Metal-Specific Reactivity in Single-Atom Catalysts: CO Oxidation on 4d and 5d Transition Metals Atomically Dispersed on MgO

[EN] Understanding and tuning the catalytic properties of metals atomically dispersed on oxides are major stepping-stones toward a rational development of single-atom catalysts (SACs). Beyond individual showcase studies, the design and synthesis of structurally regular series of SACs opens the door to systematic experimental investigations of performance as a function of metal identity. Herein, a series of single-atom catalysts based on various 4d (Ru, Rh, Pd) and Sd (Ir, Pt) transition metals has been synthesized on a common MgO carrier. Complementary experimental (X-ray absorption spectroscopy) and theoretical (Density Functional Theory) studies reveal that, regardless of the metal identity, metal cations occupy preferably octahedral coordination MgO lattice positions under step-edges, hence highly confined by the oxide support. Upon exposure to O-2-lean CO oxidation conditions, FTIR spectroscopy indicates the partial deconfinement of the monatomic metal centers driven by CO at precatalysis temperatures, followed by the development of surface carbonate species under steady-state conditions. These findings are supported by DFT calculations, which show the driving force and final structure for the surface metal protrusion to be metal-dependent, but point to an equivalent octahedral-coordinated M4+ carbonate species as the resting state in all cases. Experimentally, apparent reaction activation energies in the range of 96 +/- 19 kJ/mol are determined, with Pt leading to the lowest energy barrier. The results indicate that, for monatomic sites in SACs, differences in CO oxidation reactivity enforceable via metal selection are of lower magnitude than those evidenced previously through the mechanistic involvement of adjacent redox centers on the oxide carrier, suggesting that tuning of the oxide surface chemistry is as relevant as the selection of the supported metal.XAS experiments were performed at B18 beamline, Diamond Light Source, United Kingdom (proposals Nr. SP17377 and SP19072) and BL22 beamline, ALBA Light Source, Spain (experiment 2019023278). Beamline scientists D. Gianolio (Diamond) and L. Simonelli and C. Marini (ALBA) are acknowledged for their assistance with the beamline setup during XAS experiments. The authors are grateful to M. Garcia, E. Andres, M. E. Martinez, and I. Lopez (ITQ) for assistance during the XAS experiments. J. Ternieden (MPIKOFO) is acknowledged for the performance of XRD experiments. J.M. Salas (ITQ) is acknowledged for his experimental contribution to the CO-FTIR studies, and M.D. Soriano and A. Munoz for the recording of XP spectra. P.N.P. and F.S. acknowledge support by the state of BademWurttemberg through bwHPC (bwUnicluster and JUSTUS, RV bw17D01) and support from the Helmholtz Association is also gratefully acknowledged. This research received funding from the Alexander von Humboldt Foundation (postdoctoral grant to B.B.S.), the Max Planck Society and the Fonds der Chemischen Industry (FCI, Germany). The authors are grateful to Prof. Ferdi Schuth for the provision of lab facilities and support throughout the project. Funding from the Spanish Ministry of Science, Innovation and Universities (projects SEV 2016-0683 and RTI2018-096399-A-100) is also acknowledged.Sarma, BB.; Plessow, PN.; Agostini, G.; Concepción Heydorn, P.; Pfänder, N.; Kang, L.; Wang, FR.... (2020). 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Precisely visit the performance modulation of functionalized separator in Li-S batteries via consecutive multiscale analysis

Despite progress of functionalized separator in preventing the shuttle effect and promoting the sulfur utilization, the precise and non-destructive investigation of structure-function-performance associativity remains limited so far in Li-S batteries. Here, we build consecutive multiscale analysis via combining X-ray absorption fine structure (XAFS) and X-ray computational tomography (CT) techniques to precisely visit the structure-function-performance relationship. XAFS measurement offers the atomic scale changes in the chemical structure and environment. Moreover, a non-destructive technique of X-ray CT proves the functionalized separator role for microscopic scale, which is powerful chaining to bridge the chemical structures of the materials with the overall performance modulation of cells. Benefiting from this consecutive multiscale analysis, we report that the uniform doping of Sr2+ into the perovskite LaMnO3-δ material changes the Mn oxidation states and conductivity (chemical structure), leading to effective lithium polysulfide trapping and accelerated sulfur redox (separator function), and resulting in outstanding cell performance

A Local Proinflammatory Signalling Loop Facilitates Adverse Age-Associated Arterial Remodeling

Background: The coincidence of vascular smooth muscle cells (VSMC) infiltration and collagen deposition within a diffusely thickened intima is a salient feature of central arterial wall inflammation that accompanies advancing age. However, the molecular mechanisms involved remain undefined. Methodology/Principal Findings: Immunostaining and immunoblotting of rat aortae demonstrate that a triad of proinflammatory molecules, MCP-1, TGF-b1, and MMP-2 increases within the aortic wall with aging. Exposure of VSMC isolated from 8-mo-old rats (young) to MCP-1 effects, via CCR-2 signaling, both an increase in TGF-b1 activity, up to levels of untreated VSMC from 30-mo-old (old) rats, and a concurrent increase in MMP-2 activation. Furthermore, exposure of young VSMC to TGF-b1 increases levels of MCP-1, and MMP-2 activation, to levels of untreated VSMC from old rats. This autocatalytic signaling loop that enhances collagen production and invasiveness of VSMC is effectively suppressed by si-MCP-1, a CCR2 antagonist, or MMP-2 inhibition. Conclusions/Significance: Threshold levels of MCP-1, MMP-2, or TGF-b1 activity trigger a feed-forward signaling mechanism that is implicated in the initiation and progression of adverse age-associated arterial wall remodeling. Intervention that suppressed this signaling loop may potentially retard age-associated adverse arterial remodeling

Optimizing Nervous System-Specific Gene Targeting with Cre Driver Lines: Prevalence of Germline Recombination and Influencing Factors.

The Cre-loxP system is invaluable for spatial and temporal control of gene knockout, knockin, and reporter expression in the mouse nervous system. However, we report varying probabilities of unexpected germline recombination in distinct Cre driver lines designed for nervous system-specific recombination. Selective maternal or paternal germline recombination is showcased with sample Cre lines. Collated data reveal germline recombination in over half of 64 commonly used Cre driver lines, in most cases with a parental sex bias related to Cre expression in sperm or oocytes. Slight differences among Cre driver lines utilizing common transcriptional control elements affect germline recombination rates. Specific target loci demonstrated differential recombination; thus, reporters are not reliable proxies for another locus of interest. Similar principles apply to other recombinase systems and other genetically targeted organisms. We hereby draw attention to the prevalence of germline recombination and provide guidelines to inform future research for the neuroscience and broader molecular genetics communities

Size-Segregated Particle Number Concentrations and Respiratory Emergency Room Visits in Beijing, China

BACKGROUND: The link between concentrations of particulate matter (PM) and respiratory morbidity has been investigated in numerous studies. OBJECTIVES: The aim of this study was to analyze the role of different particle size fractions with respect to respiratory health in Beijing, China. METHODS: Data on particle size distributions from 3 nm to 1 mu m; PM10 (PM <= 10 mu m), nitrogen dioxide (NO2), and sulfur dioxide concentrations; and meteorologic variables were collected daily from March 2004 to December 2006. Concurrently, daily counts of emergency room visits (ERV) for respiratory diseases were obtained from the Peking University Third Hospital. We estimated pollutant effects in single-and two-pollutant generalized additive models, controlling for meteorologic and other time-varying covariates. Time-delayed associations were estimated using polynomial distributed lag, cumulative effects, and single lag models. RESULTS: Associations of respiratory ERV with NO2 concentrations and 100-1,000 nm-particle number or surface area concentrations were of similar magnitude-that is, approximately 5% increase in respiratory ERV with an interquartile range increase in air pollution concentration. In general, particles <50 nm were not positively associated with ERV, whereas particles 50-100 nm were adversely associated with respiratory ERV, both being fractions of ultrafine particles. Effect estimates from two-pollutant models were most consistent for NO2. CONCLUSIONS: Present levels of air pollution in Beijing were adversely associated with respiratory ERV. NO2 concentrations seemed to be a better surrogate for evaluating overall respiratory health effects of ambient air pollution than PM10 or particle number concentrations in Beijing.http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000289065900032&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701Environmental SciencesPublic, Environmental & Occupational HealthToxicologySCI(E)37ARTICLE4508-51311

Preferentially Quantized Linker DNA Lengths in Saccharomyces cerevisiae

The exact lengths of linker DNAs connecting adjacent nucleosomes specify the intrinsic three-dimensional structures of eukaryotic chromatin fibers. Some studies suggest that linker DNA lengths preferentially occur at certain quantized values, differing one from another by integral multiples of the DNA helical repeat, ∼10 bp; however, studies in the literature are inconsistent. Here, we investigate linker DNA length distributions in the yeast Saccharomyces cerevisiae genome, using two novel methods: a Fourier analysis of genomic dinucleotide periodicities adjacent to experimentally mapped nucleosomes and a duration hidden Markov model applied to experimentally defined dinucleosomes. Both methods reveal that linker DNA lengths in yeast are preferentially periodic at the DNA helical repeat (∼10 bp), obeying the forms 10n+5 bp (integer n). This 10 bp periodicity implies an ordered superhelical intrinsic structure for the average chromatin fiber in yeast

Tumor-Initiating Cells Are Enriched in CD44hi Population in Murine Salivary Gland Tumor

Tumor-initiating cells (T-ICs) discovered in various tumors have been widely reported. However, T-IC populations in salivary gland tumors have yet to be elucidated. Using the established Pleomorphic Adenoma Gene-1 (Plag1) transgenic mouse model of a salivary gland tumor, we identified CD44high (CD44hi) tumor cells, characterized by high levels of CD44 cell surface expression, as the T-ICs for pleomorphic adenomas. These CD44hi tumor cells incorporated 5-bromo-2-deoxyuridine (BrdU), at a lower rate than their CD44negative (CD44neg) counterparts, and also retained BrdU for a long period of time. Cell surface maker analysis revealed that 25% of the CD44hi tumor cells co-express other cancer stem cell markers such as CD133 and CD117. As few as 500 CD44hi tumor cells were sufficient to initiate pleomorphic adenomas in one third of the wildtype mice, whereas more than 1×104 CD44neg cells were needed for the same purpose. In NIH 3T3 cells, Plag1 was capable of activating the gene transcription of Egr1, a known upregulator for CD44. Furthermore, deletion of sequence 81–96 in the Egr1 promoter region abolished the effect of Plag1 on Egr1 upregulation. Our results establish the existence of T-ICs in murine salivary gland tumors, and suggest a potential molecular mechanism for CD44 upregulation

Isoflurane Preconditioning at Clinically Relevant Doses Induce Protective Effects of Heme Oxygenase-1 on Hepatic Ischemia Reperfusion in Rats

<p>Abstract</p> <p>Background</p> <p>Activation of heme oxygenase-1 (HO-1) has been proved to reduce damages to the liver in ischemia reperfusion injury. The objective of present study was to determine whether clinic relevant doses of isoflurane treatment could be sufficient to activate HO-1 inducing, which confers protective effect against hepatic ischemia-reperfusion injury.</p> <p>Methods</p> <p>The hepatic artery and portal vein to the left and the median liver lobes of forty male Sprague-Dawley rats were occluded for 60 minutes. Reperfusion was allowed for 4 hours before the animal subjects were sacrificed. Six groups (n = 12) were included in the study. A negative control group received sham operation and positive control group a standard ischemia-reperfusion regimen. The third group was pretreated with isoflurane prior to the ischemia-reperfusion. The fourth group received an HO-1 inhibitor zinc protoporphyrin (Znpp) prior to the isoflurane pretreatment and the ischemia-reperfusion. The fifth group received Znpp alone before ischemia-reperfusion procedure, and the sixth group was administrated with a HO-1 inducer hemin prior to IR. HO-1 in the liver was measured using an enzymatic activity assay, a Western blot analysis, as well as immunohistochemical method. Extent of liver damage was estimated by determination of the serum transaminases, liver lipid peroxidation and hepatic histology. Infiltration of the liver by neutrophils was measured using a myeloperoxidase activity assay. TNFα mRNA in the liver was measured using RT-PCR.</p> <p>Results</p> <p>Isoflurane pretreatment significantly attenuated the hepatic injuries and inflammatory responses caused by the ischemia reperfusion. Selectively inhibiting HO-1 with ZnPP completed blocked the protective effects of isoflurane. Inducing HO-1 with hemin alone produced protective effects similar in magnitude to that of isoflurane.</p> <p>Conclusions</p> <p>Clinic relevant doses of isoflurane attenuate ischemia reperfusion injury in rats by increasing the HO-1 expression and activity.</p