Regional retrograde alteration of sub-greenschist facies chlorite to smectite

Dioctahedral smectite is present as a retrograde alteration product of chlorite in Permian-Triassic red slates of the Malaguide Complex in Sierra de Espuña (Betic Cordillera). Mineral assemblages and textures, illite “crystallinity” indices, and fluid inclusion data indicate sub-greenschist facies conditions that reached at least 180°C in the higher-grade tectonic unit of the Malaguide Complex, preceding formation of smectite. Smectite, having K as the dominant interlayer cation, occurs ubiquitously intercalated with trioctahedral chlorite as thin packets of layers and as individual layers that commonly change to chlorite along layers. Although some chlorite is typically homogeneous and trioctahedral, much chlorite shows signs of alteration and has compositions corresponding to different degrees of smectite contaimination. The incompatibility of metamorphic grade with the occurrence of smectite, the general association of chlorite and smectite, and the textural relations collectively show that dioctahedral smectite is derived through replacement of trioctahedral chlorite. Such replacement occurs on a regional basis and demonstrates that caution must be used in interpreting the occurrence of smectite in pelites as being due to prograde processes. Alteration of trioctahedral chlorite under oxidizing conditions due to introduction of phreatic water after uplift of the Betic Cordillera is proposed as the cause of formation of smectite.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/47308/1/410_2004_Article_BF00310765.pd

Graphene catalyzes the reversible formation of a C–C bond between two molecules

Carbon deposits are well-known inhibitors of transition metal catalysts. In contrast to this undesirable behavior, here we show that epitaxial graphene grown on Ru(0001) promotes the reversible formation of a C–C bond between −CH2CN and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ). The catalytic role of graphene is multifaceted: First, it allows for an efficient charge transfer between the surface and the reactants, thus favoring changes in carbon hybridization; second, it holds the reactants in place and makes them reactive. The reaction is fully reversible by injecting electrons with an STM tip on the empty molecular orbitals of the product. The making and breaking of the C–C bond is accompanied by the switching off and on of a Kondo resonance, so that the system can be viewed as a reversible magnetic switch controlled by a chemical reactionJ.J.N., F.C., R.M., and A.L.V.d.P. acknowledge the Ministerio de Economía y Competitividad (MINECO) project FIS2015-67367-C2-1-P and Comunidad de Madrid projects MAD2D P2013/MIT-3007 and Nanofrontmag S2013/MIT-2850. M.P., C.D., and F.M. acknowledge the MINECO project FIS2016-77889-R and computer time from the CCC-UAM and the Red Española de Supercomputación. C.D. acknowledges a Ramón y Cajal contract from MINECO (Spain). E.M.P., J.V., and B.N.-O. acknowledge the European Research Council project MINT, ERC-StG-2012-307609. IMDEA Nanoscience acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, grant SEV-2016-0686). IFIMAC acknowledges support from the “María de Maeztu” Programme for Units of Excellence in R&D (MDM-2014-0377

Tuning Proton Conductivity in Alkali Metal Phosphonocarboxylates by Cation Size-Induced and Water-Facilitated Proton Transfer Pathways

The structural and functional chemistry of a family of alkali-metal ions with racemic R,S-hydroxyphosphonoacetate (M-HPAA; M = Li, Na, K, Cs) are reported. Crystal structures were determined by X-ray data (Li+, powder diffraction following an ab initio methodology; Na+, K+, Cs+, single crystal). A gradual increase in dimensionality directly proportional to the alkali ionic radius was observed. [Li3(OOCCH(OH)PO3)-(H2O)4]·H2O (Li-HPAA) shows a 1D framework built up by Li-ligand “slabs” with Li+ in three different coordination environments (4-, 5-, and 6-coordinated). Na-HPAA, Na2(OOCCH(OH)PO3H)(H2O)4, exhibits a pillared layered “house of cards” structure, while K-HPAA, K2(OOCCH(OH)PO3H)(H2O)2, and Cs-HPAA, Cs(HOOCCH(OH)-PO3H), typically present intricate 3D frameworks. Strong hydrogen-bonded networks are created even if no water is present, as is the case in Cs-HPAA. As a result, all compounds show proton conductivity in the range 3.5 × 10−5 S cm−1 (Cs-HPAA) to 5.6 × 10−3 S cm−1 (Na-HPAA) at 98% RH and T = 24 °C. Differences in proton conduction mechanisms, Grothuss (Na+ and Cs+) or vehicular (Li+ and K+), are attributed to the different roles played by water molecules and/or proton transfer pathways between phosphonate and carboxylate groups of the ligand HPAA. Upon slow crystallization, partial enrichment in the S enantiomer of the ligand is observed for Na-HPAA, while the Cs-HPAA is a chiral compound containing only the S enantiomer.Proyectos nacionales MAT2010-15175 y MAT2013-41836-

MAGIC Upper Limits for two Milagro-detected, Bright Fermi Sources in the Region of SNR G65.1+0.6

We report on the observation of the region around supernova remnant G65.1+0.6 with the stand-alone MAGIC-I telescope. This region hosts the two bright GeV gamma-ray sources 1FGL J1954.3+2836 and 1FGL J1958.6+2845. They are identified as GeV pulsars and both have a possible counterpart detected at about 35 TeV by the Milagro observatory. MAGIC collected 25.5 hours of good quality data, and found no significant emission in the range around 1 TeV. We therefore report differential flux upper limits, assuming the emission to be point-like (<0.1 deg) or within a radius of 0.3 deg. In the point-like scenario, the flux limits around 1 TeV are at the level of 3 % and 2 % of the Crab Nebula flux, for the two sources respectively. This implies that the Milagro emission is either extended over a much larger area than our point spread function, or it must be peaked at energies beyond 1 TeV, resulting in a photon index harder than 2.2 in the TeV band.Comment: 8 pages, 3 figures, 1 tabl

Infrared Ellipsometry Analysis of Heritage Photographic Prints

[EN] Focusing on the photographic archive of Julian Carrillo (Mexico), we study and characterize the photographic processes of a set of 13 photographs dated between 1884 and 1925. By using infrared spectroscopic ellipsometry, we classified a selected set of photographs according to its kind of binder. Thus, we recognized for each photograph, the presence of proteins, and therefore, the particular photographic process. Furthermore, we have identified the presence of baryta layer, the use of plasticizer, and the eventual coating utilized to protect the photograph, whose composition was based in natural organic components, mainly shellac, beeswax, or camphorNieto-Villena, A.; Martinez, JR.; Flores-Camacho, JM.; Lastras-Martinez, A.; De La Cruz-Mendoza, JA.; Ortega-Zarzosa, G.; Valcarcel Andrés, JC.... (2018). Infrared Ellipsometry Analysis of Heritage Photographic Prints. Studies in Conservation. 63(8):466-476. https://doi.org/10.1080/00393630.2018.1476962S466476638Brambilla, L., Riedo, C., Baraldi, C., Nevin, A., Gamberini, M. C., D’Andrea, C., … Toniolo, L. (2011). Characterization of fresh and aged natural ingredients used in historical ointments by molecular spectroscopic techniques: IR, Raman and fluorescence. Analytical and Bioanalytical Chemistry, 401(6), 1827-1837. doi:10.1007/s00216-011-5168-zCasoli, A., & Fornaciari, S. (2014). An analytical study on an early twentieth-century Italian photographs collection by means of microscopic and spectroscopic techniques. Microchemical Journal, 116, 24-30. doi:10.1016/j.microc.2014.04.003Cattaneo, B., Chelazzi, D., Giorgi, R., Serena, T., Merlo, C., & Baglioni, P. (2008). Physico-chemical characterization and conservation issues of photographs dated between 1890 and 1910. Journal of Cultural Heritage, 9(3), 277-284. doi:10.1016/j.culher.2008.01.004Daher, C., Paris, C., Le Hô, A.-S., Bellot-Gurlet, L., & Échard, J.-P. (2010). A joint use of Raman and infrared spectroscopies for the identification of natural organic media used in ancient varnishes. Journal of Raman Spectroscopy, 41(11), 1494-1499. doi:10.1002/jrs.2693Edwards, H. G. M., Farwell, D. W., & Daffner, L. (1996). Fourier-transform Raman spectroscopic study of natural waxes and resins. I. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 52(12), 1639-1648. doi:10.1016/0584-8539(96)01730-8Fujiwara, H. (2007). Spectroscopic Ellipsometry. doi:10.1002/9780470060193Hendriks, K., & Ross, L. (1988). Chemical Treatments of Discoloured Photographic Prints: Image Manipulation or Legitimate Restoration? The Journal of Photographic Science, 36(3), 132-132. doi:10.1080/00223638.1988.11736990Mallégol, J., Gardette, J.-L., & Lemaire, J. (2000). Long-term behavior of oil-based varnishes and paints. Photo- and thermooxidation of cured linseed oil. Journal of the American Oil Chemists’ Society, 77(3), 257-263. doi:10.1007/s11746-000-0042-4Nieto-Villena, A., Martínez, J. R., de la Cruz-Mendoza, J. A., Valcárcel-Andrés, J. C., Ortega-Zarzosa, G., Solbes-García, Á., & Vázquez-Martínez, E. (2018). Atomic force microscopy as a tool for binder identification in ancient photographic processes. Surface and Interface Analysis, 50(4), 496-505. doi:10.1002/sia.6408Ostroff, Eugene. 1966. “Restoration of Photographs by Neutron Activation.” Science 154 (3745): 119–123. http://science.sciencemag.org/content/154/3745/119.Othmer, Kirk, ed. 2005. Encyclopedia of Chemical Technology. Vol. 17, 5th ed. New York: Wiley.Ricci, C., Bloxham, S., & Kazarian, S. G. (2007). ATR-FTIR imaging of albumen photographic prints. Journal of Cultural Heritage, 8(4), 387-395. doi:10.1016/j.culher.2007.07.002Sifontes, Á. B., Cañizales, E., Toro-Mendoza, J., Ávila, E., Hernández, P., Delgado, B. A., … Cruz-Barrios, E. (2015). Obtaining Highly Crystalline Barium Sulphate Nanoparticles via Chemical Precipitation and Quenching in Absence of Polymer Stabilizers. Journal of Nanomaterials, 2015, 1-8. doi:10.1155/2015/510376Stulik, Dusan, Herant Khanjian, Alberto de Tagle, and Alexandra M. Botelho. 2002. “Investigation of Jean-Louis-Marie-Eugene Durieu’s Toning and Varnishing Experiments: A Non-Destructive Approach.” ICOM Committee for Conservation 13th Triennial Meeting, Río de Janeiro, 658–663.Price, Beth A., and Boris Pretzel, eds. 2009. Infrared and Raman Users Group Spectral Database. 2007 ed. Vol. 1 & 2. Philadelphia: IRUG. Accessed June 20, 2014. http://www.irug.org/.Vila, A., & Centeno, S. A. (2013). FTIR, Raman and XRF identification of the image materials in turn of the 20th century pigment-based photographs. Microchemical Journal, 106, 255-262. doi:10.1016/j.microc.2012.07.01

Gain of DNA methylation is enhanced in the absence of CTCF at the human retinoblastoma gene promoter

<p>Abstract</p> <p>Background</p> <p>Long-term gene silencing throughout cell division is generally achieved by DNA methylation and other epigenetic processes. Aberrant DNA methylation is now widely recognized to be associated with cancer and other human diseases. Here we addressed the contribution of the multifunctional nuclear factor CTCF to the epigenetic regulation of the human <it>retinoblastoma </it>(<it>Rb</it>) gene promoter in different tumoral cell lines.</p> <p>Methods</p> <p>To assess the DNA methylation status of the <it>Rb </it>promoter, genomic DNA from stably transfected human erythroleukemic K562 cells expressing a <it>GFP </it>reporter transgene was transformed with sodium bisulfite, and then PCR-amplified with modified primers and sequenced. Single- and multi-copy integrants with the CTCF binding site mutated were isolated and characterized by Southern blotting. Silenced transgenes were reactivated using 5-aza-2'-deoxycytidine and Trichostatin-A, and their expression was monitored by fluorescent cytometry. <it>Rb </it>gene expression and protein abundance were assessed by RT-PCR and Western blotting in three different glioma cell lines, and DNA methylation of the promoter region was determined by sodium bisulfite sequencing, together with CTCF dissociation and methyl-CpG-binding protein incorporation by chromatin immunoprecipitation assays.</p> <p>Results</p> <p>We found that the inability of CTCF to bind to the <it>Rb </it>promoter causes a dramatic loss of gene expression and a progressive gain of DNA methylation.</p> <p>Conclusions</p> <p>This study indicates that CTCF plays an important role in maintaining the <it>Rb </it>promoter in an optimal chromatin configuration. The absence of CTCF induces a rapid epigenetic silencing through a progressive gain of DNA methylation. Consequently, CTCF can now be seen as one of the epigenetic components that allows the proper configuration of tumor suppressor gene promoters. Its aberrant dissociation can then predispose key genes in cancer cells to acquire DNA methylation and epigenetic silencing.</p

Transient tissue priming via ROCK inhibition uncouples pancreatic cancer progression, sensitivity to chemotherapy, and metastasis.

The emerging standard of care for patients with inoperable pancreatic cancer is a combination of cytotoxic drugs gemcitabine and Abraxane, but patient response remains moderate. Pancreatic cancer development and metastasis occur in complex settings, with reciprocal feedback from microenvironmental cues influencing both disease progression and drug response. Little is known about how sequential dual targeting of tumor tissue tension and vasculature before chemotherapy can affect tumor response. We used intravital imaging to assess how transient manipulation of the tumor tissue, or "priming," using the pharmaceutical Rho kinase inhibitor Fasudil affects response to chemotherapy. Intravital Förster resonance energy transfer imaging of a cyclin-dependent kinase 1 biosensor to monitor the efficacy of cytotoxic drugs revealed that priming improves pancreatic cancer response to gemcitabine/Abraxane at both primary and secondary sites. Transient priming also sensitized cells to shear stress and impaired colonization efficiency and fibrotic niche remodeling within the liver, three important features of cancer spread. Last, we demonstrate a graded response to priming in stratified patient-derived tumors, indicating that fine-tuned tissue manipulation before chemotherapy may offer opportunities in both primary and metastatic targeting of pancreatic cancer