx and mitogen-activated protein kinase/extracellular signal-regulated kinase kinase activation. The results suggest that the zinc wave is involved in intracellular signaling events, at least in part by modulating the duration and strength of FcɛRI-mediated signaling. Collectively, our findings indicate that zinc is a novel intracellular second messenger